WO1994005633A1

WO1994005633A1 - 3-cyano-4-halogeno-2-(subst.phenyl)-pyrroles as pesticides and fungicides

Info

Publication number: WO1994005633A1
Application number: PCT/EP1993/002231
Authority: WO
Inventors: Dieter DÜRR; Josef Ehrenfreund; Roger Graham Hall
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1992-09-01
Filing date: 1993-08-20
Publication date: 1994-03-17
Anticipated expiration: 1995-03-01
Also published as: AU4950693A; IL106811A0; CN1087336A; MX9305347A

Abstract

Compounds of formula (I), wherein n is 1, 2, 3 or 4; when n is greater than 1, the radicals R3 are identical or different; R1 is halogen or 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 bonded to adjacent carbon atoms of the phenyl ring together from an unsubstituted or substituted bridge selected from the group of bridges consisting of -O-CH2-O-, -O-CH2-CH2-, -O-CH2-CH2-O-, -O-CH2-CH2-CH2- and -CH=CH-CH=CH-; 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 substituted C1-C4alkyl group; R5 is halo-C1-C6alkyl, halo-C1-C6alkoxy or -OS(=O)2R6, and R6 is C1-C6alkyl or halo-C1-C6alkyl, in free form or in salt form, can be used as agrochemical active ingredients and can be prepared in a manner known per se.

Description

3-CYANO-4-HALOGENO-2-(SUBST. PHENYL)-PYRROLES AS PESTICIDES AND FUNGICIDES The invention relates to compounds of formula

wherein

n is 1, 2, 3 or 4; when n is greater than 1, the radicals R₃ are identical or different;

R₁ is halogen or 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 bonded to adjacent carbon atoms of the phenyl ring together form a bridge that is unsubstituted or substituted by halogen, C₁-C₄alkyl,

C₁-C₄alkoxy or by halo- C₁-C₄alkyl and is selected from the group of bridges consisting of -O-CH₂-O-, -O-CH₂-CH_r, -O-CH₂-CH₂-O-, -O-CH₂-CH₂-CH₂- and -CH=CH-CH=CH-;

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 consisting of halogen, C₁-C₄alkoxy, hydroxy, C₁-C₄alkylthio, C₂-C₆alkoxyalkoxy, Cj^alkanesulfinyl, C₁-C₄alkanesulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl,

C₁-C₄alkylcarbonyloxy, cyano, C₂-C₄alkenylcarbonyloxy, phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl, it being possible for each of the phenyl nuclei contained in those phenyl, phenoxy, phenylthio, benzyloxy, benzoyloxy, benzoyl, phenylsulfinyl and phenylsulfonyl

substituents to be substituted by halogen, C₁-C₄alkyl, C₁-C₄alkoxy, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkanesuifinyl, C₁-C₄alkanesulfonyl, haloC₁-C₄alkylthio, halo- C₁-C₄alkanesulfinyl, halo-C₁-C₄alkanesulfonyl, cyano or by nitro;

R₅ is halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy or -OS(=O)₂R₆ and

R₆ is C₁-C₆alkyl or halo-C₁-C₆alkyl,

with the proviso that

R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is

-CF₃ or halogen,

and with the further proviso that

R₅ is not halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy when R₁ is -CF₂-halo-C₁-C₈alkyl, in free form or in salt form, to a process for the preparation of those compounds and to the use of those compounds, to pesticides comprising an active ingredient selected from those compounds, in free form or in agrochemically acceptable salt form, to a process for the preparation of those compositions and to the use of those compositions, to plant propagation material treated with those compositions, to a method of controlling pests, to intermediates and the salts thereof for the preparation of the compounds of formula I, and to processes for the preparation of those intermediates.

The use of pyrroles having acaricidal and insecticidal activity as pesticides has often been proposed. The biological properties of those compounds are not, however, totally satisfactory in the field of pest control, and there is therefore a need to provide further compounds having pesticidal properties, especially for controlling insects and representatives of the order Acarina. That problem is solved according to the invention by the provision of the present compounds of formula I which, surprisingly, are also suitable for controlling phytopathogenic fungi.

Compounds of formula I having at least one basic centre are capable of forming, for example, acid addition salts. Those 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, such as unsubstituted or substituted, for example halo-substituted, C₁-C₄alkanecarboxylic acids, for example acetic acid, or saturated or unsaturated dicarboxylic acids, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, or hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted,

C₁-C₄alkanesulfonic or arylsulfonic acids, for example methanesulfonic or p-toluene sulfonic acid. Furthermore, compounds of formula I having at least one acidic group are capable of forming salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium 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 ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine. Where appropriate, corresponding internal salts may also be formed. Preference is given within the scope of the invention to agrochemically advantageous salts, but salts that have disadvantages for agrochemical purposes are also included; they are used, for example, in the isolation or purification of free compounds of formula I or the agrochemically acceptable salts thereof. The expression "compound of formula I" thus always also includes the tautomers of those compounds, their salts and the salts of the tautomers.

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

Unless otherwise defined, carbon-containing groups and compounds each contain from 1 up to and including 9, preferably from 1 up to and including 6, especially from 1 up to and including 4, more especially 1 or 2, carbon atoms.

Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy, alkoxyalkoxy, haloalkoxy, alkylthio, haloalkylthio, alkanesulfinyl, haloalkanesulfinyl, alkanesulfonyl, haloalkanesulfonyl, dialkylaminosulfonyl, dialkylaminocarbonyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy - in each case taking due account of the number of carbon atoms in the corresponding group or compound - is either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or nonyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isooctyl.

Alkenyl, haloalkenyl, alkenylcarbonyloxy and alkynyl are straight-chained or branched and each contain two or preferably one unsaturated carbon-carbon bond(s). The double or triple bonds of those substituents are separated from the remainder of the compound of formula I preferably by at least one saturated carbon atom. The following may be mentioned by way of example: allyl, methallyl, but-2-en-1-yl, but-3-en-2-yl, allylcarbonyloxy, propargyl, but-2-yn-1-yl and but-3-yn-1-yl.

Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl, haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl, may be partially halogenated or perhalogenated, it being possible in the case of poly-halogenation for the halogen substituents to be identical or different. Examples of haloalkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl - are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF₂, CF₂Cl, CFCl₂ or CF₃; ethyl mono- to penta-substituted by fluorine, chlorine and/or by bromine, such as CH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CF₂Br, CF₂CHBrF or CCIFCHCIF; propyl or isopropyl mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃,

CH₂CF₂CF₃, CF₂CF₂CF₃ or CH(CF₃)₂; and butyl or one of its isomers mono- to nona-substituted by fluorine, chlorine and/or by bromine, such as CF(CF₃)CHFCF₃,

CF₂(CF₂)₂CF₃ or CH₂(CF₂)₂CF₃. Haloalkyl R₁ is preferably exclusively fluorinated, especially perfluorinated. Examples of haloalkenyl are 2-chloroprop-2-en-1-yl,

2,3-dichloroprop-2-en-1-yl and 2,3-dibromoprop-2-en-1-yl.

The two alkyl groups in dialkylaminosulfonyl and dialkylammocarbonyl substituents may in each case be identical or different The following may be mentioned by way of example: -SO₂-N(CH₃)₂, -SO₂-N(C₂H₅)₂, -SO₂-N(CH₃)C₂H₅, -SO₂-N(C₃H₇)₂,

-SO₂-N(C₄H₉)₂, -CO-N(CH₃)₂, -CO-N(C₂H₅)₂, -CO-N(CH₃)C₂H₅, -CO-N(C₃H₇)₂, -CO-N(CH₃)C₃H₇-i, -CO-N(CH₃)C₃H₇-n, -CO-N(CH₃)C₄H₉-n, -CO-N(C₄H₉)₂ and -CO-N(C₂H₅)C₃H₇-n.

