CA2076937A1 - Cyanophenylpyrroles - Google Patents

Cyanophenylpyrroles

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Publication number
CA2076937A1
CA2076937A1 CA002076937A CA2076937A CA2076937A1 CA 2076937 A1 CA2076937 A1 CA 2076937A1 CA 002076937 A CA002076937 A CA 002076937A CA 2076937 A CA2076937 A CA 2076937A CA 2076937 A1 CA2076937 A1 CA 2076937A1
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Prior art keywords
compound
formula
halo
salt
cyano
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CA002076937A
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French (fr)
Inventor
Josef Ehrenfreund
Dieter Durr
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Novartis AG
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C07D207/327—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Coating Apparatus (AREA)
  • Pyrrole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cyanophenylpyrroles Abstract Compounds of the formula

Description

~ ~ 7 , PI/S- l ~77~/A

Cvanophenvlpyrroles The invention relates to compounds of the fonnula R1--CF2~_~ (I), N, 4 (R3)n in which n is the number l~ 2, 3, 4 or 5, where, if n is greater than 1, the radicals R3 are identical or different; Rl is halo-CI-Cgalkyl; R2 is halogen; R3 is hydrogen, cyano, nitro, halogen, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4alkylthio, Cl-C4alkanesulfinyl, Cl-C4alkanesulfonyl, halo-Cl-C4alkyl, halo-Cl-C4alkoxy, halo-Cl-C4alkylthio, halo-Cl-C4aL~anesulfinyl or halo-Cl-C4alkanesulfonyl, and/or two substituents R3 which are bonded to adjacent C atoms of the phenyl ring together are a bridge selected from the group of bridges comprising -O-CH2-O-, -O-CH2-CH2-O-, -O-CH2-CH2-, -O-CH2-CH2-CH2- and -CH=CH-CH=CH-, unsubstituted or substituted by halogen, Cl-C4alkyl, Cl-C4alkoxy or halo-Cl-C4alkyl; and R4 iS hydrogen, Cl-C4alkyl, C3-C4alkenyl, halo-C3-C4alkenyl, C3-C4alkynyl, cyano, Cl-C4alkylthio, Cl-C4alkanesulfinyl, Cl-C4aLkanesulfonyl, halo-Cl-C4alkanesulfonyl, di-Cl-C4aL~cylaminosulfonyl, di-Cl-C4aL~ylaminocarbonyl or a Cl-C4aLIcyl group which is substituted by one or more substituents selected from the group comprising halogen, Cl-C4alkoxy, hydroxyl, Cl-C4alkylthio, C2-C6alkoxyalkoxy, Cl-C4alkanesulfinyl, Cl-C4alkanesulfonyl, Cl-C4alkylcarbonyl, Cl-C4alkoxycarbonyl, Cl-C4alkylcarbonyloxy, cyano, C2-C4alkenylcarbonyloxy, phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl, where the phenyl rings contained in these phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl substituents can in each case be substituted by halogen, Cl-C4alkyl, Cl-C4alkoxy, halo-Cl-C4alkyl, halo-Cl-C4alkoxy, Cl-C4alkylthio, Cl-C4alkanesulfinyl, Cl-C4alkanesulfonyl, halo-Cl-C4alkylthio, halo-Cl-C4-alkanesulfinyl, halo-Cl-C4-alkanesulfonyl, cyano or nitro, in free form or in salt form, to a process for the preparation and to the use of these compouncls, to pesticides whose active ingredient is selected from amongst these compounds in free form or in agrochemically usable salt form, to a process for the preparation and to the use of these compositions, to plant s propagation material tre~ted with these compositions, to a method for controlling pests, to interrnediates, in free fonn or in salt form, for the preparation of these compounds, and to a proeess for the preparation and the use of these interrnediates.

EP-A-O ~47 488, FP-A-O 372 263, EP-A-O 426 948, EP-A-~ 434 940 and EP-A-O 492 171 propose cyanophenylpyrrole derivatives as acaricidal and insecticidal active ingredients in pesticides. However, the biological properties of the compounds described in these publications are not entirely satisfactory in the pest control sector, and this is why it has been found necessary to provide other compounds having pest-controlling properties, in particular for the control of insects and of representatives from the order of the Acarina, and this object is achieved according to the invention by providing the present compounds I which, surprisingly, are additionally also suitable for controlling phytopathogenic fungi.

Compounds I which have at least one basic centre can form for example acid addition salts. These acid addition salts are formed, for example, with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, for example unsubstituted or halogen-substituted Cl-C4alkanecarboxylic acids, for example acetic acid, or unsaturated or saturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, or hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid, or with organic sulfonic acids for example Cl-C4alkane- or arylsulfonic acids which are unsubstituted or substituted for example by halogen, for example methane- or p-toluenesulfonic acid. Furthermore, compounds I having at least one acidic group can form salts with bases. Suitable salts with bases are, for example, metal salts such as aLkali metal salts or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl-, or dimethylpropylamine, or a rnono-, di- or trihydroxy lower-aLIcylamine, for example mono-, di- or triethanolamine. Furtherrnore, corresponding internal salts may possibly be formed. Preferred within the scope of the invention are agrochemically advantageous salts; however, the invention also comprises salts which are disadvantageous for agrochemical purposes, for example salts which are toxic to bees or fish and which are employed, for example, for the isolation or puri~lcation of free compounds I or their agrochemically usable salts. Due to the close relation between the compounds I in free form and in the forrn of their salts, the free compounds I, or salts - 3 - ~ ,7 thereof, which are menlioned hereinbefore and hereinafter are also to be understood as meaning analogously and expediently, where appropriate, the corresponding salts, or the free compounds I, respectively.

Unless otherwise defined, the general terms used hereinbefore and hereinafter have the meanings listed hereinafter.

Halogen - as a grroup per se and as structural element of other groups and compounds such as haloalkyl, haloalkenyl, haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine, in particular fluorine. Halogen R2 is especially chlorine or bromine, in particular bromine.

Carbon-containing groups and compounds contain, unless otherwise defined, in each case 1 up to and including 9, preferably 1 up to and including 6 but 1 up to and including 4 being preferred, in particular 1 or 2, carbon atoms.

Alkyl - as a group per se and as structural element of other groups and compounds such as haloaLkyl, alkoxy, alkoxyalkoxy, haloalkoxy, aL~cylthio, haloaLIcylthio, alkanesulfinyl, haloalkanesulfinyl, alkanesulfonyl, haloalkanesulfonyl, dialkylaminosulfonyl, diaLcylaminocarbonyl, alkylearbonyl, alkoxycarbonyl and alkylcarbonyloxy - is either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or nonyl, or branehed, for example isopropyl, isobutyl, see-butyl, tert-butyl, isopentyl, neopentyl or isooctyl, in each case wi~h due eonsideration of the number of earbon atoms contained in eaeh individual ease in the partieular group or compound.

Alkenyl, haloalkenyl, alkenylcarbonyloxy and alkynyl are straight-ehain or branched and contain in each ease two or, preferably, one unsaturated earbon bond(s). The double bonds or triple bonds of these substituents are separated from the remainder of the eompound I, preferably by at least one saturated earbon atom. The following may be mentioned by way of example: allyl, methallyl, but-2-enyl, but-3-enyl, allylearbonyloxy, propargyl, but-2-ynyl and but-3-ynyl.

Halogen-substituted earbon-eontaining groups and eompounds sueh as haloalkyl, haloalkenyl, haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl ean be partially halogenated or perhalogenated, where, in the ease of multiple halogenation, the 2~.~ t ~''3~ 7 halogen substituents can be identical or different. Examples of haloalkyl - as a group per se and as strucn~ral element of other groups and compounds such as haloalkyl, haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl - are methyl, mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl, mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCl2, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHClF, CF2CHBrF or CCIFCHClF;
propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorine andlor bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH~CF2CF3, CF2CF2CF3 or CH(CF3)2; and butyl or one of the isomers thereof, mono- to nonasubstituted by fluorine, chlorine andlor bromine, such as CF(CF3)CHFCF3, CF2(CF2)2CF3 or CH2(CF2)2CF3. Haloalkyl Rl is preferably exclusively fluorinaled, in particular perfluorinated. Examples of haloalkenyl are 2-chloroprop-1-en-3-yl, 2,3-dichloroprop-1-en-3-yl and 2,3-dibromoprop-1-en-3-yl.

The two aL"yl groups in dialkylaminosulfonyl and dialkylaminocarbonyl substituents can in each case be identical or different. The following may be mentioned by way ofexample: -SO2-N(CH3)2, -~O2-N(c2Hs)2~ -s02-N(cH3)c2Hs~ -S02-N(C3H7)2, -SO2-N(C4Hg)2, -CO-N(CH3)2, -co-N(c2Hs)2~ -CO-N(cH3)c2H5~ -CO-N(C3H7)2, -CO-N(CH3)C3H7-i, -CO-N(CH3)C3H7-n, -CO-N(CH3)C4Hg-n, -CO-N(C4Hg)2 and -CO-N(C2Hs)C3H7-n.

In alkoxyalkoxy, an alkoxy group bonded to the remainder of the compound I is substituted by a further alkoxy group, it being possible for both carbon chains independently of one another to be straight-chain or branched; examples are methoxymethoxy, methoxyethoxy, ethoxyethoxy, ethoxymethoxy, propoxymethoxy, methoxypropoxy, butoxymethoxy and propoxyethoxy.

If the abovementioned bridges which are formed by two substituents R3 together are substituted, then either of the hydrogen atoms in the unsubstituted skeleton is replaced by an alkyl, alkoxy or haloalkyl substituent, or one or more than one, in particular all, of the hydrogen atoms in the unsubstituted skeleton are replaced by identical or different halogen. Examples of such substituted bridges are -O-CF2-O-, for example, 2,3-O-CF2-O-or 3,4-O-CF2-O-, -O-CF2-CH2-O-, -O-CF2-CF2-O-, -O-CHF-CHCI-, -O-CH-CH(CH3)-CH2-, 2,3-CH=CH-CH=CH-, 3,4-CH=CH-CH=CH-, -CH=C(OCH3)-CH=CH- and-CH=CH-C(CF3)=CH-.

The alkyl skeleton in the substituted alkyl groups R4 has preferably two or, in particular, t7 olle of ~he abovementioned substi~uents; howe~er, if it is a halogen-substituted allcyl group ~4, then one or more than one, for example alh of the hydrogen atoms in the unsubstituted alkyl skeleton are replaced by identical or different halogen. If the substituted alkyl groups R4 contain a substituted phenyl ring, then this phenyl ring has preferably two or, in particular, one of the abovementioned substituents; however, if it is a halogen-substituted phenyl ring, then 1, 2, 3, 4 or all of the pheny~ hydrogen atoms can be replaced by identical or different halogen. The aL~cyl skeleton is preferably a methyl group.

