IL142975A - Benzimidazoles and their preparation - Google Patents

Abstract

Benzimidazoles of the formula in which R12 represents hydrogen, halogenoalkoxy or halogenoalkylthio, R15 represents hydrogen, halogenoalkoxy or halogenoalkylthio, R16 represents hydrogen, halogenoalkylthio or halogenoalkoxy, with the exception of pentafluorethoxy, 3807 כ" ח בשבט התשס" ב - February 10, 2002 R17 repesents hydrogen, halogenoalkylthio or halogenoalkoxy, with the exception of pentafluoroethoxy and, but where at least one of the radicals R12, R15, R16 and R17 is other than hydrogen, or R12 and R16, or R16 and R17, or R17 and R15, in each case together with the carbon atoms to which they are bonded, form a five-or six-membered heterocyclic ring having one or 2 (non-adjacent) oxygen atoms which is at least monosubstitued by halogen.

Description

Benzimidazoles and their preparation Bayer Aktiengesellschaft C. 132944 142975/2 142975/2 142975/ 1- -2a- -■ having ' 1 to 4 carbon atoms, or represent hydroxycarbonyl, alky lcarbonyl havin Ί to 6 carbon atoms in the straight-chain or branched, alky 1 moiety, alkoxycarbonyl having 1 to 6 carbon atoms, in the straight-chain or branched alkoxy moiety, cycloalkylcarbonyl having 3 . to 6 carbon ' atoms in the- cycioalkyl moiety, cycloalkoxycarbbnyl ■ having 3- to 6 carbon atoms in the cycloaikyl moiety, or represent -Z-RJ" · wherein ■ ' .

R1 ' represents aryl- haying 6 to 10 carbon atoms, it being possible- for each of these radicals to-be monosubstituted to trisubsticuted by identical or different substituents from the series consisting of halogen, cyanb, nitro, alkyi having 1 to 4 carbon atoms, alkoxy having 1 to .4 carbon atoms , alkylthio /having 1 to .4 ςarbo atoms, halogenoalkyl having 1 to 4 carbon atoms . and 1 to 5 identical or different, halogen -atoms,' ■halogenoalkoxy having 1 to 4 carbon atoms and 1 to .5 identical or- different halogen atoms, halogeno alky Ithio .having 1 to, 4 carbon atoms and l . to 5 identical or different halogen atoms, alkyisulphmyl having 1 ■ •to 4 carbon atoms, - alkylsulphon l having 1 to 4. carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms and/ or halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, o , . , · ' . . .

R3 represents an unsaturated heterocyciyl radical having 5 or .6 .ring members and 1 to 3 hetero atoms, such as nitrogen, oxygen and/or sulphur, it being possible -for these radicals to be monosubstituted to trisubsticuted by identical .or different substituents from the series consisting of halogen, alkyl having 1 to 4 carbon atoms , aikoxy having 1 to 4 carbon atoms , halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms , halogenoalkoxy having 1 to 4 142975/1 -2b- . carbon ; atoms an'd 1 to 5 identical or .different halogen atoms, alkoxycarbonyl having 1 to 3 carbon · atoms in the all-coxy moiety, cydoaJLkyl having 3 to ό carbon, atoms , cyano and/or nitro , .'' represents a direct bond and -CH , 0 , S , SO, S0Z or CO, ■ R1 and R2, or- R1. and R3 , or R3 and R* in each case together also represent an ■all yleae - chain having 3 or 4 members in which one or two . (non- adjacent) carbon atoms can be replaced . by oxygen atoms and which is'- optionally monosu¾stituted to hexasubstiruted by halogen, alkyl having ' . 1 to 4 carbon atoms and/or halogenoallcyl having 1 to 4 carbon atoms ..and 1 to 9 halogen. atoms, X represents fluorine, chlorine, bromine or iodine, . and.

A represents one of the groups -SQ2-RS ' - , where \ R1 1 Y represents oxygen or sulphur and R3, R10 and Ru independently of one another represent straight-chain or - branched aU yl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having Γ to 4 carbon atoms .and 1 to 5 identical or different halogen atoms, saaight-chain or branched alkoxy having 1- to 4 carbon atoms , straight-chain or branched halogenoalkoxy having 1 to • 4 carbon atoms and 1 to 5 identical or different halogen atoms , straight- 142-975/1 -2c- chain or branched alkylthio having 1 to 4 carbon. atoms, straight-chai or branched halogenoalkyl hio having I to 4 carbon atoms and 1 to 5 . identical or different halogen atoms, straight-chain .or branched alkenyl having 2 to 4 carbon atoms, straight-chain or branched halogenoalkenyl having .2 to 4 carbo atoms and 1 to 5 identical or different halogen atoms , straight-chain or branched alkenyloxy having 2 to- 4 ' carbon - atoms , straight-chain or branched alkenylthio having 2 to 4 carbon ■ atoms, . straight-chain or branched alkinyl having 2 to 4 carbon atoms,' straight-chain or branched aUdirytoxy having 2 to 4 carbo . atoms , • straight-chain or /branched -alkinylthiq '.having '2 to 4 carbon atoms, amino , a^ y [amino having 1 to 4 carbon atoms, dialkylamino. having 1 to 4 carbon atoms in each- alky! moiety, ' . .- ■ ■ or represent phenyl, phe oxy. or phenylthio, it. being possible. for eac ■ of these radicals to be monosubsticuted to trisubstituted by identical -or . different substituents from, the series consisting ., of -fluorine, chlorine, ■bromine, nitro, alkyl haying 1 to 4 carbon atoms', halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine' atoms, ' - alkoxy having 1 to 4. carbon atoms and/or halogenoalkoxy having 1 to' 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, . or' represent cycloalkyl. having 3 -to' 7' carbon atoms, cycloalkyloxy having, 3 To 7 carbon atoms, cycloalkylthio having 3 to 7 carbon atoms , cycloalkylaniino having 3 to 7 carbon .atoms, pyrro-lidinyi, piperidinyl ' or morphoiinyl, it being possible for each of these abovementioned -radicals to be monosubstioited to txisubstituted by identical or different substicuents from the series consisting .of fluorine-, chlorine, bromine, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon, atoms and 1 to 5 fluorine , chlorine and/ or bromine atoms, or represent an unsaturated hecerocyclyl radical having 5 or 6 ring members and 1 to 3 hetero atoms, such as nitrogen, oxygen and/or 142975/2 sulphur, it being possible for these radicals to be' monosubstioited to trisubstituted by identical or different substidients from , the . series consisting of halogen, cyano, nitro, hydroxyl, amino, formyi, carboxyl, ,- carbamoyl, . thiocarbamoyl, alkyi' having 1 to 4 carbon .atoms , ; aikoxy ' ..having .1 to 4 carbon atoms, halogenoalkyl; having 1 to 4 carbon atoms and l to 5 identical or different halogen atoms, haiogenoaBcoxy having 1 to 4 carbon atoms . nd 1 to 5 identical or different halogen . atoms, .. alkoxycarbonyl having 1 to 4 carbon , atoms in the aikoxy moiety,.. ·. cycloalkyl having 3 to 6 carbon atoms , halogenoalkylsulphinyL having . 1 to .4. carbon atoms and 1 to 5 identical or different halogen atoms, ■halogenoalkyisulphonyl having 1 to '4' carbon. atoms and 1- to 5 identical or ..different halogen ..atoms, ..alkylamino having 1 to 4 carbon atoms.,'-. hydroxya.lkylamino having 1 to 4. carbon atoms,- dialkylamino haying 1 to 4 carbon atoms in each alkyi group, alk icarbonyl having 1 to : ; carbon atoms ■ i .the -alkyi .moiety,' hydroximinoalkyl .having 1. to ' 4 . carbon atoms in the. alkyi moiety, aL oximinoaikyl having 1 to 4 carbon ..atoms in the aikoxy moiety and I to 4 carbon atoms in the alkyi moiety,. alk lcarbonyloxy having 1 to 4 carbon atoms in the alkyi moiety and/or halogenoalkylcarbonylox having 1 to 4 carbon', atoms in the', halogenoalkyl group and 1 to 5 identical or different halogen atoms „ F.urthermore, is has been -found in IL 122944 that halogenobenzimidazoles of the formula (I) and their acid addition salts and metal salt complexes are obtained when a) b-eriz-rnid--Zole derivatives of the formula Le A 31 266 - Foreign countries in which R1, R2, RJ, R4 and X have the abovementioned meanings, are- reacted with halides of the formula A-X1 . {TDQ · in which A has the abovementioned meaning and X1 represents halogen, ■ if appropriate in the- presence of an acid-binding agent and if appropriate" "in the presence of a diluent, and,, if appropriate, the. resulting compounds of the formula (T) are subjected to an addition reaction with an acid or a metal salt Finally, it has been found in IL 122944 that the halogenobenzimidazoles of the formula (I) and their acid addition salts and metal salt complexes have very good microbicidal properties and can be employed both in crop protection and in the protection of materials.