In C₂-C₆alkoxyalkoxy an alkoxy group bonded to the remainder of the compound of formula I is substituted by a further alkoxy group, and the two carbon chains, each independently of the other, may be straight or branched and together include from 2 to 6 carbon atoms. Examples are methoxymethoxy, methoxyethoxy, 2-ethoxyethoxy, ethoxymethoxy, isopropoxymethoxy, 3-methoxypropoxy, n-butoxymethoxy and 2-(n-propoxy)ethoxy.

In the above-mentioned bridges formed by two substituents R₃ together, when those bridges are substituted, either one of the hydrogen atoms in the unsubstituted basic structure has been replaced by an alkyl, alkoxy or haloalkyl substituent or one or more than one, especially all, of the hydrogen atoms in the unsubstituted basic structure has(have) been replaced by identical or different halogen atoms. Examples of such substituted bridges are -O-CF₂-O-, e.g. 2,3-O-CF₂-O- or 3,4-O-CF₂-O-,

-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-.

In the substituted alkyl groups R₄ the alkyl basic structure carries preferably two or, especially, one of the above-mentioned substituents; in the case of a halo-substituted alkyl group R₄, however, one or more than one, for example all, of the hydrogen atoms in the unsubstituted alkyl basic structure has(have) been replaced by identical or different halogen atoms. If the substituted alkyl group R₄ contains a substituted phenyl nucleus, that phenyl nucleus carries preferably two or, especially, one of the above-mentioned substituents; in the case of a halo-substituted phenyl nucleus, however, 1, 2, 3, 4 or all of the phenyl-hydrogen atoms may have been replaced by identical or different halogen atoms. The alkyl basic structure is preferably a methyl group.

Preferred embodiments within the scope of the invention - taking account of the two provisos mentioned above - are

(1) a compound of formula I wherein

R₁ is halogen or perfluoro-C₁-C₉alkyl, especially chlorine or perfluoro-C₁-C₄alkyl, more especially chlorine, CF₃ or C₂F₅, and most especially CF₃;

(2) a compound of formula I wherein

R₂ is chlorine or bromine, especially bromine;

(3) a compound of formula I wherein

n is 1 or 2; when n is 2, the radicals R₃ are identical or different, and

R₃ is hydrogen, 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 carbon atoms of the phenyl ring are together -O-C(halo)₂-O- or -CH=CH-CH=CH-, especially -O-CF₂-O-;

n is especially 1 and

R₃ is especially hydrogen, halogen, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy, R₃ is more especially hydrogen, trifluoromethyl, trifluoromethoxy or chlorine, preferably chlorine or hydrogen, and

R₃ is most especially hydrogen;

(4) a compound of formula I wherein

R₄ is hydrogen, C₁-C₄alkyl, C₃-C₄alkynyl, C₁-C₄alkanesulfonyl, di-C₁-C₄alkylaminosulfonyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy, C₁-C₄alkylthio, C₂-C₆alkoxyalkoxy, C₁-C₄alkanesulfonyl, C₁-C₄alkylcarbonyl, C_j-C₄alkoxycarbonyl, cyano, mono-halophenyl or by phenoxy, and is especially hydrogen, C₁-C₄alkyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy or by C₂-C₆alkoxyalkoxy, and is preferably hydrogen, C₁-C₄alkyl, halo-C₁-C₄alkyl or C₂-C₆alkoxyalkyl, more especially hydrogen, methyl, halomethyl, methoxymethyl or ethoxymethyl, most especially hydrogen, chloromethyl, bromomethyl, methoxymethyl or ethoxymethyl, preferably hydrogen, methyl, halomethyl, methoxymethyl or ethoxymethyl, and especially hydrogen or ethoxymethyl;

(5) a compound of formula I wherein

R₅ is -OS(=O)₂R₆ and

R₆ is C₁-C₄alkyl or halo-C₁-C₄alkyl, especially a compound of formula I wherein R₆ is C₁-C₂alkyl or halo-C₁-C₂alkyl, more especially trifluoromethyl or pentafluoroethyl, most especially CF₃,

the group -O-SO₂-R₆ being especially in the 4-position;

(6) a compound of formula I wherein

R₅ is halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy, especially fluoro-C₁-C₂alkyl, fluoroC₁-C₃alkoxy or fluoro-bromo-C₁-C₃alkoxy;

(7) a compound of formula I wherein

R₁ is halogen or perfluoro-C₁-C₉alkyl,

R₂ is chlorine or bromine,

n is 1 or 2,

R₃ is hydrogen, 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 carbon atoms of the phenyl ring are together -O-C(halo)₂-O-;

R₄ is hydrogen, C₁-C₄alkyl, C₃-C₄alkynyl, C₁-C₄alkanesulfonyl, di-C₁-C₄alkylaminosulfonyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy, C₁-C₄alkyl- thio, C₂-C₆alkoxyalkoxy, C₁-C₄alkanesulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, cyano, mono-halophenyl or by phenoxy, and

R₅ is -OS(=O)₂-halo-C₁-C₂alkyl, halo-C₁-C₃alkyl or halo-C₁-C₃alkoxy;

(8) a compound of formula I wherein

R₁ is chlorine or perfluoro-C₁-C₄alkyl,

R₂ is chlorine or bromine,

n is 1,

R₃ is hydrogen, halogen, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy,

R₄ is hydrogen, C₁-C₄alkyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy or by C₂-C₆alkoxyalkoxy and

R₅ is -OS(=O)₂-fluoro-C₁-C₂alkyl, fluoro-C₁-C₂alkyl or halo-C₁-C₃alkoxy;

(9) a compound of formula I wherein

R₁ is chlorine, -CF₃ or -C₂F₅,

R₂ is chlorine or bromine,

n is 1,

R₃ is hydrogen, trifluoromethyl, trifluoromethoxy or chlorine,

R₄ is hydrogen, methyl, halomethyl, methoxymethyl or ethoxymethyl,

R₅ is -OS(=O)₂-R₆, -C₂F₅ or fluoro-bromo-C₁-C₃alkoxy and

R₆ is trifluoromethyl;

(10) a compound of formula I wherein

R₁ is -CF₃ or -C₂F₅,

R₂ is chlorine or bromine,

n is 1,

R₃ is hydrogen, trifluoromethyl, trifluoromethoxy or chlorine,

R₄ is hydrogen, methyl, halomethyl, methoxymethyl or ethoxymethyl, and

R₅ is -OS(=O)₂-CF₃, -C₂F₅, -OCF₂CF₂Br or -OCF₂CHFCF₃;

(11) a compound of formula I wherein

R₁ is -CF₃,

R₂ is chlorine or bromine,

n is 1,

R₃ is hydrogen,

R₄ is hydrogen, chloromethyl, bromomethyl, methoxymethyl or ethoxymethyl and R₅ is -OS(=O)₂-CF₃, -C₂F₅, -OCF₂CF₂Br or -OCF₂CHFCF₃, and the substituent R₅ is in the 4-position; and

(12) a compound of formula I wherein

R₃ is chlorine bonded in the 3-position.

Special preference is given within the scope of the invention to the compounds of formula I mentioned in Examples A1 to A5.