The following are preferred embodiments within the scope of the invention:

(1) A compound of the formula I in which R1 is perfluoro-CI-C6alkyl, in particular perfluoro-Cl-C4alkyl, especially CF3 or C2Fs, in particular CF3;

(2) A compound of the formula I in which R2 is chlorine or bromine, in particular bromine;

(3) A compound of the formula I in which n is the number 1, 2, 3, 4 or 5, in particular 1, 2 or 3 or, if all radicals R3 simultaneously are halogen, 1, 2, 3, 4, or 5, where, if n is greater than 1, the radicals R3 are identical or different, and R3 is halogen, halo-CI-C4alkyl, halo-C1-C4alkoxy, cyano, Cl-C4alkyl, Cl-C4alkoxy, Cl-C4alkylthio or C1-C4alkanesulfonyl, andlor two substitutents R3 bonded to adjacent C atoms of the phenyl ring together are -O-C(halogen)2-O-, in particular -O-CF2-O-, or -CH=CH-CH=CH-, in particular the number 1 or 2, where, if n is 2, the radicals R3 are identical, and R3 is halogen, halo-CI-C4alkyl or halo-Cl-C4alkoxy, or two substituents R3 bonded to two adjacent C atoms of the phenyl ring together are -CH=CH-CH=CH-, especially the number 1 and R3 is trifluoromethyl, trifluoromethoxy or chlorine;

(4) A compound of the formula I in which R4 is hydrogen, Cl-C4alkyl, C3-C4alkenyl, halo-C3-C4alkenyl, C3-C4alkynyl, cyano, Cl-C4alkylthio, Cl-C4alkanesulfinyl, Cl-C4alkanesulfonyl, halo-Cl-C4alkanesulfonyl, di-CI-C4alkylaminosulfonyl, di-Cl-C4alkylaminocarbonyl or a C1-C4alkyl group substituted by one or more substituents selected from the group comprising halogen, Cl-C4alkoxy, hydroxyl, C1-C4alkylthio, C2-C6alkoxyalkoxy, Cl-C4alkanesulfinyl, Cl-C4alkanesulfonyl, Cl-C4alkylcarbonyl, Cl-C4alkoxycarbonyl, Cl-C4alkylcarbonyloxy, cyano, C2-C4alkenylcarbonyloxy, phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phellylsulfinyl and phenylsulfonyl, where the phenyl rings in these phenyl, phenoxy, phenylthio, ben~yloxy, benzoyloxy, ben~oyl, phenylsulfinyl and phenylsulfonyl substituents can in each case be substituted by halogen, Cl-C4alkyl, Cl-C4alkoxy, halo-Cl-C4alkyl, halo-Cl-C4alkoxy, Cl-C4alkylthio, Cl-C4alkanesulfonyl, halo-CI-C4alkylthio, halo-CI-C4alkanesulfinyl, halo-CI-C4alkanesulfonyl, cyano or nitro, in particular hydrogen, Cl-C4alkyl, C3-C4alkynyl, Cl-C4a1kanesulfonyl, di-CI-C4alkylaminosulfonyl, or a Cl-C4alkyl group substituted by Cl-C4alkoxy, Cl-C4alkylthio, C2-C6alkoxyalkoxy, Cl-C4alkanesulfonyl, Cl-C4alkylcarbonyl, Cl-C4alkoxycarbonyl, cyano, monohalophenyl or phenoxy, especially hydrogen, C1-C4alkyl, or a C1-C4alkyl group substituted by Cl-C4alkoxy or C2-C6alkoxyalkoxy, in particular hydrogen, C1-C4alkyl or C2-C6alkoxyalkyl, preferably methyl, methoxymethyl or ethoxymethyl, in particular hydrogen or ethoxymethyl;
(5) A compound of the formula I in which R1 is perfluoro-C1-C6alkyl, R2 is chlorine or bromine, R3 is halogen, halo-C1-C4alkyl, Halo-C1-C4alkoxy, cyano, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4alkanesulfonyl, R4 is hydrogen, C1-C4alkyl or C2-C6alkoxyalkyl, and n is the number one, two or three, where n can be the number one, two, three, four or five if all radicals R3 simultaneously are halogen;
(6) A compound of the formula I in which R1 is trifluoromethyl or pentafluoroethyl, R2 is bromine, R3 is fluorine, chlorine, trifluoromethyl, fluoro-Cl-C3aLIcoxy, methylthio, cyano or C1-C3alkoxy, R4 is hydrogen, methyl, methoxymethyl or ethoxymethyl, and n is the number one, two or three;
(7) A compound of the formula I in which R1 is trifluoromethyl, R2 is chlorine or bromine, R3 is fluorine, chlorine, trifluoromethyl, fluoro-C1-C3alkoxy, methylthio, cyano or Cl-C3alkGxy, R4 is hydrogen, methyl, methoxymethyl or ethoxymethyl, and n is thenumber one, two or three;
(8) A compound of the formula I in which n is the number 1, Rl is trifluoromethyl or pentafluoroethyl, R2 is bromine, R3 is trifluoromethyl, trifluoromethoxy or chlorine, and R4 is hydrogen or ethoxymethyl.

Particularly preferred within the scope of the invention are the compounds of the formula I
mentioned in Exarnples H2, H3, HS and H6.

~f~ I ~,'L3 Individually preferred compounds within the scope of the invention are (a) 4-Bromo-2-(4-chlorophenyl)-3-cyano-5-heptafluoropropyl-pyrrole, (b) 4-Bromo-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-pyrrole, (c~ 4-Bromo-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-heptafluoropropyl-pyrrole, (d) 4-Chloro-2-(4-chlorophenyl)-3-cyano-5-heptafluoropropyl-pyrrole, (e) 4-Chloro-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-pyrrole, (f) 4-Chloro-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-heptafluoropropyl-pyrrole, (g) 4-Bromo-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethylphenyl~-pyrrole, (h) 4-Chloro-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (i) 4-Bromo-3-cyano- l -ethoxymethyl S-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (~) 4-Chloro-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (k) 4-Bromo-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole, (1) 4-Chloro-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole, (m) 4-Bromo-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-2-(4-trinuoromethoxyphenyl)-pyrrole and (n) 4-Chloro-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole.

A further subject of the invention is the process for the preparation of the compounds of the formula I, in free form or in salt form, which comprises, for example a) introducing the halogen substituent R2 into the 4-position of the pyrrole ring of a compound of the formula CN

R,--CF2~N, ~ (II), (R3)~

in which R1, R3, R4 and n are as defined in formula I, or into a salt thereof, by reaction with a halogenating agent, preferably in the presence of a base, or b) to prepare a compound of the formula I in which R4 is other than hydrogen, or a salt thereof, reacting a compound of the formula I which can be obtained, for example, 3~ J 7 according to variant a), and in which 1~4 iS hydrogen, or a salt of such a compound, with a compound of the formula X-R4 (III) which is known or which can be prepared analogously to corresponding known compounds and in which R4 is as defined in forrnula I, with the exception of hydrogen, and X is a leaving group, or, if appropriate, with a salt thereof, preferably in the presence of a base, or c) to prepare a compound of the formula I, in which R4 is methyl or a group R2CH2-, or a salt thereof, reacting, optionally in the presence of a base, optionally in the presence of a radical initiator, a compound of the formula CN

Rl--CF2~_~ (VII), CH3 (R3)n in which Rl, R3 and n are as defined in formula I, or a salt thereof, with a halogenating agent and, in each case, if desired, converting a compound of the formula I, in free form or in salt form, which can be obtained according to the process or by a different route, into a different compound of the forrnula I, resolving an isomer mixture which can be obtained according to the process, and isolating the isomer desired and~or converting a free compound of the formula I which can be obtained according to the process into a salt, or a salt of a compound of the formula I which can be obtained according to the process into the free compound of the formula I or into a different salt.

What has been said hereinbefore for salts of compounds I applies analogously to starting materials listed hereinbefore and hereinafter with regard to salts thereof.

The reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, conventionally, in the presence of a suitable solvent or diluent or a mixture of these, the process being carried out, depending on the circumstances, with cooling, at room temperature or with heating, for example in a temperature range of approximately -~0C to the boiling point of the reaction medium, preferably from approximately -20C to approximately +lSQC, and, if required, in a sealed container, under pressure, under an inert gas atmosphere and/or under anhydrous ~tl'~' r` ~

conditions. Particularly advantageous reaction conditions can be found in the examples.

The starting materials listed hereinbefore and hereinafter which are used for the preparation of the compounds I, in free form or in salt form, are known or can be prepared by methods known per se, for example according to the instructions below.

Variant a):
Examples of suitable halogenating agents are elemental halogens, such as elemental chlorine, bromine or iodine, sulfuryl halides such as sulfuryl chloride or sulfuryl bromide, or N-halosuccinimides, such as N-chlorosuccinimide or N-bromosuccinimide.

Examples of suitable bases for facilitating ehe reaction with the halogenating agent are hydroxides, hydrides, amides. alkanolates, acetates, carbonates, diaLkylamides or alkylsilylamides of alkali metals or aL~aline earth metals, or alkylamines, aL~ylenediamines, free or N-alkylated, saturated or unsaturated cycloaLkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium acetate, sodium carbonate, potassium tert-butanolate, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine,triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can ~e reacted with each other as such, i.e. without the addition of a solvene or diluent, for example in the melt. However, the addition of an inert solvent or diluent or a mixture of these is advantageous in most cases. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, diisopropyl ether, dibutyl etl-er, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, teerahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone or methyl fd ~ J ' o~

isobutyl kelone; alcollols, such as mcthanol, ethanol, propanol, isopropanol, butanol, elhylene glycol or glycerol; amides such as N,N-dimethylformamide, N,N-diethylforrnamide, N,N-~imethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide; and acids, for example strong organic carboxylic acids such as unsubstituted or, for example, halogen-substituted, Cl-C4-alkanecarboxylic acids, for example formic acid, acetic acid or propionic acid. If the reaction is carried out in the presence of a base, bases which are employed in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range of from approximately 0C to approximately +180C, preferably from approximately +10C to approximately +130C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture. In most cases, the temperature of the reaction mixture rises automatically by the heat of reaction which is liberated. To complete the halogenation reaction, it is advantageous to finish by briefly heating the reaction mixture to reflux point.

Variant b:
Examples of suitable leaving groups X in the compounds In are hydroxyl, C1-C8alkoxy, halo-Cl-C8aLkoxy, Cl-C8alkanoyloxy, mercapto, Cl-C8alkylthio, halo-CI-C8alkylthio, Cl-C8alkanesulfonyloxy, halo-CI-C8alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen.

Examples of suitable bases for facilitating the elimination of HX are of the type described in variant a).

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or a mixture of these is advantageous in most cases. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters such as ethyl acetate; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, 2~ p 9~'' 7 tetrahydrofur;m or dioxane; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methallol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides sucl- as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles such as acetonitrile; and sulfoxides such as dimethyl sulfoxides. If the reaction is carried out in the presence of a base, bases which are employed in excess such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvents or diluents.

The reaction is advantageously caTried out in a temperature range of from approximately 0C to approximately ~180C, preferably from approximately +10C to approximately +130C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

Variant c):
Examples of suitable halogenating agents are of the type described in variant a).

Examples of suitable bases for facilitating the reaction with the halogenating agent are of the type described in variant a).

Examples of suitable radical initiators are peroxo compounds, such as dibenzoyl peroxide or di-tert.-butyl peroxide, azo compounds, such as 2,2'-azobisisobutyronitrile, and light.

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. However, the addition of an inert solvent or diluent or a mixture of these is advantageous in most cases. Examples of such solvents or diluents which may be mentioned are of the type described in variant b).

The reaction is advantageously carried out in a temperature range of from approximately 0C to approximately +180C, preferably from approximately +10C to approximately +130C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

It is possible to prepare different products of the forrnula I when variant c) is carried out, depending on the number of equivalents of halogenating agent used. At least two equivalents of halogenating agent have to be used. By means of the first equivalent the ~', ?

dihydropyrrole derivative VII is oxidised and the corresponding pyrrole intermediate is thus obtained ("compoun(l A"). By means of the second equivalent of halogenating agent the halogen substituent R2 is introduced into the 4-position of the pyrrole ring of the compound A, thus yielding the corresponding compound I, wherein R4 is methyl ("compound B"). In order to obtain the corresponding compound I, wherein R4 is a group R2CH2-, i. e. in order to mono-halogenate the methyl group R4 of the compound B, a third equivalent of halogenating agent is needed. The term "equivalent" is to be understood in this paragraph in such a way, that it comprises not only the exact amount corresponding to the exact equivalent, but also a certain range, for exarnple approximately 10%, above and below this exact amount. It is possible to isolate the cornpound A and/or the compound B, but preferably the reaction is carIied out in the form of a one-pot-reaction without isolation of the compounds A and B. It is also possible to add the whole amount of halogenating agent at the beginning of the reaction, but preferably the halogenating agent is added portionwise, for example in several portions of one equivalent each. The mono-halogenation of the methyl g~roup R4 of compound B is preferably carried out in the presence of a radical initiator.

The compounds II which are used as educts in process variant a), in free form or in salt form, are novel and also forrn a subject of the invention. Particularly preferred compounds of the formula II within the scope of the invention are those mentioned in Examples H1 and H6.