Surprisingly, the substances according to IL 122944 display a better fungicidal activity than 2-cyano-3-dimethylarninosulphonyl-6,6,7 ,7-tetrafiuoro-[l ,4]- dioxiiioC2,3-t]ben2irnidazoie and 2-cyano^,0Hiif]uQn>^ [l,3]^oxolo[4,5-f]b€nziimda∑ole, which are prior-art active cornpounds of similar constitutiori and the same direction of action Formula (I) provides a general definition of the substances according to the invention in IL 122944; R!, R2, R3 and R4 independently of one another preferably represent hydrogen, fluorine, chlorine, bromine,- iodine, cyano, nitro, straight→:hain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkoxy having 1 to " 8 carbon atoms, straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms aud i to -13 identical or different- halogen atoms, straight-chain or branched alkylthio having 1 to 8 carbon atoms, straight-chain or branched haiogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkylsulphinyl having 1 to 8 carbon atoms, straight-chain or branched halogenoaikylsuiphinyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkyisulphonyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkylsulphonyi having 1 to . 6 carbon atoms and 1 to 13 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms which is optionally monosubstituted to pentasubstituted by identical or different substituents from the series consisting of halogen and/or alkyl having 1 to 4 carbon atoms, or represent hydroxycarbonyl, aikylcarbonyl having 1 to 6 carbon atoms in.the straight-chain or branched alkyl moiety, alkoxycarbonyl having 1 to 6 carbon atoms in the · . straight hain or branched alkoxy moiety, cycloalkylcarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety, cycloaikoxycarbonyi having 3 to 6 RS carbon atoms in the cycloalkyl moiety, or represent -Z-R3 or — Q — N \ , D ' R3' preferably represents aryl having 6 to 10 carbon atoms, it being possible for each of these radicals to be monosubstituied to irisubstituted by identical or - 6 - different substituents from the series consisting of halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1. to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical Or different halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylsulphinyl having 1 to 4 carbon atoms, alkylsulphonyl having 1 to 4 carbon atoms, halogenoalkylsiilphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms and/or halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms. preferably also represents an unsaturated heterocyclyl radical having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur, it being possible for these radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyi having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, cyano and/or nitro. preferably also represents a direct bond, and -CH2-, O, S, SO, SO2 or CO, or represents -CO-O-, the oxygen atom being bonded to R5, or represents -SOj-O-, the sulphur atom being bonded to R5, or represents -S-CE^-SC , the sulphur atom of the thio group being bonded to R5.

R6 and R7 independently of one another preferably represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched - 7 - halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, aryl having 6 to 10 carbon atoms, arylcarbonyl having 6 to 10 carbon atoms in the aryl moiety, arylsulphonyl having 6 to 10 carbon atoms, arylaminocarbonyl having 6 to 10 carbon atoms in the aryl moiety, or arylmethylsulphonyl having 6 to 10 carbon atoms in the aryl moiety, it being possible for each of the abovementioned aryl radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms^ alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical or different halogen . atoms, alkylsulphinyl having 1 to 4 carbon atoms, alkylsulphonyl having 1 to 4 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms and/or halogenoalkylsulphonyl Iraving 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms.

R6 and R7 furthermore also together with the nitrogen atom to which they are bonded preferably represent a heterocyclic ring having 5 or 6 ring members which can additionally contain an oxygen atom or a CrC4-alkylimino group and which is optionally monosubstituted to trisubstituted by alkyl having 1 to 4 carbon atoms.

Q also preferably represents a direct bond or a carbonyl group.

R1 and R2, or R2 and R3, or R3 and R4 in each case together also preferably represent an alkylene chain having 3 or 4 members in which one or two (non-adjacent) carbon atoms can be replaced by oxygen atoms and which is optionally monosubstituted or hexasubstituted by halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 halog< atoms. preferably represents fluorine, cWorine, bromine or iodine. also preferably represents one of the groups -SOj-R8, -CO-R9 or Y also preferably represents oxygen or sulphur.

R8, R9, R10 and Rn independently of one another preferably represent straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkoxy having 1 to 4 carbon atoms, straight-chain or branched halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, straight-chain or branched halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight- chain or branched alkenyl having 2 to 4 carbon atoms, straight-chain or branched halogenoalkenyl having 2 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkenyloxy having 2 to 4 carbon atoms, straight-chain or branched alkenylthio having 2 to 4 carbon atoms, straight-chain or branched alkinyl having 2 to 4 carbon atoms, straight- chain or branched alkinyloxy having 2 to 4 carbon atoms, straight-chain or branched alkinylthio having 2 to 4 carbon atoms, amino, alkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkyl moiety, or represents phenyl, phenoxy or phenylthio, it being possible for each of these radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, nitro, alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and or bromine atoms, alkoxy having 1 to 4 carbon atoms and/or halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, or represents cycloalkyl having 3 to 7 carbon atoms, cycloalkyloxy having 3 to 7 carbon atoms, cycloalkylthio having 3 to 7 carbon atoms, cycloalkylamino having 3 to 7 carbon atoms, pyrrolidinyl, piperidinyl or morpholinyl, it being possible for each of these abovementioned radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, or represents an unsaturated heterocyclyl radical having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur, it being possible for these radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of halogen, cyano, nitro, hydroxy!, amino, formyl, carboxyl, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atcns, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, altylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety, hydroximinoalkyl having 1 to 4 carbon atoms in the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, - 10 - alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and/or halogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkyl group and 1 to 5 identical or different halogen atoms.