Preference is given within the scope of the invention specifically to

(a) 4-bromo-3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

(b) 4-chloro-3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

(c) 4-bromo-3-cyano-2-(4-methanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

(d) 4-chloro-3-cyano-1-ethoxymethyl-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

(e) 4-bromo-3-cyano-1-ethoxymethyl-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

(f) 4-bromo-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-5-trifluoromethylpyrrole,

(g) 4-chloro-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-5-trifluoromethyl-pyrrole,

(h) 4-bromo-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-1-ethoxymethyl¬

5-trifluoromethyl-pyrrole,

(i) 4-chloro-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-1-ethoxymethyl¬

5-trifluoromethyl-pyrrole,

(k) 4-bromo-3-cyano-1-ethoxymethyl-2-(4-pentafluoroethyl-phenyl)-5-trifluoromethylpyrrole,

(l) 4-bromo-3-cyano-2-(4-pentafluoroethyl-phenyl)-5-trifluoromethyl-pyrrole,

(m) 3-cyano-4,5-dichloro-1-ethoxymethyl-2-(4-pentafluoroethyl-phenyl)-pyrrole and

(n) 3-cyano-4,5-dichloro-1-methyl-2-(4-pentafluoroethyl-phenyl)-pyrrole.

The invention relates further to a process for the preparation of a compound of formula I or one of the salts thereof, which - taking account of the proviso that, in the compounds of formulae I, II and V, R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is -CF₃ or halogen,

and with the further proviso that

R₅ is not halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy when R_j is -CF₂-halo-C₁-C₈alkyl comprises, for example, a) introducing the halogen substituent R₂ into the 4-position of the pyrrole ring of a compound of formula

wherein R₁, R₃, R₄, R₅ and n are as defined for formula I, or into a salt thereof, by reaction with a halogenating agent, preferably in the presence of a base, or b) for the preparation of a compound of formula I wherein R₄ is other than hydrogen, or a salt thereof, reacting, preferably in the presence of a base, a compound of formula I wherein R₄ is hydrogen, or a salt thereof, obtainable, for example, in accordance with Variant a), with a compound of formula

X-R₄ (III), which is known or can be prepared analogously to corresponding known compounds and wherein R₄ has one of the definitions given for formula I with the exception of hydrogen and X is a leaving group, preferably a halogen atom, or where appropriate with a salt thereof, or c) for the preparation of a compound of formula I wherein R₅ is -OS(O=)₂R₆, reacting, preferably in the presence of a base, a compound of formula

wherein R₁, R₂, R₃, R₄, R₆ and n are as defined for formula I, or a salt thereof, with a compound of formula

Y-SO₂R₆ (IV), which is known or can be prepared analogously to corresponding known compounds and wherein R₆ has one of the definitions given for formula I and Y is a leaving group, preferably a halogen atom, or d) for the preparation of a compound of formula I wherein R₄ is methyl or a group R₂CH₂-, or a salt thereof, reacting a compound of formula

wherein R₁, R₃, R₅ and n are as defined for formula I, or a salt thereof, with a halogenating agent, where appropriate in the presence of a base, and where appropriate in the presence of a radical initiator, or e) for the preparation of a compound of formula I wherein R₅ is halo-C₁-C₆alkoxy, reacting, preferably in the presence of a base, a compound of formula

wherein R₁, R₂, R₃ and n are as defined for formula l and R₄ is other than hydrogen, or a salt thereof, with a halo-C₁-C₆alkane or a halo-C₁-C₆alkene, which are known, and in each case, if desired, converting a compound of formula I obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula I, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula I obtainable in accordance with the process into a salt or converting a salt of a compound of formula I obtainable in accordance with the process into the free compound of formula I or into a different salt.

The reactions described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, generally, in the presence of a suitable solvent or diluent or a mixture thereof, the reaction being carried out as required with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80°C to the boiling temperature of the reaction medium, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions can be found in the Examples.

Variant a):

Suitable halogenating agents are, for example, elemental halogens, such as elemental chlorine, bromine or iodine, hypochlorites, such as sodium hypochlorite, sulfuryl halides, such as sulfuryl chloride or sulfuryl bromide, N-haloamides, such as N-chloro-p-toluenesulfonamide or the sodium salt thereof, or N-halosuccinimides, such as N-chlorosuccinimide or N-bromosuccinimide.

Examples of bases suitable for facilitating the halogenation reaction are alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkoxides, acetates, carbonates, dialkylamides or alkylsilylamides; alkylamines, alkylenediamines, optionally N-alkylated, unsaturated or saturated, cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples are sodium hydroxide, hydride, amide, methoxide, acetate or carbonate, potassium-tert-butoxide, hydroxide, carbonate or 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, benzyl-trimethyl-ammonium hydroxide and l,5-diazabicyclo[5.4.0]-undec-5-ene (DBU).

The reactants can be reacted with one another as such, Le. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachlorome thane, 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile;

sulfoxides, such as dimethylsulfoxide; and acids, for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C₁-C₄alkanecarboxylic acids, for example formic acid, acetic acid or propionic acid; or water. If the reaction is carried out in the presence of a base, it is also possible for bases, such as such triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, used in excess, to serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +10°C to approximately +130°C, and in many cases in the range from room temperature to the reflux temperature of the reaction mixture. In most cases the reaction mixture is heated automatically by liberated heat of reaction. As a final step, in order to complete the halogenation reaction, the reaction mixture is advantageously heated for a short time under reflux.

In one specific embodiment, the reaction is carried out at room temperature in a mixture of glacial acetic acid and sodium acetate with bromine, and in another specific embodiment in dimethylformamide with N-chlorosuccinimide.

Variant b):

Examples of suitable leaving groups X in compounds of formula in are hydroxy,

C₁-C₈alkoxy, halo-C₁-C₈alkoxy, C₁-C₈alkanoyloxy, mercapto, C₁-C₈alkylthio, haloC₁-C₈alkylthio, C₁-C₈alkanesulfonyloxy, halo-C₁-C₈alkansulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen. Suitable bases for facilitating the HX removal are, for example, of the type indicated under Variant a).

The reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous. Examples of such solvents or diluents 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, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, it is also possible for bases, such as such triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, used in excess, to serve as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +10°C to approximately

+130°C, and in many cases in the range from room temperature to the reflux temperature of the reaction mixture.

In one specific embodiment, the reaction is carried out in tetrahydrofuran in the presence of potassium tert-butoxide with chloromethyl ethyl ether.

Variant c):

Examples of suitable leaving groups Y in compounds (IV) are hydroxy, C₁-C₈alkoxy, halo-C₁-C₈alkoxy, C₁-C₈alkanoyloxy, halogen and, when a corresponding anhydride is used, -OS(=O)₂R₆.

Suitable bases for facilitating the HY removal are, for example, of the type indicated under Variant a). The reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are those mentioned under Variant a).

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

In one specific embodiment the reaction is carried out in glacial acetic acid in the presence of triethylamine.

Variant d):

Suitable halogenating agents are, for example, of the type indicated under Variant a).

Suitable bases for facilitating the reaction with the halogenating agent are, for example, of the type indicated under 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 one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are of the type mentioned under Variant b).

Depending on the number of equivalents of halogenating agent used, it is possible to prepare different products of formula I in accordance with Variant d). At least two equivalents of halogenating agent must be used. The first equivalent oxidises the dihydro pyrrole derivative V, resulting in the corresponding pyrrole intermediate ("compound A"). The second equivalent of halogenating agent introduces the halogen substituent R₂ into the 4-position of the pyrrole ring of compound A, resulting in the corresponding compound of formula I wherein R₄ is methyl ("compound B"). In order to obtain the corresponding compound of formula I wherein R₄ is a group R₂CH₂-, i.e. in order to introduce a halogen substituent R₂ into the methyl group R₄ of compound B, a third equivalent of halogenating agent is required. In this paragraph, the term "equivalent" is to be understood to include not only the precise amount that corresponds exactly to one equivalent, but also a certain range, for example about 10 %, above and below that precise amount. It is possible to isolate compound A and/or compound B, but the reaction is preferably carried out as a one-pot reaction without the isolation of compounds A and B. It is also possible to add the whole amount of halogenating agent at the beginning of the reaction, but the halogenating agent is preferably added in portions, for example in several portions each of one equivalent. The mono-halogenation of the methyl group R₄ of compound B is preferably carried out in the presence of a radical initiator.