A further subject of the invention is the process for the preparation of the compounds of the formula Il, in free form or in salt form, which comprises, for example, d) to prepare a compound of the formula II in which R4 is hydrogen, or a salt thereof, reacting a compound of the forrnula 0~

C 2~N~C--~ (R3)n in which Rl, R3 and n are as defined in formula I, or a salt of such a compound, with 2-chloroacrylonitrile, preferably in a high-boiling polar solvent such as nitromethane, and at the reflux temperature of the reaction mixture, or e) to prepare a compound of the formula II in which R4 is other than hydrogen, or a salt of 2~?'~6,.~7 sllch a compoulld, reacting a compound of the formula II which can be obtained, for example, in accordance with variant d), and in which R4 is hydrogen, or a salt of such a compolmd, preferably in the presence of a base, for example of the type given in the case of variant a), with a compound of the formula X-R4 (III) which is known or which can be prepared analogously to corresponding known compounds and in which R4 is as defined in formula I with the exception of hydrogen, and X is a leaving group, for example of the type given in variant b), or, if appropriate, with a salt thereof, and, if desired, in each case converting a compound of the formula II which can be obtained according to the process or by a different route, in free form or in salt form, into a different compound of the formula II, resolving an isomer mixture which can be obtained according to the process, and isolating the isomer desired, and/or converting a free compound of the formula II which can be obtained according to the process into a salt, or converting a salt of a compound of the formula II which can be obtained according to the process into the free compound of the formula II or into a different salt.

The compounds IV, in free form or in salt form, are known or can be prepared analogously to known compounds, for example by reacting a compound of the formula NH2 (R3)n (V), which is known or which can be prepared analogously to corresponding known compounds and in which R3 and n are as defined in formula I, or a salt of such acompound, with a compound of the formula O O
Il 11 R1-CF2-c-O-c-cF2-Rl (VI), which is known or which can be prepared analogously to corresponding known compounds and in which R1 is as defined in formula I, the process preferably being carried out under atmospheric pressure, if appropriate in the presence of a solvent or diluent, for example of the type given in the case of variant a), in particular in the presence of a high-boiling aromatic hydrocarbon such as toluene, xylene, mesitylene or tetralin, and at temperatures between 70C and 200C, in particular between 120C and 180C, preferably at the boiling point of the reaction mixture.

The compounds VII which are used as educts in process variant c), in free form or in salt 3 ~ ~:3~7 form, are novel and also form a subject of the invention.

A further subject of the invention is the process for the preparation of the compounds of the formula VII, in free form or in salt forrn, which comprises, for example, f) reacting a compound of the forrnula O COOH
R1--CF2~ ~ (vm), CH (R3)n in which Rl, R3 and n are as defined in forrnula I, or a salt of such a compound, with acrylonitrile, preferably in a high-boiling polar solvent, such as acetonitrile, in the presence of an acid anhydride, such as acetic anhydride, and at the reflux temperature of the reaction mixture, and, if desired, converting a compound of the formula VII which can be obtained according tO the process or by a different route, in free form or in salt form, into a different compound of the formula VII, resolving an isomer mixture which can be obtained according to the process, and isolating ~he isomer desired, and/or converting a free compound of the formula VII which can be obtained according to the process into a salt, or converting a salt of a compound of the formula VII which can be obtained according to the process into the free compound of the formula VII or into a different salt.

The compounds VIII are known or can be prepared analogously to corresponding known compounds.

A compound I, II or VII which can be obtained according to the process or by a different route can be converted into a different compound I, II or VII in a manner known per se by replacing one or more substituents of the starting compound I, II or VII in the customary manner by (an)other substituent(s) according to the invention.

For example, - hydroxyl groups (as substituents of alkyl groups R4) can be alkylated to give alkoxy groups (as substituents of alkyl groups R4);
- halogen R3 can be introduced into unsubsti~uted positions of the phenyl ring;
- mercapto groups R3 andJor R4 can be oxidised to give sulfinyl or sulfonyl groups R3 and~or R4 or sulfinyl groups R3 and/or R4 can be oxidised to give sulfonyl groups R3 2 ~ ~ 7 ~ 15 ~

and/or R4;
- methyl g;oups R4 can be mono-halogenated to give mono-halomethyl groups 1~,; or - the halogen substituent present in mono-halomethyl groups R4 can be replaced by an alkoxy group to give a mono-a~coxymethyl group R4.

Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible to replace, in one reaction step, only one substituent by a different substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step.

Salts of compounds I, II or VII can be prepared in a manner known per se. For example, acid addition salts of compounds I, II or VII are obtained by treatment with a suitable acid or a suitable ion-exchanger reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion-exchanger reagent.

Salts of compounds I, II or VII can be converted in the customary manner into the free compounds I, II or VII, respectively, for example acid addition salts by treatment with a suitable basic agent or a suitable ion-exchanger reagent and salts with bases for exarnple by treatment with a suitable acid or a suitable ion-exchanger reagent.

Salts of compounds I, II or VII can be converted into other salts of compounds I, II or VII, respectively, in a manner known per se, for example acid addition salts into different acid addition salts, ~or example by treatment of a salt of an inorganic acid such as a hydrochloride with a suitable metal salt such as a sodium salt, barium salt or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and so precipitates from the reaction mixture.

Depending on the procedure or reaction conditions, the compounds I, II or VII which have salt-forming properties can be obtained in free form or in the form of salts.

The compounds I, II or VII, in free form or in salt form, can exist in the fo~n of one of the isomers which are possible or as a mixture thereof, for example as pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending, for exarnple, on the number, absolute and relative configuration of asymmetric carbon atoms in the 2~ 7 molecule and/or depending on the configuration of non-aromatic double bonds in the molecule; the invention relates to the pure isomers as well as to all isomer mixtures which are possible and is to be understood accordingly llereinbefore and hereinafter, even when stereochemical details are not mentioned specifically in each case.

Diastereomer m;xtures and racemate mixtures of compounds 1, II or VII, in free form or in salt form, which can be obtained according to the process - depending on the choice of starting materials and procedures - or by other routes can be resolved in the known manner based on the physicochemical differences of the components to give the pure diastereomers or racemates, for example by fractional crystallisation, distillation and/or chromatography.

Enantiomer mixtures such as racemates which can be obtained accordingly can be resolved by known methods to give the optical antipodes, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is sequestered, or by conversion into diastereomeric salts, for example by reacting a basic end product racemate with an optically active acid such as carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or sulfonic acid, for example camphorsulfonic acid, and resolution of the resulting diastereomer mixture, for example on the basis of their different solubilities by fractional crystallisation to give the diastereomers from which the enantiomer desired can be liberated by the action of suitable agents, for example basic agents.

In addition to the resolution of corresponding isomer mixtures, pure diastereomers, or enantiomers, can also be obtained according to the invention by generally known methods of diastereoselective, or enantioselective, synthesis, for example by carrying out the process according to the invention with educts having a suitable stereochemistry.

It is advantageous to isolate, or synthesise, in each case the biologically more active isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have different biological activities.

The compounds I, II or VII, in free form or in salt form, can also be obtained in the form of their hydrates and/or can include other solvents, for example those which can be used for the crystallisation of compounds in solid form.

The invention relates to all those embodiments of the process in which a compound which can be obtained in any step of the process is used as starting material or interrnediate and all, or some, of the missing steps are carried out, or in which a starting material in the form of a derivative or salt and/or racemates or antipodes thereof are used or, in particular, formed under the reaction conditions.

It is preferred to use those starting materials and intermediates, in each case in free form or in salt forrn, in the process of the present invention which lead to the compounds I or salts thereof which have been described at the outset as being particularly valuable.

In particular, the invention relates to the preparation processes described in Examples H1 to H6.

Another subject of the invention is novel starting materials and interrnediates, in each case in free form or in salt form, which are used according to the invention for the preparation of the compounds I or salts thereof, a process for their preparation, and their use as starting materials and intermediates for the preparation of the compounds I; in particular, this applies to the compounds II and VII.

The compounds I according to the invention are valuable active ingredients in the field of pest control which have a very favourable biocidal spectrum when used preventively and/or curatively, even at low application concentrations, while being well tolerated by warm-blooded species, fish and plants. The active ingredients according to the invention are active against all or individual development stages of norrnally sensitive, but also resistant, animal pests such as insects and representatives from the order of the Acarina, and of phytopathogenic fungi. The insecticidal and/or acaricidal action of the active ingredients according to the invention can be demonstrated either directly, i.e. in destruction of the pests, which is immediately effective or only after some time has elapsed, for example during moulting, or indirectly, for example by reduced oviposition and/or hatching rate, good action meaning a destruction rate (mortality) of at least 50 to 60%.

2~ d~

The abovementioned animal pests inchlde, for example:
from the order of the Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacoso~na spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order of the Co]eoptera, for example Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;
from the order of the Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,Periplaneta spp. and Schistocerca spp.;
from the order of the Isoptera, for example Reticulitermes spp.;
from the order of the Psocoptera, for example Liposcelis spp.;
from the order of the Anoplura, for example Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
from the order of the Mallophaga, for example Damalinea spp. and Trichodectes spp.;
from the order of the Thysanoptera, for example ' f~.3'~ 7 Frankliniella spp.~ Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii;
from the order of the Heteroptera, for example Cimex Sp?., ~)istantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp.
Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
from the order of the Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, 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., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobicn spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;
from the order of the Hymenoptera, for example Acromyrrnex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp.
and Vespa spp.;
from the order of the Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., (~lossina spp., Hypoderma spp., Hyppobosca spp.,Liriomyza spp., Lucilia spp.~ Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
from the order of the Siphonaptera, for example Ceratophyllus spp. and Xenopsylla cheopis;
from the order of the Thysanura, for example Lepisma saccharina and from the order of the Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,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, 2~? J ~ 7 Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and l`etranychus spp..

The abovementioned phytopathogenic fungi include, for example:
from the class of the Fungi imperfecti, for example Botrytis spp., Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp., Cercospora spp. and Alternaria spp.;
from the class of the Basidiomycetes, for example Rhizoctonia spp., Hemileia spp. and Puccinia spp.;
from the class of the Ascomycetes, for example Venturia spp., Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and from the class of the Oomycetes, for example Phytophthora spp., Pythium spp. and Plasmopara spp..

The active ingredients according to the invention allow the control, i.e. reduction or destruction, of pests of the abovementioned type which are found in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as *uits, flowers, foliage, staL~cs, tubers or roots, and in some cases the protection against these pests extends to parts of plants which are formed at a later point in time.

Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet such as sugar beet or fodder beet; fruit, for example pomaceous fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawbenies, raspberries or blackberries; pulses such as beans, lentils, peas or soybeans; oil crops such as oil-seed rape, mustard, poppy, olives, sunflowers, coconut, castor-oil plant, cacao or groundnuts; cucurbits such as pumpkins, cucumbers or melons; fibre plants such as cotton, fiax, hemp or jute; citrus *uit such as oranges, lemons, grapefruit or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage species, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae such as avocado, cinnamonium or camphor; and also tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, vines, hops, Musaceae, latex plants and ornamentals.

The active ingredients according to the invention are particularly suitable for controlling insects and representatives from the order of the Acarina, in particular feeding insects which are plant-injurious, such as Anthonomus grandis, Diabrotica balteata, Heliothis ~ ~ J . .

virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soybean, oil-seed rape and vegetable crops.

Other fields of application of the active ingredients according to the invention are the protection of stored products and stores and of material, and, in the hygiene sector, in particular the protection of domestic animals and productive livestock against pests of the abovementioned type.

The invention therefore also relates to pesticides such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - one of the active ingredients according to the invention and which are to be selected depending on the intended aims and prevailing circumstances.

The active ingredient in these compositions is employed as pure active ingredient, for example a solid active ingredient in a specific particle size, or, preferably, together with -at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).

The following are possible as solvents: aromatic hydrocarbons which may be partially hydrogenated, preferably the fractions C8 to Cl2 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalenes, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols as well as their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol,strongly polar solvents such as N-methyl-pyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidised or epoxidised vegetable oils such as unepoxidised or epoxidised rapeseed oil, cas~or oil, coconut oil or soya oil, and silicone oils.