R10 and Ru furthermore together with the phosphorus atom to which they are bonded preferably represent a 5- or 6-membered heterocyclyl radical which can contain one or two further heteroatoms, such as oxygen, sulphur and/or nitrogen, and which can be monosubstituted to trisubstituted . by identical or different substituents from the series consisting of fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4: carbon atoms and/or halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms.

Rl, R2, R3 and R4 independently of one another particularly preferably represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 6 carbon, atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, straight-chain or branched alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, straight- chain or branched alkylsulphinyl having 1 to 6 carbon atoms, halogenoalkylsulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, straight-chain or branched alkylsulphonyl having 1 to 6 carbon atoms, halogenoalkylsulphonyl having 1 or 2 carbon atoms and 1 to 5 , fluorine, chlorine and/or bromine atoms, cycloalkyl having 3 to 6 carbon atoms which is optionally monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, methyl and/or ethyl, or represent hydroxycarbonyl, alkylcarbonyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, alkoxycarbonyl having 1 to 4 carbon atoms in the straight-chain or branched alkoxy moiety, cycloalkylcarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety, - 11 - cycloalkoxycarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety, or Rs represent -Z-R5 or — Q — N R5 particularly preferably represents phenyl which can be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, halogenoalkylsulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms and/or halogenoalkylsulphonyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms.

R5 also particularly preferably represents an unsaturated heterocyclyl radical having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur, it being possible for each of these radicals to be monosubstituted or ^substituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, methoxycarbonyl, ethoxycarbonyl, cycloalkyl having 3 to 6 carbon atoms, cyano and or nitro.

Z also particularly preferably represents a direct bond, and also represents CH2, O, S, SO, SO2 or CO, or represents -CO-O-, the oxygen atom being bonded to R\ - 12 - or represents -SOj-O-, the sulphur atom being bonded to R5, or represents -S-CH2-S02-, the sulphur atom of the thio group being bonded to R5.

R6 and R7 independently of one another particularly preferably represent hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, straight-chain or branched alkoxyalkyl having 1 to 3 carbon atoms in the alkoxy moiety and 1 to 3 carbon atoms in the alkyl moiety, alkylcarbonyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, phenyl, phenylcarbonyl, phenylsulphonyl, phenylaminocarbonyl or phenylmethylsulphonyl, it being possible for each of the abovementioned phenyl radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, cyano, nitro, alkyl having 1 or 2 carbon atoms, alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or. bromine atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halo genoalky lthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylsulphinyl having 1 or 2 carbon atoms, alkylsulphonyl having 1 or 2 carbon atoms, halogenoalkylsulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms and/or halogenoalkylsulphonyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms.

R6 and R7 furthermore also together with the nitrogen atom to which they are bonded particularly preferably represent a saturated heterocyclic ring having 5 or 6 ring members which is optionally monosubstituted to trisubstituted by methyl and/or ethyl, it being possible for a carbon atom of the ring to be replaced by oxygen or memylimino. - - 13 - Q also particularly preferably represents a direct bond or a carbonyl group.

R1 and R2, or R2 and R3, or R3 and R4, in each case together also particularly preferably represent an alkylene chain having 3 or 4 members which is optionally monosubstituted to Irisubstituted by fluorine, chlorine, methyl and/or trifluoromethyl and in which one or two (non-adjacent) carbon atoms can be replaced by oxygen.

X also particularly preferably represents fluorine, chlorine, bromine or iodine.

A also particularly preferably represents one of the groups Y also particularly preferably represents oxygen or sulphur.

R8, R9, R10 and Ru independently of one another particularly preferably represent methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, difluorochloromemylthio, allyl, n- or s-butenyl; allyloxy, n- or s-butenyloxy; allylthio, n- or s-butenylthio; propargyl, n- or s-butinyl; propargyloxy; propargylthio; amino; memylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino; amemylamino, diethylamino, di-n- or i-propylarnino, methylemylamino, methyl-n- or i-propylamino; or represent phenyl, phenoxy or phenylthio, it being possible for each of these radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, nitro, - 14 - methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, trifluorornethyl and/or trifiuoromethoxy; or represent cyclopropyl, cyclopentyl, cyclohexyl, cyciopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclopentylamino, tyclohexylamino, 1-pyirolidinyl, 1-piperidinyl, and 1-morpholinyl, it being possible for each of these radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and/or trifluorornethyl, or represents an unsaturated heterocyciyl radical having 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur, it being possible for each of these radicals to be monosubstituted or disubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, cyano, nitro, hydroxy 1, amino, formyl, carboxyl, carbamoyl, thiocarbamoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy carbonyl having 1 or 2 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkylsulphonyl having 1 or 2 carbon atoms nd 1 to 5 fluorine, chlorine and/or bromine atoms, alkylamino having 1 or 2 carbon atoms, hydroxyalkylamino having 1 or 2 carbon atoms, dialkylamino having 1 or 2 carbon atoms in each alkyl group, alkylcarbonyl having 1 or 2 carbon atoms in the alkyl moiety, hydroximinoalkyl having 1 or 2 carbon atoms in the alkyl moiety, alkoxirninoalkyl having 1 or 2 carbon atoms in the alkoxy moiety and 1 or 2 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1 or 2 carbon atoms in the alkyl group and/or halogenoalkylcarbonyloxy having 1 or 2 carbon atoms in the halogenoalkyl group and 1 to 5 fluorine, chlorine and/or bromine atoms.

R[0 and R11 furthermore together with the phosphorus atom to which they are bonded particularly preferably represent a 5- or 6-membered heterocyclyl radical which can contain one or two further heteroaioms, such as oxygen, sulphur and/or nitrogen, and which can be monosubstituted to trisubstituted by identical or different substituents from the series consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, chlorine and/or trifluoromethyl.

R1, R2, R3 and R4 independently of one another very particularly preferably represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, or represent methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio,- n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifiuoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, acetyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, R6 cyclopropyl, cyclohexyl, or represent Z-R5 or — Q — N V R5 very particularly preferably represents phenyl which can be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, cyano, nitro, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, memylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifiuoromethylthio, difluoromethylsulphinyl and/or trifluoromethylsulphonyl.

R5 also very particularly preferably represents pyrrolyl, furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, it being possible for each of these radicals - 16 - to be monosubstituted or disubstituted by identical or different substituents from the series consisting of fluorine, chlorine, methyl, methoxy, trifluoromethyl, trifluoromethoxy and/or trifluoroethoxy.