Variant e): Suitable alkylating agents are haloalkanes mid haloalkenes, for example bromotrifluoromethane, dibromo-difluoromethane, 1,2-dibromo-1,1,2,2-tetrafluoroethane, tetrafluoroethylene, hexafluoropropylene, bromopentafluoroethane or chlorotrifluoroethylene.

Suitable bases, solvents and temperature conditions are as indicated for Process

Variant b).

The compounds of formula II used as starting materials in Process Variant a), in free form or in salt form, taking account of the two provisos indicated at the beginning, are novel and the invention relates also to those compounds.

The compounds of formula Ila used in Process Variants c) and e), in free form or in salt form, are also novel and the invention relates also to those compounds. They can be prepared in accordance with methods known per se, for example by means of a reaction analogous to Synthesis Variant e) above, or by converting a compound of formula IIa obtainable in accordance with the process or by another method in a manner known per se into a different compound of formula II by replacing one or more substituents of the starting compound II by (a) different substituent(s) of the invention in customary manner. Special preference is given within the scope of the invention to the compounds of formula II mentioned in Examples 14 and 17.

The compounds of formula V used in Process Variant d), and the salts thereof, with the proviso that R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is -CF₃ or halogen, are also novel and the present invention relates also to those compounds.

The invention relates also to a process for the preparation of compounds of formulaII, in free form or in salt form, which - taking account of the proviso that, in compounds of formulae II and VI of the following Synthesis Variants f) and g),

R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when Rj is -CF₃ or halogen,

and with the further proviso that

R₅ is not halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy when R₁ is -CF₂-halo-C₁-C₈alkyl - comprises, for example, f) for the preparation of a compound of formula II wherein R₄ is hydrogen, or of a salt thereof, reacting a compound of formula

wherein R₁, R₃, R₅ and n are as defined for formula I, or a salt thereof, with 2-chloroacrylonitrile, preferably in a high-boiling polar solvent, such as nitromethane, preferably in the presence of a base, such as triethylamine and at the reflux temperature of the reaction mixture, or g) for the preparation of a compound of formula II wherein R₄ is other than hydrogen, or a salt thereof, reacting a compound of formula II wherein R₄ is hydrogen, or a salt thereof, obtainable, for example in accordance with Variant f), preferably in the presence of a base, for example of the type indicated under Variant a), with a compound of formula

X-R₄ (III),

which is known or can be prepared analogously to corresponding known compounds, and wherein R₄ has one of the definitions given for formula I with the exception of hydrogen and X is a leaving group, for example of the type indicated under Variant b), or where appropriate with a salt thereof, or h) for the preparation of a compound of formula

wherein R₁, R₂ and R₄ are as defined for formula I, n is 1 and R₃ is halogen, reacting a compound of formula

wherein R₁, R₂ and R₄ are as defined for formula I, or a salt thereof, with a halogenating agent, and in each case, if desired, converting a compound of formula II obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula II, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula II obtainable in accordance with the process into a salt or converting a salt of a compound of formula II obtainable in accordance with the process into the free compound of formula II or into a different salt

The compounds VI, in free form or in salt form, are known or can be prepared analogously to known compounds.

The invention relates also to a process for the preparation of compounds of formula V, in free form or in salt form, which comprises, for example, i) reacting a compound of formula

wherein R₁, R₃, R₅ and n are as defined for formula I, with the proviso that R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is -CF₃ or halogen, or a salt thereof, 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 formula V obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula V, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula V obtainable in accordance with the process into a salt or converting a salt of a compound of formula V obtainable in accordance with the process into the free compound of formula V or into a different salt

The compounds of formula V II and their salts are known or can be prepared analogously to known compounds.

A compound of formula I, II or V obtainable in accordance with the process or by another method can be converted in a manner known per se into a different compound of formula I, II or V by replacing one or more substituents of the starting compound of formula I, II or V in customary manner by (a) different substituent(s) of the invention.

For example:

- hydroxy groups (as substituents of alkyl groups R₄) can be alkylated to form alkoxy groups (as substituents of alkyl groups R₄);

- hydroxy groups (as substituents at the phenyl ring) can be reacted with a compound of formula

Y-SO₂R₆ (IV); - halogen R₃ can be introduced into unsubstituted positions of the phenyl ring;

- mercapto groups R₃ and/or R₄ can be oxidised to sulfinyl or sulfonyl groups R₃ and/or R₄ or sulfinyl groups R₃ and/or R₄ can be oxidised to sulfonyl groups R₃ and/or R₄;

- methyl groups R₄ can be mono-halogenated to mono-halomethyl groups R₄;

- mono-halomethyl groups R₄ can be converted into monoalkoxymethyl groups R₄ by replacing the halogen substituent by an alkoxy group, or

- substituents R₄ can be removed by hydrolysis.

Depending on the choice of suitable reaction conditions and starting materials, it is possible to replace only one substituent by another substituent according to the invention in a reaction step, or to replace several substituents by other substituents according to the invention in the same reaction step.

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

Salts of compounds of formula I, II and V can be converted into the free compounds of formula I, II and V in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent

Salts of compounds of formula I, II and V can be converted into different salts of compounds of formula I, II and V in a manner known per se: acid addition salts, for example, can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and therefore is eliminated from the reaction mixture.

Depending upon the procedure and the reaction conditions, compounds of formula I, II and V having salt-forming properties can be obtained in free form or in the form of salts.

The compounds of formula of formula I, II and V and their salts may be in the form of one of the possible isomers or as a mixture thereof, for example according to the number of asymmetric carbon atoms occurring in the molecule and the absolute and relative configuration thereof and/or according to the configuration of non-aromatic double bonds occurring in the molecule, they may be in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.

Mixtures of diastereoisomers and mixtures of racemates of compounds I, in free form or in salt form, that are obtainable in accordance with the process depending upon the starting materials and procedures chosen, or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physicochemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.

Correspondingly obtainable mixtures of enantiomers, such as racemates, can be separated into the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example highpressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed, or by conversion into diastereoisomeric salts, for example by reaction of a basic end product racemate with an optically active acid, such as a carboxylic acid, for example camphoric, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separation of the resulting mixture of diastereoisomers, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers from which the desired enantiomer can be freed by the action of suitable, for example basic, agents.

Apart from by the separation of corresponding mixtures of isomers, it is possible according to the invention to obtain pure diastereoisomers or enantiomers also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials having correspondingly suitable stereochemistry. It is advantageous to isolate or synthesise the biologically more active isomer, for example enantiomer or diastereoisomer, or mixture of isomers, for example mixture of enantiomers or mixture of diastereoisomers, insofar as the individual components have different biological activity.

The compounds of formula I, II and V and their salts can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that may be used for the crystallisation of compounds of formula I in solid form.

The invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.

In the process of the present invention there are preferably used those starting materials and intermediates, in each case in free form or in salt form, which result in the compounds of formula I described at the beginning as being especially valuable, or their salts.

The invention relates especially to the preparation processes described in Examples 13 to 17 and A1 to A5.

In the area of pest control, the compounds of formula I according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina, and phytopathogenic fungi. The insecticidal and/or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.