Solid carriers which are generally used, for example for dusts and dispersible powders, are ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silica or s7 highly-disperse absorptive polymers Possible particulate adsorptive carriers for granules are either porous types, for example pumice, brick glit, sepiolite or bentonite, or non-sorptive carrier materials, for example calcite or sand. Moreover, a large number of pregranulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.

Suitable surface-active compounds are non-ionic, cationic andlor anionic surfactants or surfactant mixtures having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient to be forrnulated. The surfactants listed below are only exemplary; a large number of other surfactants which are customarily used in the art of the formulalion and suitable according to the invention are described in the specialist literature.

Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and aL~ylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable non-ionic surfactants are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropyleneglycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. I he compounds mentioned generally contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other suitable substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are mainly quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 C atoms as substituents and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples which may be mentioned are stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.

Suitable anionic surfactants can be either water-soluble soaps or water-soluble synthetic surface-active compounds. Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts and substituted or unsubstituted ammonium salts of higher fatty acids (Cl0-C22), such as the sodium salts or potassium salts of oleic or stearic acid or of nat~lral mixtures of fatty acids which can be oblained, for example, from coconut oil or tallow oil; fatty acid methyltaurides may furtherrnore be mentioned. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. The fatty sulfonates and fatty sulfates are generally in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and generally have an alkyl radical having 8 to 22 C atoms, alkyl also embracing the alkyl moiety of acyl radicals; exarnples which may be mentioned are the sodium or the calcium salt of ligninsulfonic acid, of the dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric acid esters and sulfonic acids of fatty alcohoVethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fat~ acid radical having 8 to 22 C atoms. Examples of alkylaryl sulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product. Other suitable compounds are corresponding phosphates, for example salts of the phosphoric acid ester of a p-nonylphenol/(4- 14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99 %, in particular 0.1 to 95 %, of active ingredient and 1 to 99.9 %, in particular 5 to 99.9 %, of - at least - one solid or liquid auxiliary, where, as a rule, 0 to 25 %, in particular 0.1 to 20 %, of the composition can be surfactants (% is in each case to be understood as meaning per cent by weight). While concentrated compositions are more preferred as commercially available goods, the end consumer generally uses dilute compositions which have considerably lower concentrations of active ingredient. In particular, preferred compositions are composed as follows (% = per cent by weight):

Emulsifiable concentrates:
Active ingredient: 1 to 90 %, preferably 5 to 20 %
Surfactant: 1 to 30 %, preferably 10 to 2û%
Solvent: 5 to 98 %, preferably 70 to 85 %

~2 D~lsts:
Active ingredient:û.l to 10 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, prei~erably g9.9 to 99 %

Suspension concentrates:
Active ingredient:5 to 75 %, preferably 10 to ~0 %
Water: 94 to 24 %, preferably 88 to 30 %
Surfactant: 1 to 40 %, preferably 2 to 30 %

~ettable powders:
Active ingredient:0.5 to 90 %, preferably 1 to ~0 %
Surfactant: 0.5 to 20 %, preferably 1 to 15 %
Solid carrier: 5 to 99 %, preferably 1~ to 98 %

Granules:
Active ingredient:0.5 to 30 %, preferably 3 to 15 %
Solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The activity of the compositions according to the invention can be broadened considerably and adapted to prevailing circumstances by adding other insecticidal, acaricidal and/or fungicidal active ingredients. Suitable examples of active ingredients which are added are representatives of the following classes of active ingredients: organophosphoruscompounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilisers, for example epoxidised or unepoxidised vegetable oils (for example epoxidised coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders andlor adhesives, and also fertilisers or other active ingredients for achieving specific effects, for example bactericides, nematicides, molluscicides or selective herbicides.

The compositions according to the invention are prepared in a manner known per se, for example in the absence of auxiliaries by grinding and/or screening of a solid active ingredient, or mixture of active ingredients, for example to obtain a certain particle size, and in the presence of at least one auxiliary for example by intimately rnixing and/or grinding the active ingredient, or mixture of active ingredients, with the auxiliary(ies).

These processes for the preparation of the compositions according to the invention and the use of the compounds I for the preparation of these compositions are also part of the invention.

The invention furthermore relates to the methods by which the compositions are applied, i.e. the methods for controlling pests of the abovementioned type, such as spraying, atomising, dusting, brushing on, dressing, scattering or pouring, to be selected depending on the intended aims and the prevailing circumstances, and to the use of the compositions for controlling pests of the abovemen~ioned type. Typical application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rates per hectare are generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.

A preferred application method in the field of crop protection is application to the foliage of the plants (foliar appiication), where the ~requency of application and the dosage rate can be adjusted as a function of the severity of infestation with the pest in question.
Alternatively, the active ingredient can reach the plants via the root system (systemic action), by allowing the locus of the plants to absorb a liquid composition or by incorporating the active ingredient in solid forrn into the locus of the plants, for exarnple the soil, such as in the form of granules (soil application). In the case of paddy rice, such granules can be metered into the flooded paddy field.

The compositions according to the invention are also suitable for protecting plant propagation material, for exarnple seeds, such as fruits, tubers or grains, or plant cuttings, against fungal infections and animal pests. The propagation material can be treated with the composition before use, for example seed can be dressed before sowing. The active ingredients according to the invention can also be applied to seed kernels (coating) either by immersing the kernels in a liquid composition or by coating them with a solidcomposition. It is also possible to apply the cornposition to the site where the propagation material is used, for example during sowing into the seed furrow. The invention also relates to these treatment methods for plant propagation material and to the plant propagation material which has been treated in this manner.

The following examples are intended to illustrate the invention. They impose no limitation on the invention. Temperatures are given in degrees centigrade.

2~ ~ ~r3iJ7 Preparation examples Example H1: 2-(4-Chlorophenyl)-3-cya~o-5-pentafluoroethyl-pyrrole (Table 2, Compound No. 2.1).
CN
F3C--CF2~ ~CI

A mixture of 47 g of 4-(4-chlorophenyl)-2,5-dihydro-5-oxo-2-pentafluoroethyl-oxazole, 131.1 g of 2-chloroacrylonitrile and 750 ml of nitromethane is refluxed for 22 hours and then cooled to approx. +5. The solid which has precipitated is filtered off and washed with a little cold dichloroethane. This gives, if desired with additional working up of the mother liquor, the title compound which melts at 223.5 to 224.

Example H2: 4-Bromo-2-(4-chlorophenyl)-3-cyano-5-pentafluoroethyl-pyrrole (Table 1, CompoundNo. 1.1).
Br CN
F3C--C F2~3 Cl H

20 g of 2-(4-chlorophenyl)-3-cyano-S-pentafluoroethyl-pyrrole and 12.8 g of sodium acetate are introduced into 400 ml of acetic acid. The mixture is stirred for lS minutes (a clear solution forms~, treated dropwise in the course of 1 hour at room temperature with a solution of 49.8 g of bromine in 100 ml of acetic acid, stirred for 2 hours at room temperature, poured into 2 l of sodium hydrogen sulfite solution (10 %) and filtered. The colourless crystals obtained are washed with water and dried in vacuo at +50. This gives the title compound which melts at 213 to 215 with decomposi~ion.

Example H3: 4-Bromo-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-S-pentafluoroethyl-pyrrole (Table 1, Compound No. 1.3).
Br CN
F3C--CF2~- ~ Cl CH2-O-C2Hs 5 g of 4-bromo-2-(4-chlorophenyl)-3-cyano-5-pentafluoroethyl-pyrrole are dissolved in t;J

50 rnl of dry tetrahydrofuran, and the solution is treated with 2.7 g of potassium tert-butanolate at room ~emperature. 2.7 g of chloromethyl ethyl ether are subsequently added dropwise. The reaction mixture is stirred for 22 hours at room temperature, poured into 400 ml of water and extracted three times with diethyl ether. The organic phases are combined, wasl~ed with NaCI solution, dried over Na2SO4 and evaporated in vacuo. The result is yellow crystals ~hich are recrystallised from 10 ml of hexane. This gives the title compound which melts at 69 to 70.5".

Example H4: 2-(4-Chlorophenyl)-3-cyano-4,5-dihydro-1-methyl-5-pentafluoroethyl-pyrrole.
CN
F3C--CF2 1~ ,~3 Cl A mixture of 15 g of N-c~rboxy-4-chlorophenyl-methyl-N-methyl-N-pentafluoroethyl-carbonyl-amine, 100 ml of acetonitrile, 4.2 ml of acrylonitrile, 11 g of acetic anhydride and 15 drops of triethylamine is heated under reflux for 5.5 hours and then evaporated to dryness. Purification of the residue by column chromatography [SiO2; hexane/ethyl acetate (9:1)] yields the title compound, which melts at 113 to 116.

Example HS: 4-Chloro-2-(4-chlorophenyl)-3-cyano-1-methyl-5-pentafluoroethyl-pyrrole (Table 1, Compound No. 1.29).
Cl CN

F3C CF2~\~3cl A saturated solution of 12 g of N-chlorosuccinimide in N,N-dimethylformamide is added over a period of 30 minutes to a mixture of 10 g of 2-(4-chlorophenyl)-3-cyano-4,5-dihydro-1-methyl-5-pentafluoroethyl-pyrrole and 10 ml of N,N-dimethylformamide.
The reaction mixture is heated to 100 for 30 minutes and is then poured, while stilTing, into 1 1 of water. The oily precipitate is taken up in ethyl acetate, and the ethyl acetate phase is washed several times with water, dried and evaporated to dryness.
Recrystallisation of the residue using ethyl acetate/hexane yields the title compound, which melts at 120.

2~7'~ 7 Example H6: In a manner analogous to that described in Examples H1 ~o HS, it is possible to also prepare the other compounds listed in Tables 1 and 2. In the column "physical data" of these tables, temperatures given in each case denote the melting point of the compound in question, and "nD " is the refractive index of the compound in question at a temperature of T~C.

- 29 - ~.~ t ~7 'I`.lble 1 R1 CF2 ~ (R3)n Comp Rl R2 R3 n R4 Physical No. data 1.1 CF3 Br 4-CI 1 H 213-215 1.2 C2Fs Br 4-CI 1 H 199-201 1.3 cr3 Br 4-CI 1 CH2oc2H5 69-70.5 1.4 C2Fs Br 4-Cl 1 CH2OC2Hs 79-80 1.5 C2Fs Br 4-F 1 H 219-220.5 1.6 CF3 Br 4-F 1 CH2Oc2Hs 85.5-86 1.7 C2F5 Br 4-F 1 CH2OC2Hs 81.5-83 1.8 CF3 Br 4-F 1 H 222.5-224 1.9 CF3 Br 4-CI 1 CH3 137-139 1.10 CF3 Br 4-CF3 1 H 238-239.5 1.11 C2Fs Br 4-CF3 1 H 201-202 1.12 C2Fs Br 4-CI 1 CH2O(CH2)2OCH3 81.5-82 1.13 C2Fs Br 4-Cl l CH3 162.5-163.5 1.14 CF3 Br 4-CF3 1 CH2OC2Hs 86-87.5 1.15 C2F5 Br 4-CF3 1 CH2OC2Hs 100.5-102.5 1.16 C6FI3-n Br 4-Cl 1 H 189-190 1.17 C6Fl3-n Br 4-CI 1 CH2OC2Hs 67-69 1.18 CF3 Br 4-CI 1 CH2O(CH2)2OCH3 n ~ = 1.5228 1.19 CF3 Br 2~4(cl)2 2 H 172-174 1.20 C2Fs Br 2~4(cl)2 2 H 155-156 1.21 CF3 Br 2,4(CI)2 2 CH2oc2H5 n2l.6~5 = 1 5325 1.22 C2Fs Br 2,4(C1)2 2 CH2OC2Hs n265 1 5134 1.23 CF3 Br 3,4(Cl)2 2 CH3 1.24 CF3 Br 3.4(CI)2 2 CH2oc2H5 114-116 1.25 CF3 Br 3,4(Cl)2 2 CH2CN
1.26 CF3 Br 3,4(Cl)2 2 CH2C-CH