Z also very particularly preferably represents a direct bond, or represents C¾ O, s, so, sa, co, or represents -CO-O-, the oxygen atom being bonded to R5, or represents -SOj-O-, the sulphur atom being bonded to R3, or represents -S-CHJ-SOJ-, the sulphur atom of the thio group being bonded to R5.

R6 and R7 independently of one another very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl or phenyl.

R6 and R7 furthermore also together with the nitrogen atom to which they are bonded very particularly preferably represent pyrrolidinyl, piperidinyl, morpholinyl or 4-methylpiperazinyl.

Q also very particularly preferably represents a direct bond or a carbonyl group.

R1 and R2, or R2 and R3, or R3 and R4, in each case together, also very particularly preferably represent the groups -CFrO-CFr, -O-CF2-O-, -0-CFrCHF-0-, -O-CHF-CHF-O-, -O-CF2-CF2-O-, -0-CF2-CFCl-O- or -0-CFC1-CFC1-O-.

X also very particularly preferably represents fluorine, chlorine, brornine or iodine.

A also very particularly preferably represents one of the groups - - 17 - Y D 10 -SC^R8, -CO-R9 \ 11 R Y also very particularly preferably represents oxygen or sulphur.

R8, R9, R10 and R11 independently of one another particularly preferably represent methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, difluoromethoxy, trifiuoromethoxy, difluorochlorornethoxy, trifluoroeuioxy, methyllhio, ethylthio,. n- or i-propylthio, difluoromethylthio, trifluoromethylthio, difluorochloro- methylthio, allyl, n- or s-butenyl; allyloxy, n- or s-butenyloxy; allylthio, n- or s-butenylthio; propargyl, n- or s-butinyl; propargyloxy; propargylthio; amino; methylarnino, emylarnino, n- or i-propylamino, n-, i-, s- or t-butylamino; dimemylarnino, diemylarnino, di-n- or i-propylarnino, memylemylamino, methyl-n- or i-r opylarnino; or represent phenyl, phenoxy or phenylthio, it being possible for each of these radicals to be monosubstituted to ^substituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, trifluoromethyl and/or trifiuoromethoxy; or represent cyclopropyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclopentylthio, cyclohexylthio, cyclopropylarnino, cyclopentylamino, cyclohexylamino, 1-pyrrolidinyl, 1-piperidinyl, and 1-morpholinyl, it being possible for each of these radicals to be monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl and/or trifluoromethyl, or represent pyrroiyl furyi, thienyl, pyrazolyl, imidazolyl, thiazol l, isoLbiazoiyl, oxazolyi, isoxazolyl. oxadiazolyl, thiadiazoiyl, lJZJ-taazinyl, l,2,4-triaziayl, lJ,5-Criazinyl, pyridinyi, pyrirriidinyL, pyrazinyl or pyridazihyl, it being possible for each of these radicals to be monosubstituted or constituted by identical or different substituents from the series consisting of fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy!, formyl, carboxyt, carbamoyl, thiocarbamoyL, methyl,- ethyl, n- or i-propy , n-, i-, s- or t-butyl, me hoxy, ethoxy, n- or i-propoxy, methylthio, emyithio, n- or i-propylthio, memylsuiphinyi, ethylsulphinyl, methylsulphonyl, ethylsuiphonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, ' Gifluoromethylthio, trifluoromemylsuipmnyl or.trifluoromerhylsulphonyl, mefoylamino, emylamino, " n- or ί-propylarnino, dimemyiamino, diemylamino, acetyl, propionyl, ace yloxy, - methoxy carbony I, ethoxycaxbonyl, methylsulphonyloxy, ethylsulphonyloxy, hydroxyiminomethyl, hydroxy iminoethyl, methoxyiminomethyl, emoxyiminomethyl, memoxyirninoethyl and/or ethoxyiminoethyl.

R10 and R11 furthermore also together with the phosphorus atom to which they are bonded very particularly preferably represent a 5- or 6-membered heterocyclyl radical which can contain one or two further heteroatoms, such as oxygen, sulphur, and/or nitrogen, and which can be monosubstituted to trisubstituted by identical or different substituents frorrrthe series consisting of methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, chlorine and/or trifluoromethyl.

The definitions of radicals given above, in general or in preferred ranges, apply to the . end products of the formula (I) and, analogously, to the starting materials or intermediates required in each case for the preparation.

Other preferred compounds according to IL 122944 are addition products of acids and those halogenocCTzimidazoles of the formula (I) in which Rl, R2, RJ, R4, A and X have those meanings which have been mentioned as being preferred for these radicals.

The acids which can be subjected to the adciiion reaction preferably include hydrohaiic - - 19 - acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrcchloric acid, furthermore phosphoric acid, sulphuric acid, nitric acid, mono- and bifunctional carboxylic acid and hydroxycarboxylic acids, such as, for example, acetic acid, rnaleic acid, succinic acid, furnaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic a d, and also- sulphonic acids, such as, for example, p-fcoluenesulphonic acid, 1,5-naphtbalenedisulphonic acid, saccharine and triosaccharine.

Other .preferred compounds according to IL 122944 are addition products of salts of metals of main- groups Π to IV . and sub-groups. I and Π and also IV to Vffl of the Periodic Table of the Elements and those halogenobenzimidazoles of the formula (I) in which R1, R2, R3, R4, A and X have those meanings which have' been mentioned as being preferred for these radicals.

Particularly preferred in this. context are salts of copper, zinc, manganese, magnesium, tin, iron and of nickel. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Particularly preferred acids of this type are, in this context, the hydrohalic- acids, such as, for example, hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, nitric acid and sulphuric acid.

"Examples of substances according to- IL 122944 . which may be mentioned are the halogenob«nz3inidazoles listed in the tables which follow: Table 1 where A represents the following substituencs: Table 2 where A represents the substituents mentioned in Table 1.

Table 3 where A represents the substituents mentioned in Table 1.

Table 4 where A represents the substituents mentioned in Table 1. i - - 22 - ' Table 5 where A represents the substituents mentioned in Table Table 6 where A represents the substituents mentioned in Table Table 7 where A represents the substituents mentioned in Table 1.

Table 8 N CI (In) \ - 23 -where A represents the substituents mentioned in Table Table! where A represents the substituents mentioned in Table 1.

T HelO where A represents the substituents mentioned in Table 1.

TabJeJLi where A represents the substituents mentioned in Table 1.

Table 12 where A represents the substituents mentioned in Table Table 13 where A represents the substituents mentioned in Table 1.

Table 14 where A represents the substituents mentioned in Table Table 15 where A represents the substituents mentioned in Table 1.

Tabte 16 where A represents the substituents mentioned in Table 1.

If '2-chiorc^.lH-benzirridazole and toluene-4-sulphonyl chloride are used, as starting substances, the course of process a) according to IL 1229.44 can be illustrated by the ■ following equation: , ■ .

Formula ΓΠ) provides a general definition of the benzimidazole derivatives required as starting substances for carrying out process, (a) according to IL 122944, In this formula (Π), R1, R2, R3,;R4 and X preferably, or in particular, have, those meanings which have already been- mentioned in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for 1, R2, R3, R4 and X. .