The mentioned animal pests include, for example: of the order Lepidoptera, for example,

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., Malacosoma 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.;

of the order Coleoptera, 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.;

of the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,

Periplaneta spp. and Schistocerca spp.;

of the order Isoptera, for example,

Reticulitermes spp.;

of the order Psocoptera, for example,

Liposcelis spp.;

of the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;

of the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

of the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii;

of the order Heteroptera, for example,

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp.,

Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,

Scotinophara spp. and Triatoma spp.;

of the order 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., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;

of the order Hymenoptera, for example,

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,

Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;

of the order Diptera, for example,

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,

Fannia spp., Gastrophilus spp., Glossina 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.;

of the order Siphonaptera, for example,

Ceratophyllus spp. and Xenopsylla cheopis;

of the order Thysanura, for example,

Lepisma saccharina; and

of the order 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, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora,

Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp..

The mentioned phytopathogenic fungi include, for example:

of the class of the Fungi imperfecti, for example,

Botrytis spp., Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp.,

Cercospora spp. and Alternaria spp.;

of the class of the Basidiomycetes, for example,

Rhizoctonia spp., Hemileia spp. and Puccinia spp.;

of the class of the Ascomycetes, for example,

Venturia spp., Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and of the class of the Oomycetes, for example,

Phytophthora spp., Pythium spp. and Plasmopara spp..

With the compounds according to the invention it is possible to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruit blossom, leaves, stems, tubers or roots, while some of the parts of the plants which grow later are also protected against those pests.

Target crops are especially cereals, such as wheat barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit such as pomes, stone fruit and soft fruit such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucumber plants, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of the invention are suitable especially for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soybean, rape and vegetable crops. Further areas of use of the compounds according to the invention are the protection of stored goods and stocks and materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type.

The invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.

The active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).

Suitable solvents are, for example: optionally partially hydrogenated aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rape oil, castor oil, coconut oil or soybean oil or epoxidised rape oil, castor oil, coconut oil or soybean oil, and silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand. In addition, a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.

Depending on the nature of the compound to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties. The surfactants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit

Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as substituent at least one C₈-C₂₂alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.

Both water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants. Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurin salts. More frequently, however, synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C₈-C₂₂alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

The compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of active ingredient and 1 to 99.9 %, preferably 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25 %, preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which have considerably lower active ingredient concentrations. Preferred formulations have especially the following composition

(throughout percentages are by weight):

Emulsifiable concentrates:

active ingredient: 1 to 90 %, preferably 5 to 20 %

surfactant: 1 to 30 %, preferably 10 to 20 %

solvent: 5 to 98 %, preferably 70 to 85 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:

active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surfactant: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 99 %, preferably 15 to 98 %

Granules:

active ingredient: 0.5 to 30 %, preferably 3 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The activity of the compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal, acaricidal and/or fungicidal active ingredients. Examples of suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations. The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example bactericides, nematicides, molluscicides or selective herbicides.

The compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding and/or sieving a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one adjuvant for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvants). The invention relates also to that process for the preparation of the compositions according to the invention and to the use of the compounds of formula I for the preparation of those compositions.

The invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type. Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

A preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.

The compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit tubers or grains, or plant cuttings, from fungal infections and animal pests. The propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown. The compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation. The formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to that method of treating plant propagation material and to the plant propagation material thus treated.

Preparation Examples

Intermediates

Example II: 3-Cyano-2-(4-hydroxy-phenyl)-5-trifluoromethyl-pyrrole

Under a nitrogen atmosphere, 16 g of 2-chloroacrylonitrile are added to 62.5 g of 4-[4-(trifluoroacetoxy]-phenyl)-2-trifluoromethyl-oxazolin-5-one in 200 ml of acetonitrile. With stirring, 18.5 g of triethylamine are added dropwise thereto and the reaction mixture is then heated for one hour at the reflux temperature. 300 ml of water and 300 ml of ethyl acetate are added to the reaction mass, the organic phase is separated off and concentrated by evaporation and the residue is recrystallised from ethyl acetate/hexane 1:1 to yield the title compound having a melting point of 228 - 229°C. (Compound 1.11)

Example 12: 4-Bromo-3-cyano-2-(4-acetoxy-phenyl)-5-trifluoromethyl-pyrrole

15 g of 3-cyano-2-(4-hydroxy-phenyl)-5-trifluoromethyl-pyrrole are stirred for 5 hours at 90°C in 100 ml of glacial acetic acid together with 4.8 g of sodium acetate and 6.6 g of acetic anhydride. The reaction mixture is allowed to cool to room temperature, 10 g of sodium acetate and 50 ml of glacial acetic acid are added and, in the course of one hour, 10 g of bromine are added dropwise thereto. The reaction mixture is stirred for a further 2 hours, 250 ml of water are added and the compound which has precipitated is filtered off and dried in an oven to yield the title compound having a melting point of 206 - 209°C. (Compound 1.9) Example 13: 4-Bromo-3-cyano-1-ethoxymethyl-2-(4-hydroxy-phenyl)-5-trifluoromethylpyrrole

19 g of 4-bromo-3-cyano-2-(4-acetoxy-phenyl)-5-trifluoromethyl-pyrrole are stirred with 100 ml of tetrahydrofuran and 5.8 g of potassium tert-butoxide. After 15 minutes, 5 ml of chloromethyl ethyl ether are added and the reaction mixture is stirred for a further 5 hours. After the addition of a further 5.8 g of potassium tert-butoxide and 10 ml of water, the reaction mixture is concentrated by evaporation on a rotary evaporator, 100 ml of water are added to the residue and the product is extracted with 100 ml of ethyl acetate. The organic phase is concentrated by evaporation and the residue is recrystallised from ethylene chloride to yield the title compound having a melting point of 170 - 172°C.

(Compound 1.15)

Example 14: 3-Cyano-5-trifluoromethyl-2-(4-trifluorosulfonyloxy-phenyl)-pyrrole

10 g of 3-cyano-2-(4-hydroxy-phenyl)-5-trifluoromethyl-pyrrole are introduced into 50 ml of acetonitrile with 4.4 g of triethylamine. At room temperature, 11.3 g of trifluoromethanesulfonic acid anhydride are added dropwise thereto and the reaction mixture is stirred for five hours. 200 ml of water are added, and the product that has precipitated is filtered off, recrystallised from ethyl acetate/hexane 1:1 and dried in an oven to yield the title compound having a melting point of 180 - 185°C. (Compound 1.2). Example 15: 3-Cyano-2-(4-[1,1,2,3,3,3-hexafluoropropoxy]-phenyl)-5-trifluoromethylpyrrole

504 mg of 3-cyano-2-(4-hydroxy-phenyl)-5-trifluoromethyl-pyrrole, 20.2 mg of triethylamine, 60 ml of water and 3 ml of dimethylformamide are mixed together and, with stirring, hexafluoropropene is introduced until none of the starting materials can be detected by thin-layer chromatography (2 to 4 hours). The reaction mixture is

concentrated by evaporation and the residue is purified by crystallisation from hexane/diethyl ether 1:1 to yield the title compound having a melting point of 199 - 200°C.

(Compound 1.18).

Example 16: 4-Bromo-3-cyano-2-(3-chloro-4-hydroxy-phenyl)-1-ethoxymethyl-5-trifluoromethyl-pyrrole

3.4 g of 4-bromo-3-cyano-1-ethoxymethyl-2-(4-hydroxy-phenyl)-5-trifluoromethylpyrrole are mixed with 0.8 g of sodium acetate and 30 ml of glacial acetic acid. With stirring at room temperature, 1.3 g of sulfuryl chloride are added thereto and the reaction mixture is stirred for a further 12 hours. The reaction mixture is poured into water and extracted with ethyl acetate. The solvent is concentrated until the product crystallises out, yielding the title compound having a melting point of 159 - 160°C (compound 2.5).