J r~7 Comp Rl R2 R3 n R4 Physical No. data . _ . _ . _ 1.27 C2Fs Br 3,4(CI)2 2 (: H3 1.28 C2Fs Br 3,4(C1)2 2 CH2OC2Hs 107-108 1.29 CF3 Cl 4-CI 1 CH3 120 1.30 CF3 Cl 4-Cl 1 CH2OC2~s 76.5-77 1.31 C2F5 Cl 4-CI 1 CH3 1.32 C2F5 Cl 4-CI 1 CH2OC2Hs 78.5-80 1.33 CF3 Cl 4-CF3 1 CH3 1.34 CF3 Cl 4-CF3 1 CH2OC2Hs 1.35 C2Fs Cl 4-CF3 1 CH3 1.36 C2Fs Cl 4-CF3 1 CH2OC2Hs 1.37 CF3 Cl 2,4(C1)2 2 CH3 1.38 CF3 Cl 2,4(Cl)2 2 CH2OC2Hs 1.39 C2Fs Cl 2,4(CI)2 2 CH3 1.40 C2Fs Cl 2,4(C1)2 2 CH2OC2Hs 1.41 CF3 Cl 3,4(C1)2 2 CH3 1.42 CF3 Cl 3,4(Cl)2 2 CH2OC2Hs 1.43 C2Fs Cl 3,4(C1)2 2 CH3 1.44 C2F5 Cl 3,4(Cl)2 2 CH2OC2Hs 1.45 CF3 Br 4-CI 1 C2Hs 1.46 CF3 Br 4-Cl 1 CH2C--CH
1.47 CF3 Br 4-CI 1 CH2CN
1.48 CF3 Br 4-CI 1 CH2O-C6Hs 1.49 CF3 Br 4-CI 1 CH2OCH3 1.50 CF3 Br 4-CI 1 CH2SCH3 1.51 CF3 Br 4-CI 1 CH2COCH3 1.52 CF3 Br 4-CI 1 CH2COOCH3 1.53 CF3 Br 4-Cl 1 SO2CH3 1.54 CF3 Br 4-CI 1 SO2N(CH3)2 1.55 CF3 Br 4-CI 1 CH2SC2Hs 1.56 CF3 Br 4-CI 1 CH2SO2c2Hs 1.57 CF3 Br 4-Cl 1 CH2-C6H4-Cl(4) 1.58 C2Fs Br 4-Cl 1 C2Hs Cump R I R2 R3 n R4 Physical No. data 1.59 C2Fs Br 4-Cl 1 CH2C.-CH
1.60 C2F5 Br 4-CI 1 CH2CN
1.61 C2F5 Br 4-Cl 1 CH2o-c6H5 1.62 C2Fs Br 4-CI 1 CH2OCH3 1.63 C2Fs Br 4-CI 1 CH2SCH3 1.64 C2Fs Br 4-CI 1 CH2COCH3 1.65 C2Fs Br 4-CI 1 CH2COOCH3 1.66 C2Fs Br 4-CI 1 SO2CH3 1.67 C2Fs Br 4-CI 1 SO2N(CH3)2 1.68 C2Fs Br 4-C1 1 CH2SC2Hs 1.69 C2Fs Br 4-CI 1 CH2SO2c2Hs 1.70 C2Fs Br 4-Cl 1 CH2-C6H4-Cl(4) 1.71 CF3 Br 2,4,6(CI)3 3 CH3 1.72 CF3 Br 2,4,6(CI)3 3 CH2OC2Hs 1.73 C2Fs Br 2,4,6(Cl)3 3 CH3 1.74 C2Fs Br 2,4,6(C1)3 3 CH2oc2Hs 1.75 CF3 Br 4-Br 1 CH3 1.76 CF3 Br 4-Br 1 CH2OC2Hs 1.77 C2Fs Br 4-Br 1 CH3 1.78 C2Ps Br 4-Br 1 CH2OC2Hs 1.79 CF3 Br 4-OCF3 1 CH3 1.80 CF3 Br 4-OCF3 1 CH2OC2Hs nD=1.4872 1.81 C2Fs Br 4-OCF3 1 CH3 22.s 1.82 C2Fs Br 4-OCF3 1 CH2OC2Hs nD= 1.4732 1.83 CF3 Br 4-ocF2cHF2 1 CH3 1.84 CF3 Br 4-OCF2CHF2 1 CH2OC2Hs 1.85 C2Fs Br 4-OCF2CHF2 1 CH3 1.86 C2Fs Br 4-OCF2CHF2 1 CH2OC2Hs 1.87 CF3 Br 4-OCF2CHFCF3 1 CH3 1.88 CF3 Br 4-OCF2CHFCF3 1 CH2OC2~s 1.89 C2Fs Br 4-OCF2CHFCF3 1 CH3 ;~ ' I d ' P ~3 ~ ~ ~

Comp Rl R2 R3 n R4 Physical No. data 1.90 C2Fs Br 4-OCF2CHFCF3 1 CH2OC2Hs 1.91 CF3 Br 2,3,4,5,6(F)s 5 CH3 1.92 CF3 Br 2,3,4,5,6(F)s ~ CH2OC2H~
1~93 C2Fs Br 2,3,4,5,6(F)5 5 CH3 1.94 C2Fs Br 2,3,4,5,6(F)s S CH2OC2H5 1.95 CF3 Br 4-OCH2CF3 1 CH3 1.96 CF3 Br 4-OCH2CF3 1 CH2OC2Hs 1.97 C2Fs Br 4-OCH2CF3 1 CH3 1.98 C2Fs Br 4-OCH2CF3 1 CH2OC2Hs 1.99 CF3 Br 2,6(Cl)2,4CF3 3 CH3 1.100 CF3 Br 2,6(CI)2,4CF3 3 CH2OC2Hs 1.101 C2Fs Br 2,6(C1)2,4CF3 3 CH3 1.102 C2Fs Br 2,6(Cl)2,4CF3 3 CH2OC2Hs 1.103 CF3 Br 3,4-(CH=CH)2 2 CH3 1.104 CF3 Br 3,4-(CH=CH)2 2 CH2OC2Hs 110-112 1.105 C2Fs Br 3,4-(CH=CH)2 2 CH2OC2Hs 131.5-133.5 1.106 C2Fs Br 3,4-(CH=CH)2 2 CH3 1.107 CF3 Br 2,3-(CH=CH)2 2 CH3 1.108 CF3 Br 2,3-(CH=CH)2 2 CH2OC2Hs 1.109 C2Fs Br 2,3-(CH=CH)2 2 CH2OC2H5 1.110 C2Fs Br 2,3-(CH=CH)2 2 ~H3 1.111 CF3 Br 2,3-(CH=CH)2,4-Cl 3 CH3 1.112 CF3 Br 2,3-(CH=CH)2,4-Cl 3 CH2OC2Hs 1.113 C2Fs Br 2,3-(CH=CH)2,4-Cl 3 CH3 1.114 C2F5 Br 2,3-(CH=CH)2,4-Cl 3 CH2Oc2Hs 1.115 CF3 Br 3,4-OCF20 2 CH3 1.116 CF3 Br 3,4-OCF20 2 CH2OC2Hs 1.117 C2Fs Br 3,4-OCF20 2 CH2OC2Hs 1.118 C2Fs Br 3,4-OCF20 2 CH3 1.119 CF3 Br 4-CH3SO2 1 CH3 1.120 CF3 Br 4-CH3S02 1 CH2OC2Hs 1.121 C2Fs Br 4-CH3S02 1 CH2OC2Hs ~'~1~`! ~` .:3~ 7 Comp Rl R2 R3 n R4 Physical No. dat~

1.122 C2Fs Br 4-CH3S02 1 CH3 1.123 CF3 Br 4-CH3S 1 CH3 1.124 CF3 Br 4-CH3S 1 CH2OC2Hs 1.125 C2Fs Br 4-CH3S 1 CH2OC2Hs 1.126 C2Fs Br 4-CH3S 1 CH3 1.127 CF3 Br 4-CH3 1 CH3 1.128 CF3 Br 4-CH3 I CH2OC2Hs 1.129 C2F5 Br 4-CH3 1 CH2OC2Hs 1.130 C2F5 Br 4-CH3 1 CH3 1.131 CF3 Br 4-OCH3 1 CH3 1.132 CF3 Br 4-OCH3 1 CH2OC2Hs 1.133 C2Fs Br 4-OC2Hs 1 CH20C2Hs 1.134 C2Fs Br 4-OC2Hs 1 CH3 1.135 CF3 Br 3-CI 1 C~3 1.136 CF3 Br 3-C1 1 CH2OC2Hs 1.137 C2Fs Br 3-Cl 1 CH2OC2Hs 1.138 C2Fs Br 3-Cl 1 CH3 1.139 CF3 Br 3-CF3 1 CH3 1.140 CF3 Br 3-CF3 1 CH2OC2Hs 1.141 C2Fs Br 3-CF3 1 CH2OC2Hs 1.142 C2Fs Br 3-CF3 1 ~H3 1.143 CF3 Br 4-CN 1 CH3 1.144 CF3 Br 4-CN 1 CH2OC2Hs 1.145 C2Fs Br 4-CN ] CH2OC2Hs 1.146 C2Fs Br 4-CN 1 CH3 1.147 CF3 Br 3~4(cl)2 2 H 207.5-209 1.148 CF3 Cl 4-Cl 1 H 211.5-213 1.149 C2Fs Br 3,4(Cl)2 2 H 195.5-197 1.150 C2Fs Cl 4-Cl 1 H 195.5-197 1.151 CF3 Br 3,4-(CH=CH~2 2 H 247-248 1.152 C2Fs Br 3,4-(CH=CH)2 2 H 197-198.5 1.153 CF3 Br 4-OCF3 1 H 212.5-215 ~2~ .' t ~0~3 Comp Rl R2 R3 n R4 Physical No. clata 1.154 C2Fs Br 4-OCF3 1 H 209.5-211 1.1~5 CF3 Cl 4-OCF3 1 H 214-214.5"
1.156 C2Fs Cl 4-OCF3 1 H 206-208 1.157 CF3 Cl 4-OCF3 1 CH2OC2Hs nD= 1.4761 1.158 C2F5 Cl 4-OCF3 1 CH2OC2Hs nD- 1.4636 l.lS9 CF3 Cl 4-F 1 H
1.160 CF3 Cl 4-F 1 CH2OC2Hs 1.161 CF3 Cl 4-CF3 1 H
1.162 C2Fs C1 4-F 1 H
1.163 C2Fs Cl 4-F 1 CH2OC2Hs 1.164 CF3 Cl 2,4(Cl)2 2 H
1.165 C2Fs Cl 2~4(cl)2 2 H
1.166 CF3 Cl 3,4(C1)2 2 H
1.167 C2Fs Cl 3,4(Cl)2 2 H
1.168 CF3 Cl 4-Br 1 H
1.169 C2Fs Cl 4-Br 1 H
1.170 CF3 Cl 4-Br 1 CH2OC2Hs 1.171 C2Fs Cl 4-Br 1 CH2OC2Hs 1.172 CF3 Br 4-E~r 1 H
1.173 C2Fs Br 4-Br 1 H
1.174 CF3 Br 4-ocF2cHF2 1 H
1.175 C2Fs Br 4-ocF2cHF2 1 H
1.176 CF3 Cl 4-ocF2cHF2 1 H
1.177 CF3 Cl 4-OCF2CHF2 1 CE~2OC2Hs 1.178 C2Fs Cl 4-OCF2CHF2 1 CH2OC2Hs 1.179 CF3 Br 3,4-OCF20 2 H
1.180 C2Fs Br 3,4-OCF20 2 H
1.181 CF3 Cl 3,4-OCF20 2 H
1.182 CF3 Cl 3,4-OCF20 2 CH2OC2Hs 1.183 C2Fs Cl 3,4-OCF~O 2 H
1.184 C2Fs Cl 3,4-OCF20 2 CH2OC2Hs 2~ 7 ~"9~7 Comp Rl R2 R3 n ~4 Physical No. data 1.185 CF3 Br 2,3-OCF2O 2 H
1.186 CF3 Br 2,3-OCF20 2 CH2OC2Hs 1.187 C2F5 Br 2,3-OCF20 2 H
1.188 C2Fs Br 2,3-OCF20 2 CH2OC2Hs 1.189 CF3 Cl 2,3-OCF20 2 H
1.190 CF3 Cl 2,3-OCF2O 2 CH2OC2Hs 1.191 C2Fs Cl 2,3-QCF20 2 H
1.192 C2Fs Cl 2,3-OCF20 2 CH2OC2Hs 1.193 C2Fs Br 4-OCH3 1 CH3 1.194 C2Fs Br 4-8CH3 1 CH2OC2Hs Table 2 CN