Some of the benzi idazole derivatives of the formula (EE) are known (compare Chem Pharm. Bull. 1981 , 29, 2403; Synthesis 1988. 767; J. Chem. Soc. 1922, 947; WO-A 9408456; WO-A 9207867 Bull. Sec. Chim. Fr. 1988, i, 139-142; EP-A 308918; J. C.. S. Chem. Com. 1976. 430; Liebigs. Ann. Chem. 1961. 649, 114 and J. Prakt. Chem. J9 , 28, 297). . ' Le A, 3 ! 266 - Forei n countries derivatives of the formula in which Rn, R14 and R independently .of one another represent hydrogen, halogenoalkoxy or halogenoaikyithio, at least one of Che radicals mentioned, representing halogenoalkoxy or halogenoalkylthio, or R12 and R13,. or R° and R14, or R14 and R , in each case together with the carbon atoms to which they are bonded form a five- or six-membered heterocyclic ring which has one or two (non-adjacent) oxygen atoms and which is at least monosubstituted- by halogen and X represents halogen, are described and claimed in IL application No. 138924 which was divided out of IL 122944.

Benzimidazole derivatives of the formula (Ha) can be prepared by (b) reacting benzimidazoies of the formula in widen - 27 R , R , R and R15 have the abovementioned meanings with halogenaiing agents, if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent, or c) reacting bromobenzimidazoles of the formula in which R12, R13, R14 and Rls have the abovementioned meanings with hydrofluoric, hydrochloric or hydriodic acid or with a salt of the formula NfX2' (V) in which M represents a metal equivalent or a quaternary ammonium, sulphonium, sulphoxonium or phosphonium ion and X2 represents fluorine, chlorine or iodine, if appropriate in the presence of a diluent Formula (Ha) provides a general definition of the new benzimidazole derivatives.

R12, R13, R14 and R15 independently of one another preferably represent hydrogen, straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and I to 13 identical or different halogen atoms, straight-chain or branched haiogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, at least one of the radicals mentioned representing halogenoalkoxy or haiogenoalkylthio.

R12 and R13, or R13 and R14, or R14 and R15, in each case together with the carbon atoms to which they are bonded, also preferably represent a five- or six-membered heterocyclic ring having one or two (non-adjacent) oxygen atoms which is monosubstituted to tetrasubstituted by halogen.

X preferably represents fluorine, chlorine, bromine or iodine.

R12, R13, R14 and R15 independently of one another particularl preferably represent hydrogen, difluromethoxy, trifluoromethoxy, difluorochloromethoxy, difluorobromomethoxy, tafluoroethoxy, difluoromethylthio, trifluoromethylthio, . c^uorcchloromethylthio or difluorobromomethylthio, at least one of the radicals being other than hydrogen.

R12 and R13, or R13 and R14, or R14 and R15, in each case together with the carbon atoms to which they are bonded, also particularly preferably form a five- or six- membered, heterocyclic ring having one or two (non-adjacent) oxygen atoms which is monosubstituted to tetrasubstituted by fluorine, chlorine and/or bromine.

X also particularly preferably represents fluorine, chlorine, bromine or iodine.

If 5-trifluoromemoxy-lH-berizirnidazole and N-bromosuccinimide are used as starting substances, the course of process (b) according to the invention can be illustrated by the following equation: Formula (TV) provides a general definition of the benzimidazoles required as starting substances for carrying out process (b) according to the inventioa In this formula, Ku, R13, R14 and R15 preferably, or in particular, have those meanings which have already been given in connection with the description of the compounds of the formula (Ha) as being preferred, or particularly preferred, for Rn, R13, R14 and R15.

Some of the bermmidazoles of the formula (TV) are known. 5-Pentafluoroethoxy-lH-bermmidazole, for example, has already been described (cf. Biomed Enviroa Mass Spectrom (1989), 18(10), 872-877).

The benzirnidazoles of the formula in which R12 represents hydrogen, halogenoalkoxy or halogenoalkylthio, R15 represents hydrogen, halogenoalkoxy or halogenoalkylthio, R16 represents hydrogen, halogenoalkylthio or halogenoalkoxy, with the exception of pentafiuoroethoxy, R17 represents hydrogen, halogenoalkylthio or halogenoalkoxy, with the exception e - ore gn countr es - 30 - ' of peni-afiiioroetfaoxy, but where ai least one of the radicals R12, Rli, Rt0 and R17 is other than hydrogen, or R12 and R'6, or Rt6 and R17, or R17 and Ru,' in each case together vvith the carbon atoms to which they are bonded, form a five- or six-membered heterocyclic ring having one or 2 (non-adjacent) oxygen atoms which is at least monosubstituted by haloge . . . . . . are new and constitute an aspect of the present invention. : Tne berrzirrndazoles of the formula (TVa) can be prepared by reacting phenylenecaamines of the formula in which R12, R15, R16 and R17 have the abovementioned meanings- w th -formic acid, with one of its salts, or with one of its derivatives, such as, for example, formamide, nhrnethyl orthoformate, diallylformarriide acetate, formarnide, s-triazine or carbon monoxide, at a temr^raiure of from 0°C to 180QC, preferably from °C to 150°C, if appropriate in the presence of a diluent, such as, for example, water, methanol, ethanol or methoxyethanol.

Formula (TV-a) provides a general definition of the new berizimidazoles.

R12 preferably represents hydrogen, straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents straight-chain or branched nalogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms.

R15 preferably represents hydrogen, straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents straight-chain or branched halogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms.

R16 preferably represents hydrogen, straight-chain or branched halogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, but with the exception of pentafiuoroethoxy.

R17 preferably represents hydrogen, straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, but with the exception of pentafluoroethoxy.

However, one of the radicals R12, R15, R16 and R17 must be other than hydrogen.

R12 and R16, or R16 and R17, or R17 and R15, can, in each case, together with the carbon atoms to which they are bonded, also preferably form a five- or six-member ed heterocyclic ring having one or two (non-adjacent) oxygen atoms which is - 32 - monosubstituted to tetrasubstituted by halogen.

Ru, R15, R16 and R17 independently of one another particularl preferably represent hydrogen, difluoromethoxy, trifluoromethoxy, difluoromethoxy, difluorobromo- methoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluoromethylthio or diflucirobromomemylthio, at least one of the radicals being other than hydrogen.

R12 and R16, or R16 and R17, or R17 and R15, in each case together with the carbon atoms to which they are bonded, also particularly preferably form a five- or six- membered heterocyclic ring having one or two (non-adjacent) oxygen atoms which is monosubstituted to tetrasubstituted by fluorine, chlorine and/or bromine. .

If 4-trifluoromemoxy- phenylenediamine and formic acid are used as starting substances, the course of process (d) according to the invention can be illustrated by the following equation: Formula (VI) provides a general definition of the phenylenediamines required as starting substances for carrying out process (d) according to the inventioa In this formula (VI), R12, R15, R16 and R17 preferably, or in particular, have those meanings which have already been mentioned in connection with the description of the compounds of the formula (TVa) as being preferred, or particularly preferred, for R12, R15, R16 and R17.