Example 17: The other compounds listed in Tables 1 to 3 can also be prepared in a manner analogous to that described in Examples II to 16. Melting points are given in °C.

Active ingredients

Example A1: 4-Bromo-3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole

10.2 g of 3-cyano-2-(4-trifluoromemanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole are introduced together with 5.4 g of sodium acetate into 50 ml of glacial acetic acid. With stirring at room temperature, 5.4 g of bromine are added dropwise in the course of 2 hours and the mixture is stirred for a further 16 hours. 200 ml of water are added, the reaction mixture is filtered and recrystallised from 100 ml of methylene chloride and the product is dried in an oven to yield the title compound having a melting point of 197 - 199°C.

(Compound 4.3)

Example A2: 4-Chloro-3-cvano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole

13 g of 3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole are introduced into 20 ml of dimethylformamide and in the course of two hours, with stirring, a solution of 6.3 g of N-chlorosuccinimide in 30 ml of dimethylformamide is added thereto. The reaction mixture is then heated to 100°C and stirred for one hour and then 150 ml of water and 150 ml of ethyl acetate are added. The organic phase is concentrated to a volume of 30 ml and the product is purified over silica gel with ethyl acetate/hexane 1:3 to yield the title compound having a melting point of 186 - 189°C. (Compound 4.5) Example A3: 4-Bromo-3-cyano-1-ethoxymethyl-2-(4-trifluoromethanesulfonyloxyphenyl)-5-trifluoromethyl-pyrrole

6 g of 4-bromo-3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethylpyrrole, together with 1.8 g of potassium tert-butoxide, are introduced into 100 ml of tetrahydrofuran. In the course of one hour, at room temperature, 1.8 ml of chloromethyl ethyl ether are added thereto. The mixture is concentrated by evaporation and the residue is purified over silica gel with ethyl acetate/hexane 1:3 to yield the title compound in the form of a viscous oil, n_D ²³: 1.5030. (Compound 4.2)

Example A4: 4-Bromo-3-cyano-1-ethoxvmethyl-2-(4-methanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole

3 g of 4-bromo-3-cyano-1-ethoxymethyl-2-(4-hydroxy-phenyl)-5-trifluoromethyl-pyrroleare introduced into 20 ml ofglacial acetic acid and 1 ml of triethylamine and, at room temperature, 0.9 g of methanesulfonic acid chloride are added thereto. The undissolved portions are filtered off, the filtrate is concentrated to dryness by evaporation and the residue is recrystallised from diethyl ether to yield the title compound having a melting point of 75 - 76 °C. (Compound 4.4)

Example A5: The other compounds listed in Tables 4 to 6 can also be prepared in a manner analogous to that described in Examples Al to A4. Melting points are given in °C.

Formulation Examples (throughout, percentages are by weight)

Example F1: Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol

ether (36 mol of ethylene oxide) 5% - - tributylphenol polyethylene glycol

ether (30 mol of ethylene oxide) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%

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

Example F2: Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl

ether 20% - - - polyethylene glycol

(mol. wt.400) - 70% - -

N-methyl-2-pyrrolidone - 20 % - - epoxidised coconut oil - - 1 % 5 % petroleum fraction

(boiling range 160- 190°C) - - 94% -

These solutions are suitable for application in the form of microdrops.

Example F3: Granules a) b) c) d) active ingredient 5% 10% 8% 21% kaolin 94% - 79% 54% highly dispersed silicic acid 1% - 13% 7% attapulgite - 90% - 18%

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. Example F4: Dusts a) b)

active ingredient 2% 5%

highly dispersed silicic acid 1% 5%

talcum 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)

active ingredient 25% 50% 75%

sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5%

sodium diisobutylnaphthalenesulfonate - 6% 10%

octylphenol polyethylene

glycol ether (7-8 mol of

ethylene oxide) - 2% - highly dispersed silicic acid 5% 10% 10%

kaolin 62% 27% -

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

Example F6: Emulsifiable concentrate

active ingredient 10 %

octylphenol polyethylene glycol ether

(4-5 mol of ethylene oxide) 3 %

calcium dodecylbenzenesulfonate 3 %

castor oil polyglycol ether

(36 mol of ethylene oxide) 4 %

cyclohexanone 30 %

xylene mixture 50 % Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

Example F7: Dusts a) b)

active ingredient 5 % 8 %

talcum 95 % - kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mature in a suitable mill.

Example F8: Extruder granules

active ingredient 10 %

sodium lignosulfonate 2 %

carboxymethylcellulose 1 %

kaolin 87 %

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

Example F9: Coated granules

active ingredient 3 %

polyethylene glycol (mol. wt 200) 3 %

kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Example F10: Suspension concentrate

active ingredient 40 %

ethylene glycol 10 %

nonylphenol polyethylene glycol ether

(15 mol of ethylene oxide) 6 %

sodium lignosulfonate 10 % carboxymethylcellulose 1 %

37 % aqueous formaldehyde solution 0.2 %

silicone oil in the form of a 75 %

aqueous emulsion 0.8 %

water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples (throughout percentages are by weight unless otherwise indicated)

Example B1: Action against Boophilus microplus

Adult female ticks which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab. For treatment 10 ml of an aqueous solution comprising 125 ppm of the test compound are poured over the test insects. The cotton wool swab is then removed and the ticks are incubated for 4 weeks until oviposition has taken place. The action against Boophilus microplus manifests itself either as mortality or sterility of the females or as ovicidal action in the eggs.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.1, 4.21 to 4.24, 4.26 and 4.33 to 4.35 are more than 80 % effective.

Example B2: Action against Nilaparvata lugens

Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.1, 4.19, 4.20, 4.23, 4.24 and 4.26 are more than 80 % effective.

Example B3: Action against Diabrotica balteata larvae

Maize seedlings are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and placed in a plastics container.

Evaluation is made 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test. In particular, compounds 4.1 to 4.5, 4.17, 4.19 to 4.24, 4.26, 4.28 and 4.34 to 4.36 are more than 80 % effective in this test.

Example B4: Action against Anthonomus grandis adults

Young cotton plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead beetles and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.1 to 4.5, 4.17 to 4.24, 4.26, 4.28 and 4.33 to 4.36 are more than 80 % effective in this test.

Example B5: Action against Heliothis virescens caterpillars

Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Heliothis virescens caterpillars in the first stage and placed in a plastics container.

Evaluation is made 6 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.1, 4.2, 4.3, 4.5, 4.18 to 4.24, 4.26, 4.28, 4.29, 4.33 and 4.34 are more than 80 % effective.

Example B6: Action against Spodoptera littoralis caterpillars

Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and placed in a plastics container.

Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.1, 4.2, 4.3, 4.5, 4.18 to 4.24, 4.34 and 4.35 are more than 80 % effective in this test.

Example B7: Action against Crocidolomia binotalis caterpillars

Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10 Crocidolomia binotalis caterpillars in the third stage and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.17 to 4.20 are more than 80 % effective.

Example B8: Systemic action against Nilaparvata lugens

Pots containing rice plants are placed in an aqueous emulsion comprising 400 ppm of the test compound. The rice plants are then populated with larvae in the 2nd and 3rd stages. Evaluation is made 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of cicadas on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test In particular, compounds 4.1, 4.23, 4.24, 4.26 and 4.34 are more than 80 % effective.

Example B9: Ovicidal action against Tetranychus urticae

Young bean plants are populated with Tetranychus urticae females which are removed after 24 hours. The plants that are populated with eggs are sprayed with an aqueous emulsion comprising 400 ppm of test compound. The plants are then incubated for 6 days at 25°C and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.

Compounds of Tables 4 to 6 exhibit good activity in this test. In particular, compounds 4.21, 4.22, 4.26 and 4.28 are more than 80 % effective.