R1---CF2~ ~` (R3)n Comp No. Rl E~3 n Physical da~a 2.1 CF3 4-C1 1 223.5-224 2.2 C2Fs 4-C1 1 189.5-192 2.3 CF3 4-F 1 223-226 2.4 C2Fs 4-F 1 190.5-191 2.5 CF3 4-CF3 1 230-231.5 2.6 C2Fs 4-CF3 1 187.5-188.5 2.7 C6FI3-n 4-Cl 1 193-193.5 2.8 CF3 274(CI)2 2 164-166 2.9 C2Fs 2,4(Cl)2 2 153-156 2.10 CF3 3~4(Cl)2 2 196.5-198 2.11 C2Fs 3~4(C1)2 2 198-198.5 2.12 CF3 2,4,6(Cl~3 3 2.13 C2Fs 2,4,6(CI)3 3 2.14 CF3 4-Br i 7 Cornp No. Rl R3 n Physical data 2.15 C2Fs 4-Br 2.16 CF3 4-OCF3 1 224.5-226 2.17 C2Fs 4-OCF<3 1 195.5-197 2.18 CF3 4-OCF2CHF2 2.19 C2Fs 4-OCF2CHF2 2.20 CF3 4-OCF2CHFCF3 2.21 C2Fs 4-OCF2CHFCF3 2.22 CF3 2,3,4,5,6(F)s S
2.23 C2Fs 2,3,4,5,6(F)s S
2.24 CF3 4-OCH2CF3 2.25 C2Fs 4-ocH2cF3 2.26 CF3 2,6(C1)2,4CF3 3 2.27 C2Fs 2,6(CI)2,4CF3 3 2.28 CF3 3,4-(CH=CH)2 2 141.5-143 2.29 C2Fs 3,4-(CH=CH)2 2 148-149 2.30 CF3 2,3-(CH=CH)2 2 2.31 C2F5 2,3-(CH=CH)2 2 2.32 CF3 2,3-(CH=CH~2,4CI 3 2.33 C2Fs 2,3-(CH=CH)2,4CI 3 2.34 CF3 3,4-OCF20 2 2.35 C2Fs 3,4-OCF20 2 2.36 CF3 4-CH3sO2 2.37 C2Fs 4-CH3SO2 2.38 CF3 4-CH3S
2.39 C2Fs 4-CH3S
2.40 CF3 4-CH3 2.41 C2Fs 4-CH3 2.42 CF3 4-OCH3 2.43 C2Fs 4-OCH3 2.44 CF3 3-Cl 2.45 C2Fs 3-C1 2.46 CF3 3-CF3 2.47 C2F5 3-CF3 Comp No. Rl R3 n Physical data _ _ . _ . _ .

2.48 CF3 4-CN
2.49 C2F5 4-CN
2.~0 C2Fs 4-OC2Hs 2.51 CF3 2,3-OCF20 2 2.52 C2Fs 2,3-OCF2O 2 Formulation examples (% = per cent by weight) Example F1: Emulsion concentrates a) b) c) ActiveingredientNo. 1.23 25 % 40 % 50%
Calcium dodecylbenzenesulfonate 5 % 8 % 6 %
Castor oil polyethylene glycol ether (36 mol of EO) 5 %
Tributylphenol polyethylene glycol ether (30 mol of EO) - 12 % 4 %
Cyclohexanone - 15 % 20 %
xylene mixture 65 % 25 % 20%

Emulsions of any desired concentration can be prepared from such concentrates bydilution with water.

Example F2: Solutions a) b) c) d) ActiveingredientNo. 1.23 80 % 10 % 5 % 95 %
Ethylene glycol monomethyl ether 20 % - - -Polyethylene glycol MW 400 - 70 %
N-methyl-2-pyrrolidone - 20 %
Epoxidisedcoconutoil - - 1 % 5 %
Petroleum spirit (boiling range 160-190C) - - 94 %

The solutions are suitable for use in the form of microdrops.

2~?~rr1 ExampleF3: Granules a) b) c)d) Active ingredient No. 1.22 5 % 10 % 8 %21 %
Kaolin 94 % - 79 %54 %
Highly-disperse silica 1% - 13 %7 %
Attapulgite - 90 % - 18 %

The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.

ExampleF4: Dusts a) b) Active ingredientNo. 1.22 2 % 5 %
Highly-disperse silica 1 % 5 %
Talc 97 % -Kaolin - 90 %

Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Example F5: Wettable Powders a) b) c) ActiveingredientNo. 1.2 25 % 50 % 75 %
Sodium ligninsulfonate 5 % 5 %
Sodium laurylsulfate 3 % - 5 %
Sodium diisobutylnaphthalene-sulfonate - 6 % 10 %
Octylphenol polyethylene glycol ether (7-8 mol of EO) - 2 %
Highly-disperse silica 5 % 10 % 10 %
Kaolin 62 % 27 %

The active ingredient is mixed with the additives, and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsion concentrate Active ingredient No. 1.3 ~0 %

~'7~ 7 Octylpilenol polyethylene glycol ether (4-5 mol of EO) 3 %
Calcium dodecylbenzenesulfonate 3 %
Castor oil polyglycol ether (36 mol of EO) 4 %
Cyclohexanone 30 %
Xylene mixture 50 %

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.

E mple F7: Dusts a) b) Active ingredient No. 1.2 5 % 8 %
Talc 95 %
Kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carlier and glinding the mixture on a suitable mill.

Example F8: Extruder ~ranules Active ingredient No. 1.4 10 %
Sodium ligninsulfonate 2 %
Carboxymethylcellulose 1 %
Kaolin 87 %

The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded, granulated and subsequently dried in a stream of air.

Example F9: Coated granules Active ingredient No. 1.2 3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %

In a mixer, the kaolin which has been moistened with polyethylene glycol is coated uniformly with the finely ground active ingredient. Dust-free coated granules are obtained in this manner.

- 40 - 2~ Jg~7 xample F I O: Suspension concelltrate Active ingredientNo. 1.3 40 %
Ethylene glycol 10 %
Nonylphenol polyethylene glycol ether (15 mol of EO~ 6 %
Sodium ligninsulfonate 10 %
(~arboxymethylcellulose 1 %
37% aqueous formaldehyde solution 0.2 %
Silicone oil in tlle form of a 75 %
aqueous emulsion 0.8 %
Water 32 %

The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Biolo~ical examples (% = per cent by weight, unless otherwise indicated) A. Insecticidal action Example B l: Action a~ainst Nilaparvata lugens Rice plants are treated with an aqueous emulsion spray mixture comprising 400 ppm of active ingredien~. When the spray coating has dried on, the rice plants are populated with cicada larvae of the 2nd and 3rd stage. 21 days later, the test is evaluated. The percentage reduction in the population (% action) is determined by comparing the number of surviving cicadas on the treated and on the untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B2: Action a~ainst Heliothis virescens (ovi-/larvicide) Eggs of Heliothis virescens which have been deposited on cotton wool are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After 8 days, the percentage hatching rate of the eggs and the survival rates of the caterpillars are evaluated by comparing them with untreated control batches (% reduction of the population).

In this test, a good action is shown by the compounds of Table 1. An action of more than ~0 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B3: Action a~ainst Heliothis virescens Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. When the spray coating has dried on, the plants are populated with 10 caterpillars of the first stage of Heliothis virescens and placed in a plastic container. The tcst is evaluated 6 days later. The percentage reduction in the population and in the damage caused by feeding (% action) is determined by the comparisons of the number of dead caterpillars and damage caused by feeding between the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B4: Action against ~podoptera littoralis Young soybean piants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. When the spray coating has dried on, the plants are populated with 10 caterpillars of the third stage of ~podoptera littoralis and placed in a plastic container. The test is evaluated 3 days later. The percentage reduction in the population and the percentage reduction in the damage caused by feeding (% action) is determined by the comparisons of the number of dead caterpillars and damage caused by feeding between the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B5: Action a~ainst Aphis craccivora Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture comprising 400 ppm of active ingredient and then incubated at 20C. The test is evaluated after 3 and 6 days. The percentage reduction in the population (% action) is deterrnined by comparing the number of dead aphids on the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B6: Action a~ainst Crocidolmia binotalis Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. When the spray coating has dried on, the cabbage plants are 2~ t r~7 populated with lO caterpillars of the third stage of Crocidolmia binotalis and placed in a plastic container. The test is evalllated 3 days later. The percentage reduction in the population and the percentage reduction in the damage caused by feeding (% action) are determined by the comparisons of the number of dead caterpillars and damage caused by feeding between the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B7: Action a~ainst Nilaparvata lu~ens (systemic) Pots with rice plants are placed in an aqueous emulsion solution comprising 10 ppm of the active ingredient. The plants are subsequently populated with larvae of the 2nd and 3rd stage. The test is evaluated 6 days later. The percentage reduction in the population (%
action) is determined by comparing the number of cicadas on the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of over 80 %
is shown, in particular, by compound No. 1.4.

Example B8: Action a(Jainst Diabrotica balteata Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. When the spray coating has dried on, the seedlings are populated with 10 larvae of the second stage of Diabrotica balteata and placed in a plastic container. The test is evaluated 6 days later. The percentage reduction in the population (% action) is determined by comparing the number of dead larvae between the treated and untreated plants.
In th;s test, a good action is shown by the compounds of Table 1. An action of over 80 %
is shown, in particular, by the compounds Nos. 1.2, 1.3, 1.4 and 1.14.

Example B9: Action a~ainst Anthonomus ~randis Young cotton plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray coating has dried on, the cotton plants are populated with 10 adult Anthonomus grandis and placed in a plastic container. The test is evaluated 3 days later. The percentage reduction in the population and the percentage reduction in the damage caused by feeding (% action) are determined by the comparisons of the number of dead beetles and damage caused by feeding between the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 43 2~

80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B10: Actio~ainst Plutella xylostella Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. When the spray coating has dried on, the plants are populated with 10 caterpillars of the 3rd stage of Plutella xylostella and placed in a plastic container. The test is evaluated 3 days later. The percentage reduction in the population and the percentage reduction in the damage caused by feeding (% action) are determined by the comparisons of the number of dead caterpillars and damage caused by feeding between the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1.

Example B11: Action a~ainst Aonidiella aurantii Potato tubers are populated with crawlers of Aonidiella aurantii. After about 2 weeks, the potatoes are dipped into an aqueous emulsion spray mixture, or suspension spray mixture, comprising 400 ppm of active ingredient. After the tubers have dried, they are incubated in a plastic container. To evaluate the test after 10 to 12 weeks, the survival rate of the crawlers of the first subsequent generation of the treated population is compared with that of untreated control batches. In this test, a good action is shown by compounds of Table 1.

Example B12: Action a~ainst Bemisia tabaci Dwarf bean plants are placed in gauze cages and populated with adult Bemisia tabaci.
After oviposition, all adults are removed. 10 days later, the plants together with the nymphs thereon are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After a further 14 days, the percentage hatching rate of the eggs is evaluated by comparing them with untreated control batches.
In this test, a good action is shown by the compounds of Table 1.