The phenylenediamines of the formula (VI) are known; their preparation is described, for example, in DE-A 3 605 977, DE-A 3 621 215 or DE-A 4 237 564.

When carrying out process (b) according to the invention, suitable halogenating agents are, preferably, elemental halogen or N-halogenoimides, such, as N-r omo-succiiiiinide or N-Chiorchsuccinimide.

Diluents which are suitable for carrying out process (b) according to the invention are all' customary inert organic solvents. The following can preferably be used: aliphatic, alicyclic or .aromatic .hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; furthermore halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, ' tetrachloromethane, dichloroethane or trichloroethane; moreover ethers, ■ such as diethyl ether, diisopropyl-- ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimemoxyethane, 1^2-diethoxyethane or anisole; furtherrnore nitrites, such as acetonitrile, propionitrile, n- or i-butyronitrile or berizonitrile, or else amides, such as Ν,Ν-dmiemylformamide, N^-dimethylacetarnide, N-memylformanilide, N-methylpyrrolidone and hexamethylphosphoric triamide.

Suitable acid-binding agents for carrying out process (b) according to the invention are all customary inorganic and organic acid acceptors. The following can preferably be used: the hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates of alkaline earth metals or alkali metals, such as sodium hydride, sodium' amide, sodium methylate, sodium ethylate, potassium tert-butylate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, furthermore ammonium acetate or ammonium carbonate, or tertiary amines, such as trimethytamine, triemylamine, tributylamine, N,N-dimethytaniline, Ν,Ν-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, diazabicyciooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

When carrying out process (b), the reaction temperatures can : be varied within a substantial range. In general, the process is · carried out - at temperatures between -20°C and +120°C, preferably between 0°C and 80°C. e -- ore gn coun r es When carrying out process (b) and also when carrying out the other processes according to the invention, the reactions are generally carried out .under atmospheric pressure. However, it is also possible to cany out the reactions under elevated pressure or, in the event that no gaseous components are employed, under reduced nressure.

When carrying out process (b), an equivalent amount, or else an excess, of halogenaring agent is generally employed per mole of the 'formula (TV). Worlring-up is carried oui by customary" methods.

If 2 -bromo-S-trifluoromethoxy- lHrbenzirni dazole and. sodium chloride are used as starting substances, the course of process (c) can be illustrated by the following : equation: Formula (Hb) provides a general definition of the bromor^n2imidazoles required for carrying . out process (c). In this formula (lib), R12, R13, ~R14 and R ~ preferably, or in particular, have those meanings which have already been mentioned in connection with the description of the- compounds of the formula (Ha) according to the invention as being preferred,, or particularly preferred, for R12, R", R14 and R15.

The compounds of the formula (lib) are intermediates and can be prepared by process (b) according to the invention.

Hydrofluoric acid, hydrochloric acid or hydriodic acid, furthermore required for carrying out process (c), are generally known chemicals for synthesis.. - - 35 - Formuia (V) 'provides a general definition of the salts alternatively also inquired as reactants for carrying out process (c). In this formula, M ' preferably represents an alkali metal, in particular lithium, sodium or potassium, or a quaternary airmonium, sulphoniurn, sulphoxonium or phosphonium ion, preferably tetraan ylammo urn, having in each case 1 to 12 carbon atoms in the individual alkyl chains, and X2 represents fluorine, chlorine or iodine.

Tne salts of the formula (V) are known chemicals for synthesis.

Suitable diluents for carrying. out . process ' (c) are all customary inert organic solvents.: The following can .preferably be used: aliphatic, ali cyclic or aromatic hydrocarbons such as petroleum ether, hexane, .heptane, cyclohexaue, meth lc clohexane, benzene, toluene, xylene or decalin; furthermore haiogenated hyarocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, . chloroform, tetrachloromethane, dichloroethane or cric oroethane; furthermore ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, '.dioxane, teixahydrofurau, 1 ,2-dimemoxyethane, 1 ,2-diemoxyethane or anisoie; moreover • ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; in addition nitriles, such as acetonitrile, propionitrile, n- or. i-buryroriitrile or benzonitrile; furthermore amides, such as N^-dimemyliormamide, Ν,Ν-dimemylacetamide, N-memyu¾rmaniUde, N-methylpyrrolidone orJiexamethyiphosphoric triamide; and also esters, such as methyl acetate or ethyl acetate, and sulphoxides, such as dimethyl sulphoxide, and sulphones, such as sulpholane. If appropriate, the reaction can also be carried out in a two-phase system, for example in a mLxture of toluene and water.

When carrying out process (c), the reaction temperatures can, again, be varied within a substantial range. In - general, the process is carried out at temperatures between -20°C and +150°C, preferably between 0°C and 120°C.

When carrying out process (c), an equivalent amount, or . else an excess, of the reactant in question is generally employed per mole of bromo- benzirnidaole. Working-up is carried out by customary methods.

Le Λ 31 266 - Foreign countries Formula . (EH) provides a general definition of the haiides furthermore required as reactants for carrying out process (a). In this formula (III)/ A preferably, or in particular, has the meaning which has already been mentioned in connection with .the description of the compounds of the formula (I) being preferred, or particularly preferred, for A X1 preferably represents chlorine or bromine. · The haiides of the formula (HI) are known and or can be prepared" by known processes (I. Heterocyclic Chem. 1981, 997-1006).

Suitable diluents for carrying . out process ' . (a) are all · inert ■ organic solvents. The following .can preferably be used aliphatic, alicyclic or aromatic hydrocarbons, such as petroieum ether, hexane, heptane, . cyclohexane, . methylcyclohexane, benzene, toluene, xylene or decaiin; haiogenated hydrocarbons, such as. chlorobenzene, dichloro benzene, dichloromethane, chloroform, telxachloromethane, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl . ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tec^ydrofuran, 1,2-dixnethox ethane, 1,2-diemoxyethane or anisoie; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n-or i-buryronitrile or amides, such as Ν,Ν-dimemylformamide, N,N-dimethylacetamide, N-methyifonnaniiide, N-methylpyrrolidone or hexamethylphosphoric triamide .esters, such as methyl acetate or .ethyl acetate, sulphoxides, such as dimethyl sulphoxide, and suiphones, such as sulpholane.

If appropriate, process (a) is carried out in the presence of a suitable acid acceptor. Suitable acid acceptors are all customary inorganic or organic bases. The following can preferably be use± the hydrides, hydroxides, amides, alcoholat.es, acetates, carbonates or hydrogen carbonates of alkaline earth metals or alkali metals, such as sodium hydride, sodium amide, sodium methyiate, sodium eihylaie, potassium tert-butyiate, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, furthermore ammonium When carrying out process (a), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 150°C,. preferably between 20°C and 120QC.

To carry . out process, .(a), ' I - to 15 mol, preferably 1 to- 2 mol, . in particular 1 to 13 moL. of halide of the formula (UJ) are generally employed per mole of bensrmdazoie derivative of the formula (II).