Example B10: Action against Dermanyssus gallinae

2 to 3 ml of a solution comprising 10 ppm of test compound, and approximately 200 mites at various stages of development, are placed in a glass container that is open at the top. The container is then closed with a cotton wool swab, shaken for 10 minutes until the mites are completely wetted, and then inverted for a short time so that the remaining test solution can be absorbed by the cotton wool. After 3 days, the mortality of the mites is determined as a percentage by counting the number of dead individuals.

Compounds of Tables 4 to 6 exhibit good activity against Dermanyssus gallinae. In particular, compounds 4.1, 4.2, 4.24 and 4.26 are more than 80% effective.

Example B 11: Action against Blattella germanica

A 0.1 % solution of test compound in acetone is introduced into a Petri dish until the amount corresponds to a rate of application of 2 g/m². When the solvent has evaporated, 20 Blattella germanica nymphs (final nymph stage) are introduced into the prepared dish and exposed to the action of the test compound for 2 hours. The nymphs are then narcotised with CO₂, introduced into a fresh Petri dish and kept in the dark at 25°C and 50 to 70 % humidity. After 48 hours the insecticidal action is evaluated by determining the mortality rate.

Compounds of Tables 4 to 6 exhibit good activity against Blattella germanica in this test. In particular, compounds 4.1, 4.2 and 4.24 are more than 80 % effective.

Example B12: Action against Lucilia cuprina blowflies

Small portions of freshly deposited eggs of the blowfly species Lucilia cuprina (30 to 50 eggs) are placed in test tubes in which 4 ml of nutrient medium have previously been mixed with 1 ml of test solution comprising 16 ppm of test compound. After inoculation of the culture medium, the test tubes are closed with a cotton wool plug and incubated in an incubator at 30°C for 4 days. By that time, larvae approximately 1 cm long (stage 3) have developed in the untreated medium. If the compound is active, by that time the larvae are either dead or clearly retarded. Evaluation is made after 96 hours.

The compounds of Tables 4 to 6 exhibit good activity against Lucilia cuprina in this test. In particular, compound 4.28 is more than 80 % effective.

Example B 13: Action against Musca domestica

A sugar cube is so treated with a solution of the test compound that the concentration of test compound in the sugar, after drying overnight, is 250 ppm. The treated cube is placed on an aluminium dish with a wet cotton wool swab and 10 Musca domestica adults of an OP resistant strain, covered with a glass beaker and incubated at 25°C. After 24 hours the mortality rate is determined.

The compounds of Tables 4 to 6 exhibit good activity against Musca domestica in this test In particular, compounds 4.1 to 4.5 and 4.21 to 4.24 are more than 80 % effective.

Example B14: Action against Plutella xylostella caterpillars

Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10 Plutella xylostella caterpillars in the third stage and placed in a plastics container.

Compounds of Tables 4 exhibit good activity against Plutella xylostella in this test In particular, compounds 4.1 to 4.3, 4.5, 4.21 to 4.24 and 4.33 to 4.35 are more than 80 % effective.

Claims

What is claimed is:

1. A compound of formula

or a salt thereof, wherein

R₁ is halogen or halo- C₁-C₉alkyl;

R₂ is halogen;

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 bonded to adjacent carbon atoms of the phenyl ring together form a bridge that is unsubstituted or substituted by halogen, C₁-C₄alkyl,

C₁-C₄alkoxy or by halo-C₁-C₄alkyl and is selected from the group of bridges consisting of -O-CH₂-O-, -O-CH₂-CH₂-, -O-CH₂-CH₂-O-, -O-CH₂-CH₂-CH₂- and -CH=CH-CH=CH-;

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 consisting of halogen, C₁-C₄alkoxy, hydroxy, C₁-C₄alkylthio, C₂-C₆alkoxyalkoxy, C₁-C₄alkanesulfinyl, C₁-C₄alkanesulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl,

substituents to be substituted by halogen, C₁-C₄alkyl, C₁-C₄alkoxy, halo-C₁-C₄alkyl, halo-C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkanesulfinyl, C₁-C₄alkanesulfonyl, haloC₁-C₄alkylthio, halo-C₁-C₄alkanesulfinyl, halo-C₁-C₄alkanesulfonyl, cyano or by nitro; R₅ is halo-C₁-C₆alkyl, halo-C₁-C₆alkoxy or -OS(=O)₂R₆ and

R₆ is C₁-C₆alkyl or halo-C₁-C₆alkyl,

with the proviso that

-CF₃ or halogen,

and with the further proviso that

R₅ is not halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy when R₁ is -CF₂-halo-C₁-C₈alkyl.

2. A compound according to claim 1 of formula I in free form.

3. A compound according to either claim 1 or claim 2 of formula I wherein

R₁ is halogen or perfluoro-C₁-C₄alkyl.

4. A compound according to any one of claims 1 to 3 of formula I wherein

R₂ is chlorine or bromine.

5. A compound according to any one of claims 1 to 4 of formula I wherein

n is 1 or 2; when n is 2, the radicals R₃ are identical or different, and

C₁-C₄alkoxy, C₁-C₄alkylthio or C₁-C₄alkanesulfonyl and/or two substituents R₃ bonded to adjacent carbon atoms of the phenyl ring are together -O-C(halo)₂-O- or -CH=CH-CH=CH-.

6. A compound according to any one of claims 1 to 5 of formula I wherein

R₄ is hydrogen, C₁-C₄alkyl, C₃-C₄alkynyl, Cj^alkanesulfonyl, di-C₁-C₄alkylaminosulfonyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy, C₁-C₄alkylthio, C₂-C₆alkoxyalkoxy, C₁-C₄alkanesulfonyl, C₁-C₄alkylcarbonyl,

C₁-C₄alkoxycarbonyl, cyano, mono-halophenyl or by phenoxy.

7. A compound according to claim 6 of formula I wherein

R₄ is hydrogen, C₁-C₄alkyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy or by C₂-C₆alkoxyalkoxy.

8. A compound according to any one of claims 1 to 7 of formula I wherein

R₅ is -OS(=O)₂R₆ and

R₆ is C₁-C₄alkyl or halo-C₁-C₄alkyl.

9. A compound according to claim 8 of formula I wherein

R₆ is C₁-C₂alkyl or halo-C₁-C₂alkyl.

10. A compound according to any one of claims 1 to 7 of formula I wherein

R₅ is halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy.

11. A compound according to claim 10 of formula I wherein

R₅ is fluoro-C₁-C₂alkyl, fluoro-C₁-C₃alkoxy or fluoro-bromo-C₁-C₃alkoxy.

12. A compound according to claim 2 of formula I wherein

R₂ is halogen or perfluoro-C₁-C₉alkyl,

R₂ is chlorine or bromine,

n is 1 or 2,

C₁-C₄alkoxy, C₁-C₄alkylthio or C₁-C₄alkanesulfonyl and/or two substituents R₃ bonded to adjacent carbon atoms of the phenyl ring are together -O-C(halo)₂-O-;

R₄ is hydrogen, C₁-C₄alkyl, C₃-C₄alkynyl, C₁-C₄alkanesulfonyl, di-C₁-C₄alkylaminosulfonyl, or a C₁-C₄alkyl group substituted by halogen, C₁-C₄alkoxy, C₁-C₄alkylthio, C₂-C₆alkoxyalkoxy, C₁-C₄alkanesulfonyl, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, cyano, mono-halophenyl or by phenoxy, and

R₅ is -OS(=O)₂-halo-C₁-C₂alkyl, halo-C₁-C₃alkyl or halo-C₁-C₃alkoxy.