Example B13: Action against Blattella germanica A solution (0.1 %) of the active ingredient in acetone is placed into a Petri dish in such an amount that this corresponds to an application rate of 2 g/m2. When the solvent has evaporated, 20 nymphs of Blattella germanica (last nymphal stage) are placed in the dish and exposed to the action of the test substance over 2 hours. The nymphs are then anaesthetised using CO2, transferred to a fresh Petri dish and kept in the dark at 25 and 50 to 70 % atmospheric humidity. After 48 hours, the insecticidal action is deterrnined by calculating the destruction rate.

- 44 - 2 ~ 7 In this test, a good action is shown by the compounds of l`able 1. An action of over 80 %
is shown, in particular, by compo~lnd No. 1.3.

Example B 14: Action a~ainst Lucilla cuprin Batches of 30 to 50 freshly deposited eggs of Lucilia cuprina are placed in test tubes in which 4 ml of nutrient medium have previously been mixecl with 1 ml of test solution comprising 16 ppm of active ingredient. After inoculation of the culture medium, the test tubes are sealed with a cotton wool plug and incubated in the incubator for 4 days at 30.
Up to this point in time, larvae approximately 1 cm in length (stage 3) develop in thc untreated medium. If the test substance is active, then the larvae are either dead or their development is clearly slowed down at this point in time. The test is evaluated after 96 hours.
In this test, a good action is shown by the compounds of Table 1.

Example B 15: Action a~ainst Musca domestica A sugar lump is treated with such an amount of test substance solution that the concentration of test substance in the sugar is 250 ppm after drying overnight. The lump which has been treated in this manner is placed on an aluminium dish together with a wet cotton wool ball and 10 adults of an OP-resistant strain of Musca domestica. The dish is covered with a glass beaker and incubated at 25. The mortality rate is determined after 24 hours.
In this test, a good action is shown by the compounds of Table 1. An action of over ~0 %
is shown, in particular, by the compounds Nos. 1.3 and 1.4.

Example B16: Action a~ainst Ctenocephalides felis 20 to 25 flea eggs are placed into a horizontally positioned 50 ml cell culture flask containing 15 g of flea larvae nutrient medium comprising 100 ppm of active ingredient.
The flasks are incubated in an incubator at 26-27 and 60-70 % atmospheric humidity.
After 21 days, the flasks are checked for the presence of adult fleas, pupae which have not hatched and larvae.
In this test, a good action is shown by the compounds of Table 1.

B. Acaricidal action Example B 17: Action a~ainst Dermanvssus gallinae Into a glass container which is open at the top there are introduced 2 to 3 ml of a solution ?'t~ r`~r3~7 comprising 10 ppm of active ingrcdient alld approx. 200 individuals of Derrnanyssus gallinae in various developmellt stages. The container is sealed with a cotton wool plug, shaken for 10 minutes (until the mites are wetted completely~ and then briefly turned upsicle down so that the remainder of the test solution can be absorbed by the cotton wool.
After 3 days, the mortality of the mites is determined (in per cent) by counting the dead individuals.
In this test, a good action is shown by the compounds of Table 1.

Example B18: Action aYain.st Tetranvchus urticae Young bean plants are populated with a mixed population of Tetranychus urticae and, 1 day later, sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. The plants are subsequently incubated for 6 days at 25C and then evaluated.
The percentage reduction in the population (% action) is determined by the comparisons of the number of dead eggs, larvae and adults on the treated and untreated plants.
In this test, a good action is shown by the compounds of Table 1. An action of more than 80 % is shown, in particular, by the compounds Nos. 1.2, 1.3 and 1.4.

Example B 19: Action a~ainst Boophilus ~
Adult female ticks which have sucked themselves full are glued onto a PVC plate and covered with a cotton wool ball. For the treatment, 10 ml of an aqueous test solution comprising 125 ppm of active ingredient is poured over the test animals. The cotton wool ball is then removed, and the ticks are incubated for 4 weeks for oviposition. The action against Boophilus microplus is demonstrated either in the fonn of mortality or sterility in the case of females or in the forrn of an ovicidal action in the case of the eggs.
In this test, a good action is shown by the compounds of Table 1.

C. Fun~icidal action Example B20: Action against Puccinia Framinis on wheat a~ Residual-protective action Test method: 6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0.02 % active substance) prepared with a wettable powder comprising one of the active ingredients according to the invention, and, 24 hours later, infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atmospheric humidity at 20), the plants are placed in a greenhouse at 22. The assessment of the action of the active substallce is based on the ~C~r~ .3~7 rust pustule development 12 days after infection.
_est result: Compounds of Table I show a good residual-protective action againstPuccinia graminis on wheat, for example the compounds Nos. 1.2 and 1.3 reduce fungal infestation to 20 to 5 %. In contrast, infected control plants which have not been treated with the active substance show a fungal infestation of 100 %.

b) Svstemic action Test method: 5 days after sowing, an aqueous spray mixture (0.006 % active substance relative to the soil volume) prepared with a wettable powder comprising one of the active ingredients according to the invention is poured next to wheat plants. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are infected with a uredospore suspension of the fungus. After an incubation time of 48 hours (conditions: 95 to 100 per cent relative atrnospheric humidity at 20), the plants are placed in a greenhouse at 22. The assessment of the action of the active substance is based on the rust pustule development 12 days after infection.
Test result: Compounds of Table 1 show a good systemic action against Puccinia graminis on wheat.

Example B21: Action against Phvtophthora infestans on tomatoes a) Residual-protective action Test method: Tomato plants are grown for three weeks and then sprayed to drip point with an aqueous spray mixture (0.02 % of active substance) prepared with a wettable powder comprising one of the active ingredients according to the invention, and, 24 hours later, infected with a sporangia suspension of the fungus. The assessment of the action of the active substance is based on the fungal infestation S days after infection, during which a relative atmospheric humidity of 90 to 100 per cent and a temperature of 20 aremaintained.
Test result: Compounds of Table 1 show a good residual-protective action againstPhytophthora infestans on tomatoes, for example the compounds Nos. 1.2, 1.3 and 1.4 reduce the fungal infestation to 20 to 0 %. In contrast, infected control plants which have not been treated with the active substance show a fungal infestation of 10() %.

b) Svstemic action Test method: Tomato plants are grown for three weeks, and an aqueous spray mixture (0.006 % of active substance relative to the soil volume) which has been prepared with a wettable powder com.prising one of the active ingredients according to the invention is 2~7r9~ 7 then poured nexl to the tomato plants. Care is taken that the spray mixture does not come into contact with aerial parts of the plants. After 48 hours, the plants are infected with a sporangia suspension of the fungus. The assessment of the action of the active substance is based on the fungal infestation 5 days after infection, during which a relative aemospheric humidity of 90 to 100 per cent and a temperature of 20 are maintained.
Test result: Compounds of Table 1 show a good systemic action against Phytophthora infestans on tomatoes.

Example B22: Residual-protective action against Cercospora arachidicola on ~roundnuts Test method: Groundnut plants 10 to 15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02 % of active substance) prepared with a wettable powder comprising one of the active ingredients according to the invention, and, 48 hours later, infected with a conidia suspension of the fungus. The plan~s are incubated for 72 hours at 21 C and high atmospheric humidity and subsequently placed in a greenhouse until the typical lesions on the leaves occur. The action of the active substance is assessed 12 days after infection based on number and size of the lesions on the leaves.
Test result: Compounds of Table 1 show a good residual-protective action againstCercospora arachidicola on groundnuts.

Example B23: Action against Plasmopara viticola on vines a) Residual-protective action Test method: Vine seedlings in the 4- to 5-leaf stage are sprayed to drip point with an aqueous spray mixture (0.02 % of active substance) prepared with a wettable powder comprising one of the active ingredients according to the invention and, 24 hours later, infected with a sporangia suspension of the fungus. The assessment of the action of the active substance is based on the fungal infestation 6 days after infection, during which a re;ative atmospheric humidity of 95 to 100 per cent and a temperature of 20 aremaintained.
Test result: Compounds of Table 1 show a good preventive residual-protective action against Plasmopara viticola on vines, for example the compounds Nos. 1.2, 1.3 and 1.4 reduce the fungal infestation to 20 to 5 %. In contrast, infected control plants which have not been treated with the active substance show a fungal infestation of 100 %.

b) Residual-protective action Test method: Vine seedlings in the 4- to S-leaf stage are infected with a sporangia suspension of the fungus, incubated for 24 hours in a humid chamber (conditions: 95 to 100 per cent relative atmospl-eric humidity at 20) and then sprayed to drip point with an aqueous spray mixture (0.02 % of active substance) prepared with a wettable powder cornprising one of the active ingredients according to the invention. When the spray coating has dried on, the plants are returned to the humid chamber. The assessment of the action of the active substance is based on the fungal infestation 6 days after infection.
Test result: Compounds of Table 1 show a good curative residual-protective action against Plasmopara viticola on vines, for example the compounds Nos. 1.2, 1.3 and 1.4 reduce the fungal infestation to ~0 to 5 %. In contrast, infected control plants which have not been treated with the active substance show a fungal infestation of 100 %.

Example B24: Action against Erysiphe raminis on barley a) Residual-protective action Test method: Barley plants approximately 8 cm in height are sprayed to drip point with an aquoous spray mixture (0.()2 % of active substance) prepared with a wettable powder comprising one of the active ingredients according to the invention and, 3 to 4 hours later, dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22.
The assessment of the action of the active substance is based on the fungal infestation 10 days after infection.
Test result: Compounds of Table 1 show a good residual-protective action againstErysiphe graminis on barley, for example the compounds Nos. 1.2, 1.3 and 1.4 reduce the fungal infestation to 20 to 5 %. In contrast, infected control plants which have not been treated with the active substance show a fungal infestation of 100 %.

b) Svstemic action Test method: An aqueous spray mixture (0.002 % of active substance relative to the soil volume) prepared with a wettable powder comprising one of the active ingredientsaccording to the invention is poured next to barley plants approximately 8 cm in height.
Care is taken that the spray mixture does not come into contact with aerial parts of the plants. 48 hours later, the plants are dusted with conidia of the fungus. The infected plants are placed in a greenhouse at 22. The assessment of the action of the active compound is based on the fungal infestation 10 days after infection.
Test result: Compounds of Table 1 show a good systemic action against EIysiphe graminis on barley.

Claims (30)