Process (a) is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under elevated or reduced pressure, in general between 0.1 bar- and 10 bar..

Working-up is carried out by customary methods.

The hdogenobeazimidazoles of the formula (I) can be converted into acid addition salts or metal salt complexes.

Suitable acids for preparing acid addition salts of the compounds of the formula (I) are preferably those which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.

The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent.

Suitable salts for the preparation of metal salt complexes of the compounds of the formula (I) are preferably those salts of metals which have already been mentioned as being preferred metal salts in connection with the description of the metal salt complexes according to the invention.

The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary methods, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to compounds of the formula (I). Metal salt complexes can be isolated in a known manner, for example by filtration, and, if appropriate, purified by recrystallization.

The active compounds according to the invention have a potent microbicidal activity and can be employed in practice for controlling undesirable microorganisms. The active compounds are suitable for use as crop protection agents, in particular as fungicides in crop protection and also in the protection of materials.

Fungicidal agents are employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericidal agents are employed in σορ protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation: Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticoia Brernia species, such as, for example, Brernia lactucae, Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Exysiphe species, such as, for example, Erysiphe grarninis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea Podosphaera species, such as, for example, Podosphaera leucotricha Venturia species, such as, for example, Venturia inaequaiis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn: Helrninthosporium); Cochliobolus species, such as, for example, Cochliobolus sarivus (conidia · form: Drechslera, syn: Helminmosporium) Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita; Scierotinia species, such as, for example, Scleroti ia. sclerotiorum Tilletia species, such as, for example, Tilletia caries; Ustilago species, such, as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusariurn culmorum Botrytis species, such as, for example, Botrytis cinerea .

Septoria species, such as, for -example, Septoria nodorum Leptosphaeri species, such as, for example, Leptosphaeria nodorum Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae and Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of aerial parts of plants, of propagation stock and seeds, and of the soil.

Tne active compounds according to . IL 122944 can be employed particularly successfully for controlling diseases in fruit and vegetable growing and viticulture, such - 40 - as, for example, against Phytophthora or Plasmopara species, or for controlling rice diseases, such as, for example, against the pathogen causing rice blast disease (Pyricularia oryzae).

In the protection of materials, the substances according to the invention can be employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaning non-live materials which have, been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be glues, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the multiplication of microorganisms may also be mentioned within the scope of the materials to be protected Industrial materials which may be mentioned within the scope of the present invention are preferably glues, sizes, papers and boards, leather, wood, paints, cooling lubricants and heat-transfer liquids.

Microorganisms, capable of bringing about degradation of, or change in, the industrial materials, which may be mentioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds or agents according to the invention preferably act against fungi, in particular moulds, and against slime organisms and algae.

Microorganisms of the following genera may be mentioned as examples: Altemaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa and Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and or chemical properties, the active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are mainly suitable as liquid solvents: aromatics such as xylene, toluene or all Adhesives such as carboxymethyicelluiose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and . synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalccyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

, The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90% The activity and the spectrum of action of the active compounds can be increased by adding, if appropriate, other antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds for widening the spectrum of action or achieving specific effects, such as, for example, an additional protection against insects. These rriixtures may have a wider spectrum of action than the compounds according to the invention.

In many cases, synergistic effects are achieved, i.e. the activity of the mixture exceeds the activity of the individual components. Examples of particularly advantageous co- components in mixtures are the following compounds: Fungicides: 2-aminobutane; 2-amlmo-4-methyl--6^cloprop 2',6'-dibromo-2-methyl-4'-trifluoromeiho^^,-trifluorcHmethyl-l ,3-thiazole-5^arboxamlide; 2,6-dichloroN-(4-1rifluoromet_hylben2 I)benzamide; (E)-2-methoxyirnino-N-methyl-2-(2-phenoxy-phenyl)acetamide; 8-hydroxyc ino.in.e sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy methyl (E)-methoximino[alpha-(o-tolyloxy)-otolyl]-acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapaciyl, biphenyL, bitertanol, blasticidin-S, bromuconazole, bijpirimate, buthiobate, calcium polysulphide, captafol, captan, carbenda2irn, carboxin, quinomethionate, . chloroneb, cWoropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cypro-conazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditali fos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminurn, fthalide, iliberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, irninoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mLxture, mancopper, mancozeb, maneb, mepanipyrirn, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel dimemylditrdocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxy carboxin, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, - 44 - pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, tniram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, Iriflurnizole, triforine, triticonazole, validamycin A, vinclozolin, zineb, zirara Bactericides: bronopol, dichlorophen, rdtrapyrin, nickel dimethylditrdocarbamate, kasugamycin, octhilinone, iurancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations Jhsecu^ides/Acaricides/ ematicides: abamectin, acephate, acrinatririn, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541 , azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, 4-bromo-2-(4-chlorophenyl)- 1 -(ethoxymethyl)- bendiocarb, benfunacarb, bensultap, betacyfluthrin , bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridmyl)-memyl]-N'-<^ancHN-mem^ cWo^yrifos, chlorpyrifosM, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, c^uthrin, cyhalothrin, cyhexatin, cyperme hrin, cyromazine, deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, emamectin, esfenvaierate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, - 45 - fenoxycarb, fenproparhrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, fliifenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH,.heptenophos, hexaflumuron, hexythiazox, irnidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cylialothrin, lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, pennethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirirnicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrirnidifen, pyriproxifen, quinalphos, salithion, sebufos, silafiuofen, sulfotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetiacUorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, t onazin, muringiensin, Irdometlirin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators is also possible.

The active compound combinations preferably comprise 0.1 to 99.9%, in particular 1 to 75%, particularly preferably 5 to 50%, of the active compound, the remainder to 100% being made up by one or more of the abovementioned co-components.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable - 46 - powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, spreading, dusting, foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation, or the active compound itself, into the soil. The seed of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight- In the treatment of seed, amounts of active compound of from 0.001 to 50 g, preferably 0.01 to 10 g, are generally required per kilogram of seed.

In the treatment of the soil, active compound concentrations of from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weigtrt, are required at the site of actioa The compositions used for the protection of industrial materials generally comprise an amount of 1 to 95%, preferably 10 to 75%, of the active compounds.

The use concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal rate of application can be determined by test series. In general, the use concentrations are in the range of from 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the material to be protected.

The preparation and use of active compounds according to the invention are illustrated by the examples which follow.