13. A compound according to claim 2 of formula I wherein

R₁ is chlorine or perfluoro-C₁-C₄alkyl,

R₂ is chlorine or bromine,

n is 1,

R₃ is hydrogen, halogen, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy,

R₅ is -OS(=O)₂-fluoro-C₁-C₂alkyl, fluoro-C₁-C₂alkyl or halo-C₁-C₃alkoxy.

14. A compound according to claim 13 of formula I wherein

R₅ is -OS(=O)₂-CF₃, -C₂F₅, -OCF₂CF₂Br or -OCF₂CHFCF₃.

15. A compound according to claim 2 of formula I wherein R₁ is -CF₃,

R₂ is chlorine or bromine,

n is 1,

R₃ is hydrogen,

R₄ is hydrogen, chloromethyl, bromomethyl, methoxymethyl or ethoxymethyl and

R₅ is -OS(=O)₂-CF₃, -C₂F₅, -OCF₂CF₂Br or -OCF₂CHFCF₃, and the substituent R₅ is in the 4-position.

16. A compound according to claim 2 of formula I selected from the group consisting of the compounds

4-bromo-3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole, 4-chloro-3-cyano-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole, 4-bromo-3-cyano-2-(4-methanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

4-chloro-3-cyano-1-ethoxymethyl-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

4-bromo-3-cyano-1-ethoxymethyl-2-(4-trifluoromethanesulfonyloxy-phenyl)-5-trifluoromethyl-pyrrole,

4-bromo-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-5-trifluoromethylpyrrole,

4-chloro-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-5-trifluoromethylpyrrole,

4-bromo-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-1-ethoxymethyl-5-trifluoromethyl-pyrrole,

4-chloro-2-(4-[2-bromo-1,1,2,2-tetrafluoroethoxy]-phenyl)-3-cyano-1-ethoxymethyl-5-trifluoromethyl-pyrrole,

4-bromo-3-cyano-1-ethoxymethyl-2-(4-pentafluoroethyl-phenyl)-5-trifluoromethylpyrrole,

4-bromo-3-cyano-2-(4-pentafluoroethyl-phenyl)-5-trifluoromethyl-pyrrole,

3-cyano-4,5-dichloro-1-ethoxymethyl-2-(4-pentafluoroethyl-phenyl)-pyrrole and

3-cyano-4,5-dichloro-1-methyl-2-(4-pentafluoroethyl-phenyl)-pyrrole.

17. A process for the preparation of a compound of formula I, in free form or in salt form, which - taking account of the proviso that in compounds of formulae I, II and V,

R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is -CF₃ or halogen,

and with the further proviso that R₅ is not halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy when R₁ is -CF₂-halo-C₁-C₈alkyl - comprises a) introducing the halogen substituent R₂ into the 4-position of the pyrrole ring of a compound of formula

wherein R₁, R₃, R₄, R₅ and n are as defined in claim 1, formula I, or a salt thereof, by reaction with a halogenating agent or b) for the preparation of a compound of formula I wherein R₄ is other than hydrogen, or a salt thereof, reacting a compound of formula I wherein R₄ is hydrogen, or a salt thereof, with a compound of formula

X-R₄ (III), wherein R₄ has one of the definitions given for formula I with the exception of hydrogen and X is a leaving group, or where appropriate with a salt thereof, or c) for the preparation of a compound of formula I wherein R₅ is -OS(O=)₂R₆, reacting a compound of formula

wherein R₁, R₂, R₃, R₄, R₆ and n are as defined in claim 1 for formula I, or a salt thereof, with a compound of formula

Y-SO₂R₆ (IV), wherein R₆ has one of the definitions given for formula I and Y is a leaving group, or d) for the preparation of a compound «f formula I wherein R₄ is methyl or a group R₂CH₂-, or a salt thereof, reacting a compound of formula

wherein R₁, R₃, R₅ and n are as defined in claim 1 for formula I, or a salt thereof, with a halogenating agent or e) for the preparation of a compound of formula I wherein R₅ is halo-C₁-C₆alkoxy, reacting a compound of formula

wherein R₁, R₂, R₃ and n are as defined in claim 1 for formula I and R₄ is other than hydrogen, or a salt thereof, with a halo-C₁-C₆alkane or a halo-C₁-C₆alkene, and in each case, if desired, converting a compound of formula I obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula I, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula I obtainable in accordance with the process into a salt or converting a salt of a compound of formula I obtainable in accordance with the process into the free compound of formula I or into a different salt

18. A pesticide which comprises at least one compound according to claim 1 of formula I, in free form or in agrochemically acceptable salt form, as active ingredient and where appropriate at least one adjuvant

19. A composition according to claim 18 for controlling insects, representatives of the order Acarina and/or phytopathogenr fungi.

20. A composition according to claim 19 for controlling feeding insects.

21. A process for the preparation of a composition according to claim 18 comprising at least one adjuvant, which process comprises intimately mixing and/or grinding the active ingredient with the adjuvant(s).

22. A method of controlling pests, which comprises applying a composition according to claim 18 to the pests or to the locus thereof.

23. A method according to claim 22 of controlling insects, representatives of the order Acarina and/or phytopathogenic fungi.

24. A method according to claim 22 of controlling feeding insects.

25. A method according to claim 22 of protecting plant propagation material, which comprises treating the propagation material or the site of planting of the propagation material.

26. Plant propagation material treated in accordance with the method described in claim 25.

27. A compound of formula

wherein R₁, R₃, R₄, R₅ and n are as defined in claim 1 for formula I, or a salt thereof, with the proviso that

R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is -CF₃ or halogen, and with the further proviso that

28. A process for the preparation of a compound of formula II, or a salt thereof, which taking account of the proviso that, in the compounds of formulae II and VI of the following Synthesis Variants f) and g),

R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R. is -CF₃ or halogen,

and with the further proviso that

R₅ is not halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy when R₁ is -CF₂-halo-C₁-C₈alkyl - comprises f) for the preparation of a compound of formula II wherein R₄ is hydrogen, or of a salt thereof, reacting a compound of formula

wherein R₁, R₃, R₅ and n are as defined in claim 1, formula I, or a salt thereof, with 2-chloroacrylonitrile, or g) for the preparation of a compound of formula II wherein R₄ is other than hydrogen, or a salt thereof, reacting a compound of formula II wherein R₄ is hydrogen, or a salt thereof, with a compound of formula

X-R₄ (III), wherein R₄ has one of the definitions given for formula I with the exception of hydrogen and X is a leaving group, or where appropriate with a salt thereof, or h) for the preparation of a compound of formula

wherein R₁, R₂ and R₄ are as defined for formula I, or a salt thereof, with a halogenating agent and in each case, if desired, converting a compound of formula II obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula II, separating a mature of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula II obtainable in accordance with the process into a salt or converting a salt of a compound of formula II obtainable in accordance with the process into the free compound of formula II or into a different salt

29. A compound of formula

wherein R₁, R₃, R₅ and n are as defined in claim 1, formula I, or a salt thereof.

30. A compound of formula

wherein R₁, R₂ R₃, R₄ and n are as defined in claim 1, formula I.

31. A process for the preparation of a compound according to claim 29 of formula V, in free form or in salt form, which comprises i) reacting a compound of formula

wherein R₁, R₃, R₅ and n are as defined in claim 1 for formula I, with the proviso that R₅ is not -CF₃, -OCF₃, -OCHF₂, -OCF₂CHF₂, -OCF₂CHFCl or -OC₂F₅ when R₁ is -CF₃ or halogen, or a salt thereof, with aciylonitrile and, if desired, converting a compound of formula V obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula V, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula V obtainable in accordance with the process into a salt or converting a salt of a compound of formula V obtainable in accordance with the process into the free compound of formula V or into a different salt