1. A compound of the formula (I), in which n is the number 1, 2, 3, 4 or 5, where, if n is greater than 1, the radicals R3 are identical or different; R1 is halo-C1-C9alkyl; R2 is halogen; R3 is hydrogen, cyano, nitro, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, halo-C1-C4alkyl, halo-C1-C4alkoxy, halo-C1-C4alkylthio, halo-C1-C4alkanesulfinyl or halo-C1-C4alkanesulfonyl, and/or two substituents R3 which are bonded to adjacent C atoms of the phenyl ring together are a bridge selected from the group of bridges comprising -O-CH2-O-, -O-CH2-CH2-O-, -O-CH2-CH2-, -O-CH2-CH2-CH2- and -CH=CH-CH=CH-, unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy or halo-C1-C4alkyl; and R4 is hydrogen, C1-C4alkyl, C3-C4alkenyl, halo-C3-C4alkenyl, C3-C4alkynyl, cyano, C1-C4alkylthio, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, halo-C1-C4alkanesulfonyl, di-C1-C4alkylaminosulfonyl, di-C1-C4alkylaminocarbonyl or a C1-C4alkyl group which is substituted by one or more substituents selected from the group comprising halogen, C1-C4alkoxy, hydroxyl, C1-C4alkylthio, C2-C6alkoxyalkoxy, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, C1-C4alkcylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyloxy, cyano, C2-C4alkenylcarbonyloxy, phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl, where the phenyl rings contained in these phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl substituents can in each case be substituted by halogen, C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkyl, halo-C1-C4alkoxy, C1-C4alkylthio, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, halo-C1-C4alkylthio, halo-C1-C4-alkanesulfinyl, halo-C1-C4-alkanesulfonyl, cyano or nitro, in free form or in salt form.
2. A compound of the formula I, according to claim 1, in free form.
3. A compound of the formula I, according to claim 2, in which R1 is perfluoro-C1 -C6alkyl.
4. A compound of the formula 1, according to claim 2, in which R2 is chlorine or bromine.
5. A compound of the formula 1, according to claim 2, in which n is the number 1, 2, 3, 4 or 5, where, if n is greater than 1, the radicals R3 are identical or different, and R3 is halogen, halo-C1-C4alkyl, halo-C1-C4alkoxy, cyano, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4alkanesulfonyl, and/or two substituents R3 bonded to adjacent C
atoms of the phenyl ring together are -O-C(halogen)2-O-, in particular -O-CF2-O-, or -CH=CH-CH=CH-.
6. A compound of the formula 1, according to claim 2, in which R4 is hydrogen, C1-C4alkyl, C3-C4alkenyl, halo-C3-C4alkenyl, C3-C4alkynyl, cyano, C1-C4alkylthio, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, halo-C1-C4alkanesulfonyl, di-C1-C4alkylaminosulfonyl, di-C1-C4alkylaminocarbonyl or a C1-C4alkyl group substituted by one or more substituents selected from the group comprising halogen, C1-C4alkoxy, hydroxyl, C1-C4alkylthio, C2-C6alkoxyalkoxy, C1-C4alkanesulfinyl, C1-C4alkanesulfonyl, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyloxy, cyano, C2-C4alkenylcarbonyloxy, phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl, where the phenyl rings in these phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl substituents can in each case be substituted by halogen, C1-C4alkyl, C1-C4alkoxy, halo-C1-C4alkyl, halo-C1-C4alkoxy, C1-C4alkylthio, C1-C4alkanesulfonyl, halo-C1-C4alkylthio, halo-C1-C4alkanesulfinyl, halo-C1-C4alkanesulfonyl, cyano or nitro.
7. A compound of the formula I, according to claim 2, in which R4 is hydrogen, C1-C4alkyl, C3-C4alkynyl, C1-C4alkanesulfonyl, di-C1-C4alkylaminosulfonyl, or a C1-C4alkyl group substituted by C1-C4alkoxy, C1-C4alkylthio, C2-C6alkoxyalkoxy, C1-C4alkanesulfonyl, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, cyano, monohalophenyl or phenoxy.
8. A compound of the formula I, according to claim 2, in which R1 is perfluoro-C1-C6alkyl, R2 is chlorine or bromine, R3 is halogen, halo-C1-C4alkyl,Halo-C1-C4alkoxy, cyano, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio or C1-C4alkanesulfonyl, R4 is hydrogen, C1-C4alkyl or C2-C6alkoxyalkyl, and n is the number one, two or three, where n can be the number one, two, three, four or five if all radicals R3 simultaneously are halogen.
9. A compound of the formula I, according to claim 8, in which R1 is trifluoromethyl or pentafluoroethyl, R2 is bromine, R3 is fluorine, chlorine, trifluoromethyl, fluoro-C1-C3alkoxy, methylthio, cyano or C1-C3alkoxy, R4 is hydrogen, methyl, methoxymethyl or ethoxymelhyl, and n is the number one, two or three.
10. A compound of the formula I, according to claim 8, in which R1 is trifluoromethyl, R2 is chlorine or bromine, R3 is fluorine, chlorine, trifluoromethyl, fluoro-C1-C3alkoxy, methylthio, cyano or C1-C3alkoxy, R4 is hydrogen, methyl, methoxymethyl or ethoxymethyl and n is the number one, two or three.
11. A compound of the formula I, according to claim 9, in which n is the number 1, R1 is trifluoromethyl or pentafluoroethyl, R2 is bromine, R3 is trifluoromethyl, trifluoromethoxy or chlorine, and R4 is hydrogen or ethoxymethyl.
12. A compound of the formula I, according to claim 2, selected from the group comprising the compounds (a) 4-Bromo-2-(4-chlorophenyl)-3-cyano-5-heptafluoropropyl-pyrrole, (b) 4-Bromo-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-pyrrole, (c) 4-Bromo-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-heptafluoropropyl-pyrrole, (d) 4-Chloro-2-(4-chlorophenyl)-3-cyano-5-heptafluoropropyl-pyrrole, (e) 4-Chloro-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-pyrrole, (f) 4-Chloro-2-(4-chlorophenyl)-3-cyano-1-ethoxymethyl-5-heptafluoropropyl-pyrrole, (g) 4-Bromo-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (h) 4-Chloro-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (i) 4-Bromo-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (j) 4-Chloro-3-cyano-1-ethoxymethyl-5-pentafluoroethyl-2-(4-trifluoromethylphenyl)-pyrrole, (k) 4-Bromo-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole, (1) 4-Chloro-3-cyano-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole, (m) 4-Bromo-3-cyano- l-ethoxymethyl-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole and (n) 4-Chloro-3-cyano- l-ethoxymethyl-5-pentafluoroethyl-2-(4-trifluoromethoxyphenyl)-pyrrole.
13. A process for the preparation of a compound of the formula I, according to claim 1, in free form or in salt form, which comprises a) introducing the halogen substituent R2 into the 4-position of the pyrrole ring of a compound of the formula (II), in which R1, R3, R4 and n are as defined in formula I, or into a salt thereof, by reaction with a halogenating agent, preferably in the presence of a base, or b) to prepare a compound of the formula I in which R4 is other than hydrogen, or a salt thereof, reacting a compound of the formula I which can be obtained, for example, according to variant a), and in which R4 is hydrogen, or a salt of such a compound, with a compound of the formula X-R4 (III) which is known or which can be prepared analogously to corresponding known compounds and in which R4 is as defined in formula I, with the exception of hydrogen, and X is a leaving group, or, if appropriate, with a salt thereof, preferably in the presence of a base, or c) to prepare a compound of the formula I, in which R4 is methyl or a group R2CH2-, or a salt thereof, reacting, optionally in the presence of a base, optionally in the presence of a radical initiator, a compound of the formula (VII), in which R1, R3 and n are as defined in formula I, or a salt thereof, with a halogenating agent and, in each case, if desired, converting a compound of the formula I, in free form or in salt form, which can be obtained according to the process or by a different route, into a different compound of the formula I, resolving an isomer mixture which can be obtained according to the process, and isolating the isomer desired and/or converting a free compound of the formula I which can be obtained according to the process into a salt, or a salt of a compound of the formula I which can be obtained according to the process into the free compound of the formula I or into a different salt.
14. A pesticide which comprises, as active ingredient, at least one compound of the formula I, according to claim 1, in free form or in agrochemically usable salt form, and, if desired, at least one auxiliary.
15. A composition according to claim 14 for controlling insects, representatives from the order of the Acarina and/or phytopathogenic fungi.
16. A process for the preparation of a composition comprising at least one auxiliary, according to claim 14, which comprises intimately mixing and/or grinding the active ingredient with the auxiliary(ies).
17. The use of a compound of the formula I, according to claim 1, in free form or in agrochemically usable salt form, for the preparation of a composition according to claim 14.
18. The use of a composition according to claim 14 for controlling pests.
19. The use according to claim 18 for controlling insects, representatives from the order of the Acarina and/or phytopathogenic fungi.
20. The use according to claim 18 for the protection of plant propagation material.
21. A method of controlling pests which comprises applying a composition according to claim 14 to the pests or to their environment.
22. A method according to claim 21 for controlling insects, representatives of the order of the Acarina and/or phytopathogenic fungi.
23. A method according to claim 21 for the protection of plant propagation material which comprises treating the propagation material or the site where the propagation material is used.
24. Plant propagation material treated according to the process described in claim 23.
25. A compound of the formula (II), in which R1, R3, R4 and n are as defined in formula I, in free form or in salt form.
26. A process for the preparation of a compound of the formula II, according to claim 25, in free form or in salt form, which comprises d) to prepare a compound of the formula II in which R4 is hydrogen, or a salt thereof, reacting a compound of the formula (IV) in which R1, K3 and n are as defined in formula I, or a salt of such a compound, with 2-chloroacrylonitrile, preferably in a high-boiling polar solvent such as nitromethane, and at the reflux temperature of the reaction mixture, or e) to prepare a compound of the formula II in which R4 is other than hydrogen, or a salt of such a compound, reacting a compound of the formula II which can be obtained, for example, in accordance with variant d), and in which R4 is hydrogen, or a salt of such a compound, preferably in the presence of a base, for example of the type given in the case of variant a), with a compound of the formula X-R4 (III) which is known or which can be prepared analogously to corresponding known compounds and in which R4 is as defined in formula I with the exception of hydrogen, and X is a leaving group, for example of the type given in variant b), or, if appropriate, with a salt thereof, and, if desired, in each case converting a compound of the formula II which can be obtained according to the process or by a different route, in free form or in salt form, into a different compound of the formula II, resolving an isomer mixture which can be obtained according to the process, and isolating the isomer desired, and/or converting a free compound of the formula II which can be obtained according to the process into a salt, or convcrting a salt of a compound of the fonnula Il which can be obtained according to the process into the free compound of the formula II or into a different salt.
27. The use of a compollnd of the formula II, according to claim 25, in free form or in salt form, for the preparation of a compound according to claim 1.
28. A compound of the formula (VII), in which R1, R3 and n are as defined in formula I, in free form or in salt form.
29. A process for the preparation of a compound of the formula VII, according to claim 28, in free form or in salt form, which comprises f) reacting a compound of the formula (VIII), in which R1, R3 and n are as defined in formula I, or a salt of such a compound, with acrylonitrile, preferably in a high-boiling polar solvent, such as acetonitrile, in the presence of an acid anhydride, such as acetic anhydride, and at the reflux temperature of the reaction mixture, and, if desired, converting a compound of the formula VII which can be obtained according to the process or by a different route, in free form or in salt form, into a different compound of the formula VII, resolving an isomer mixture which can be obtained according to the process, and isolating the isomer desired, and/or converting a free compound of the formula VII which can be obtained according to the process into a salt, or converting a salt of a compound of the formula VII which can be obtained according to the process into the free compound of the formula VII or into a different salt.
30. The use of a compound of the formula VII, according to claim 28, in free form or in salt form, for the preparation of a compound according to claim 1.
CA002076937A 1991-08-28 1992-08-26 Cyanophenylpyrroles Abandoned CA2076937A1 (en)

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US5817691A (en) * 1997-04-09 1998-10-06 American Cyanamid Company Arylthio, -sulfinyl and -sulfonyl pyrrole insecticidal agents
US6242613B1 (en) 1996-08-02 2001-06-05 American Cyanamid Co. Stable arylpyrrole particles, process for their preparation and suspension concentrate compositions comprising them
MD1934B2 (en) * 1996-08-02 2002-06-30 Эмерикэн Сайенэмид Компэни Stable arylpyrol particles

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AU1274295A (en) * 1993-12-30 1995-07-17 Ciba-Geigy Ag Heteroarylpyrroles
US5631379A (en) * 1994-11-22 1997-05-20 American Cyanamid Company Oxazole amines as intermediates in the manufacture of insecticidal pyrroles
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US5908858A (en) 1996-04-05 1999-06-01 Sankyo Company, Limited 1,2-diphenylpyrrole derivatives, their preparation and their therapeutic uses
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US6077863A (en) * 1997-08-08 2000-06-20 American Cyanamid Company 2-aryl-4-halo-5-(trifluoromethyl)pyrrole-3-carbonitriles for the protection of wood, wood products and wooden structures from insect attack
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CN103539716A (en) * 2013-10-31 2014-01-29 青岛农业大学 One group of 2-para chlorphenyl-4-substituted methyl-5- trifluoromethyl-3-cyanpyrrole compounds
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US5496845A (en) * 1994-05-25 1996-03-05 American Cyanamid Co. Suspension concentrate compositions of arylpyrrole insecticidal and acaricidal agents
CN1083238C (en) * 1994-05-25 2002-04-24 美国氰胺公司 Suspension concentrate compositions of arylpyrrole insecticidal and acaricidal agents
US6242613B1 (en) 1996-08-02 2001-06-05 American Cyanamid Co. Stable arylpyrrole particles, process for their preparation and suspension concentrate compositions comprising them
MD1934B2 (en) * 1996-08-02 2002-06-30 Эмерикэн Сайенэмид Компэни Stable arylpyrol particles
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