Process (a) 0.2 g (5 mmol) of sodium hydride (60%) is added at room temperature to a stirred mixture of 1.4 g (5 mmol) of 2-bromcH0,6 iij_luorc>-[l,3]dw^ and 30 ml of absolute tetrahydrofuran, and the reaction mixture is then stirred for 30 minutes at room temperature. 1.0 g (5.5 mmol) of 3,5-dunethylisoxazole-4-sulphonyl chloride is then added, and the mixture is stirred for a further 3 hours at room temperature. For working-up, the reaction mixture is poured into 100 ml of water. The resulting mixture is extracted twice using in each case 50 ml of ethyl acetate. The combined organic phases are dried over sodium sulphate and concentrated under reduced pressure. The residue which remains is chromatographed on silica gel using methylene chloride as the eluent This gives 1.2 g (75% of theory) of l-(3,5-dime ylisoxazole-4-sulphonyl)-2-to^ benzimidazole in the form of a colourless solid of melting point 130-134°C. 48 Preparation of precuisois Process (b) 2.0 g (10 mmol) of 6,6-difluoro[l,3]dioxolo[4,5-fjbenzimidazole are added to a suspension of 0.48 g (12 mmol) of 60% sodium hydride in 20 ml of absolute dimemylformamide, the mixture is stirred for 30 minutes at 20°C, 2.2 g (12 mmol) of N-bromosucxinimide are. then added, and the mixture is stirred for a further 30 minutes at the same temperature. The mixture is poured onto 250 g of ice, brought to pH = 4 using glacial acetic acid and extracted three times using in each case 100 ml of ethyl acetate. The combined organic extracts are dried over sodium sulphate and concentrated in vacuo. The residue which remains is stirred with 50 ml of water, and the resulting residue is filtered off and dried.

This gives 2.3 g (83% of theory) of 2-bromo-6,6 lifluoro[l,3]dioxolo[4,5-fJbenzimida2Dle as a white solid of a melting range of 160 to 164°C.

Process (d) 80 ml of 98% strength formic acid are added to 37.6 g (0.2 mol) of 5,6-diamino-2,2-difiuorobenzodioxole, and the mixture is refluxed for 4 hours. After cooling, the mixture is rendered alkaline using 2N sodium hydroxide solution. The precipitate is filtered off, washed using 200 ml of water and dried. - 49 - This gives 38.1 g (95% of theory) of 6,6-difluOTo[l,3]doxolo[4,5-fJbenzimidazole in the form of a solid.

The substances listed in the table which follows are also prepared by the methods given above. 50 - Table 17: Ex. l R2 R3 R4 A X Physical , No. constant 2 H -0-CF2-CF2-0- H Br m.p.: 90°C (Decomp.) 3 H -0-CFrCF2-O- H HaC Br m.p.: 115- 3 \ N — SO-- 119°C / z H3C 4 H -0-CF2-0- H H3C Br m.p.: 112- N — SO,-. 115°C H3C H H H HaC SO,— CI m.p.: 48-. 53°C 6 H -0-CFj-O- H Br m.p.: 117- 124° C Table 17 (continued) Tahle 17 (continued) -53 - Table 17 (continued) Tabfe 17 (continued) Tabie 17 (continued) Table 17 (continued) *) The ¾ NMR spectra were recorded in hexa-deuterodimethyl sulphoxide (DMSO-D^ using tetramethylsilane (TMS) as the internal standard. The value given is the chemical shift, δ, in ppm. 57 - Example 36 Process (c) Hydrogen chloride gas- is passed for 2 hours at 120°C into a solution of 2.8 g (10 mmol) of 2-bromo-6,6-di£luoro[1 ]diox in 30 ml of dimemylforrnamide. The mixture is poured onto 200 g of ice/water and extracted three times using in each case 80 ml of ethyl acetate. The combined organic extracts are dried over sodium sulphate and concentrated under reduced pressure. The residue is chromatographed on silica gel using diethyl ether. This gives 0.5 g (21.5% of theory) of 2-cbloro-6,6-difluoro[l,3]&ox as a white solid of melting point > 220°C.

Example 37 2-Bromo-6,6,7,7-tetrafluoro[l,4]dioxino[2,3-f]benziinidazole is also prepared by the method described in Example 1.

Melting point: 170-174°C Example 38 (Π-4) - 58 - 2-CMoro[l,4]dioxino[2,4-f]beiiziiriida2ole is also prepared by the method described in Example 1.

Melting point: 150°C Example 39 e^^ -Tetrafluorofl^Jdioxmop^-fl enzir idazole is also prepared by the method described in Example 1.

Melting point: 70-74°C - 59 - Use Examples Exampte A Phytophthora test (tomato)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dew moist. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans.

The plants remain in an incubation cabin at 100% relative atmospheric humidity and approx. 20°C.

The test is evaluated 3 days after inoculation. 0% means an efficacy which corresponds to the control while an efficacy of 100% means that no disease is observed.

Active compounds, active compound concentrations and test results can be seen from the table which follows. 60- Table.A Phytophthora test (tomato)/protective) -61'- Table A (Continued) Phytophthora test (tomato)/protective) Table A (Continued) Phytophthora test (tomato)/protective) Table A (Continued) Phytophthora test (tomato)/protective) Table A (Continued) Phytophthora test (tomato)/protective) - 65 - Example B Plasmopara test (vines)/protective Solvent: 4.7 parts by weight of acetone Emulsifier 0.3 part, by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in a humid chamber at 20 to 22°C and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse at 21°C and about 90% atmospheric humidity for 5 days. The plants are then moistened and placed in a humid chamber for 1 day.

The test is evaluated 6 days after inoculation. 0% means an efficacy which corresponds to the control while an efficacy of 100% means that no disease is observed Active compounds, active compound concentrations and test results can be seen from the table which follows. . -66- Table B: Plasmopara test (vines)/protective Table B (continued) Plasmopara test (vines)/protective Active compound Efficacy in % based on the untreated control at an active compound concentration of 50 ppm 1 100 H,C SO, w , - CH 96 F SOj— CH3 ^2Q) - 69 - Exam le C Venturia test (apple) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with, the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the pathogen causing apple scab (Venturia inaequalis) and then remain in an incubation cabin at 20°C and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20°C and a relative atmospheric humidity of about 70% .

The test is evaluated 12 days after inoculation. 0% means an efficacy which corresponds to the control while an efficacy of 100% means that no disease is observed.

Active compounds, active compound concentrations and test results can be seen from the table which follows.

Table C Venturia test (apple)/protective Passages of the description which are not within the scope of the claims do not constitute part of the invention.

Claims (2)

142975/2 71 CLAIMS:

1. Benzimidiazoles of the formula in which R represents hydrogen, halogenoalkoxy or halogenoalkylthio, R15 represents hydrogen, halogenoalkoxy or halogenoalkylthio, R16 represents hydrogen, halogenoalkylthio or halogenoalkoxy, with the exception of pentafluoroethoxy, 17 R represents hydrogen, halogenoalkylthio or halogenoalkoxy, with the exception of pentafluoroethoxy and, 12 15 16 17 but where at least one of the radicals R , R , R'° and R" is other than hydrogen, or R12 and R16, or R16 and R17, or R17 and R15, in each case together with the carbon atoms to which they are bonded, form a five-or six-membered heterocyclic ring having one or 2 (non-adjacent) oxygen atoms which is at least monosubstituted by halogen. 142975/2 72

2. Process for the preparation of benzimidazoles of the formula (IVa) according to Claim 1 , characterized in that d) phenylendiamines of the formula in which R , R , R and R have the above mentioned meanings are reacted with formic acid, with one of its salts or with one of its derivatives, if appropriate in the presence of a diluent. For the Applicants, REINHOLD COH AND PARTNERS