CA2148613C - 2-perhalogenalkyl-substituted benzimidazoles, their preparation and their use as pesticides - Google Patents

Abstract

The invention relates to new substituted benzimidazoles of the general formula (I)

Description

., BAYER AKTIENGI:SELLSCHAFT 51368 Leverkusen Konzernverwaltung RP
Patente Konzern RT/li-359w Substituted benzimidazoles The invention relates to new substituted benzimidazoles, to a number of processes for their preparation and their use as agents for combating pests.
It is known that certain phosphoric acid esters or carbamates, such as, for example, the compound O,S-dimethyl-thiolo-phosphoric acid amide or the compound N-methyl-O-(2 isopropoxyphenyl)-carbamate possess insecticidal properties (cf. e.g. DE-12 10 835 or DE 11 08 202).
However, the extent and/or duration of the action of these previously known compounds, especially on certain insects or at low application concentrations, is not completely satisfactory in all areas of application.
New substituted benzi;midazolea of the general formula (I) X
a X. N
yRs ~I) Xs ~ N

X y R
have now been found, in which Le A 29 089-PCT

~~~~~1~
R1 represents hydrogen, alkyl or optionally substituted aryl, RZ represents hydroxyl, cyano, alkoxy or optionally substituted amino, R3 represents perhalol;enoalkyl, and Xt, X2, X3 a~ld X4, iindependently of one another, in each case represent hydrogen, halogen., nitro or optionally substituted aryloxy, but with at least one of the substituents X1, X2, X3 or X4 being different from hydrogen, with the exception of t:he compound 1-cyanomethyl-2-trifluoromethyl-5,6-dichlorbenzimidazole.
The compounds of the formula (I) may if appropriate, depending on the nature and number of the substitvuents, be; present as geometric and/or optical isomers or regio-isomers, or their isomer mixtures in varying composition. Both the pure isomers and the isomer mixtures a~-e claicne;d according to the invention.
It has also been found that the new substituted benzimidazoles of the general formula (I) X
z X. w N
3 ~ / ~~ R3 X ~N
X CH-R
R
l5 in which R~ represents hydrogen, alkyl or optionally substituted aryl, R2 represents hydroxyl, cyano, alkoxy or optionally substituted amino, Le A 29 089-PCT - 2 -~~~~~~3 R3 represents perhalo~;enoalkyl, and X~, X2, X3 at~d X4, independently of one another, in each case represent hydrogen, halogen, nitro or optionally substituted aryloxy, but with at least one of the substitu~ents Xt, X2, X3 or X4 being different from hydrogen, with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-dichlorbenzimidazole, are obtained if 1 H-benzimidazoles of the formula (II) X
r 2 N
y Rs X3 ~ N
H
X
(II) in which l0 R3, X~, X'', X3 and X4 have the meaning given above, are reacted with compounds of the formula (III) R
A-CH z (III) R
in which A represents a suitable leaving group, R~ has the meaning given above and Le A 29 089-PCT - 3 -R2 has the meaning given above optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary.
Finally, it has been found that the new substituted benzimidazoles of the general formula (I) possess a l;ood actiivity against pests.
Surprisingly, the substiituted be:nzimidazoles of the general formula (I) according to the invention exhibit a considerably improved insecticidal activity in comparison to the phosphoric acid esters or carbtunates known from the prior art, such as, for example, the compound O,S-dimethyl-thiolo-phosphoric acid amide or the compound N-methyl-l.0 O-(2-isopropoxyphenyl)-carbarnate, which are closely related compounds in terms of their action.
A general definition of the substituted benzimidazoles according to the invention is given by the formula (;I). Preferred compounds of the formula (I) are those in which R~ represents hydrogen, slxaight-chain or branched alkyl having 1 to 8 carbon 1'a 5 atoms or phenyl which is optionally substituted once or more than once by identical or different substituents, possible substituents being:
halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case I to 6 carbon atoms, in each case straiight-chain or branched halogenoalkyl, haIogenoalkoxy, :?0 halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case sl:raight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl, alkoxycarbonyl or alko;~iminoalkyl having in each case 1 to 6 carbon atoms in the individual alkyl moieties, divalent dioxyalkylene having I to 5 carbon atoms :?5 which is optionally substituted once or more than once by identical or different substituents comprising halogen and/or straight-chain or branched alkyl having 1 to 6 carbon atoms and/or straight-chain or branched halogenoalkyl having 1 Le A 29 089-PCT - 4 -V ~ ~. 4-~ ~ :~
to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or phenyl which is optionally substituted once or more than once by identical or different substituents comprising halogen and/or straight-chain or branched alkyl having 1 to 6 carbon atoms and/or straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, R2 represents hydroxyl, cyano, alkoxy having 1 to 8 carbon atoms or amino which is optionally substituted once or twice by identical or different substituents, possible substi~:uents being:
straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or l0 branched alkenyl having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, alkoxyc:arbonyl., alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-thiocarbonyl having in each case 1 to 8 carbon atoms in the individual straight-chain or branched alkyl. moieties, a divalent closed alkanediyloxycarbonyl ring having 2 to 6 carbon atoms in the alkanediyl moiety, or arylalkyl or aryl having t 5 in each case 6 to 10 carbon atoms in the aryl moiety and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, each of which is optionally substituted once or more than once by identical or different substit-uents, possible substituents of aryl in each case being those mentioned for R1, R3 represents straight-chain or branched perhalogenoalkyl having 1 to 8 carbon :?0 atoms and 1 to 17 identical or different halogen atoms, and Xl, X2, X3 and X4, independently of one another, in each case represent hydrogen, fluorine, chlorine, bromine, iodine, nitro or aryloxy having 6 to 10 carbon atoms in the aryl moiety which is optionally substituted in the aryl moiety once or more than once by identical or different substituents, possible possible 25 substituents of aryl being those mentioned for R1, but with at least one of the substituents X~, X2, X3 or X4 being different from hydrogen, and with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-dichlorobenzimidazole.
Le A 29 089-PCT - S -~14~~~3 Particularly preferred compowlds of the formula (I) are those in which Ri represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl which is optionally substituted once to three times by identical or different suhstituents, possible substituents being:
halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 4 carbon atoms, in each case straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case' straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl, alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 4 carbon atoms in the individual ~31ky1 moities, divalent dioxyalkylene having 1 to 4 carbon atoms which is optionally substituted once to six times by identical or different substituents comprising. halogen and/or straight-chain or branched alkyl having 1 to 4 carbon ;atoms and/or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, or phenyl which is optionally substituted once to five times by identical or different substituents comprising halogen and/or straight-chain or branched alkyl having I to 4 carbon ,atoms and/or straight-chain or branched halogenoalkyl having I
to 4 carbon atoms and 1 to 9 identical or different halogen atoms, R2 represents hydroxyl, cyano, alkoxy having 1 to 6 carbon atoms or amino which is optionally substituted once or twice by identical or different substituents, possible substi tuents being:
straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, alkoxy~~arbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-thiocarbonyl h;iving in each case 1 to 6 carbon atoms in the individual straight-chain or branched alkyl moieties, a divalent closed alkanediyloxycarbonyl ring having 2 to 5 carbon atoms in the alkanediyl moiety, or arylalkyl or aryl having Le A 29 089-PCT - 6 -~~~.~6~3 in each case E~ or 10 carbon atoms in the aryl moiety and optionally 1 to 6 carbon atoms iin the straight-chain or branched alkyl moiety, each of which is optionally substituted once to five times by identical or different substituents, possible substituents of aryl being those mentioned for R~, R3 represents straight-chain or branched perhalogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, and X~, X2, X3 and X4, independently of one another, in each case represent hydrogen, fluorine, chlorine, bromine, iodine, nitro or aryloxy having 6 or 10 carbon atoms in the aryl moiety, which is optionally substituted once to five times by identical or tii:fferent substituents, possible possible substituents of aryl being those mentioned for R~, but with at least one of the substituents X1, X2, X3 or X4 being different from hydrogen, with the exception of tlhe compound 1-(cyanomethyl-2-trifluoromethyl-5,6-dichlorobenzimidazole. Prefewed aryl radicals which can be mentioned are phenyl and naphthyl.
Compounds of the formula (I) which are very particularly preferred are those in which Rt represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or phenyl which is optionally substituted once or twice by identical or different substiituents, I>ossible substituents being:
halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 3 carbon atoms, in each case straight-chain or brmched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, in each case straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl, alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 3 carbon atoms in the individual alkyl moiieties, divalent dioxyalkylene having 1 to 3 carbon atoms Le A 29 089-PCT - 7 -which is optionally sulbstituted once to four times by identical or different substituents comprising halogen and/or straight-chain or branched alkyl having 1 to 3 carbon ~~toms and/or straight-chain or branched halogenoalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, or phenyl S which is optionally substituted once to tluee times by identical or different substituents comprising halogen and/or straight-chain or branched alkyl having 1 to 3 carbon atoms and/or straight-chain or branched halogenoalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, R2 represents hydroxyl, cymo, alkoxy having 1 to 6 carbon atoms or amino which is optionally substituted once or twice by identical or different substituents, possible substituents being:
straight-chain or branched alkyl having I to 4 carbon atoms, straight-chain or branched alken,yl having; 2 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-thiocarbonyl having in each case 1 to 4 carbon atoms in the individual straight-chain or branched alkyl moieties, a divalent closed alkanediyloxycarbonyl ring having 2 to 4 carbon atoms in the alkanediyl moiety, or phenylalkyl or phenyl having optionalily 1 to :3 carbon atoms in the straight-chain or branched alkyl moiety, each of which is optionally substituted once or twice by identical or a0 different substctuents, possible substituents of phenyl in each case being those mentioned for lfZl, R3 represents straight-chain or branched perhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, or cyano, and X~, X2, X3 and X4, independently of one another, in each case represent hydrogen, chlorine, bromiine, nitro or phenyloxy which is optionally substituted in the phenyl moiety up to three times by identical or different substituents, possible substituents of phenyl being those mentioned for R~, but with at least one of the substituents X~., X2, X3 or X4 being different from hydrogen, Le A 29 089-PCT - 8 -~.~~3~~3 with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-dichlorobenzimidazole.
Apart from the compounds mentioned in the Preparation Examples, the following individual substituted benzimidazoles of the general formula (I) may be mentioned:
Le A 29 089-PCT - 9 -~~4~~~
x x..~ ~, N
s~l , \~R3 ~N
\C H-R2 X
R

Br H CI H H i zHs CF3 N
~COOCZHS

Br H Br H H i zHs CF3 N
~COOCZHs Br H NO2 H H CzHs CF3 N
~COOCZHs CI H Ca H H i zHs CF3 N
~COOCZHS

CI H Br H H i zHs CF3 /N
~COOCZHS
H H N02 H H i zHs CF3 N
~COOCzHs Le A 29 089-PCT - 10 -Br H CE;H50 H H CZHS CF3 N
~ ~COOCZHS

C1 H c~ H H C2H5 CF3 cy ~ o- N
C ~ ~

c~ COOCZHs Cl H c~
H H CI.~HS CF3 cy~o- N
C~ ~ ~

COOCZHS

Br H ~Cl H H CI.~Hs CZFS
/N
~COOC~HS
Br H Br H H C~..~Hf C2F5 /N
~COOCzHs H CI ' Cl H H i~Hs C2F5 /N
~COOC~HS
Cl H c' H H -O-C2H5 CF3 cy ~ o-C1 H c' H H -O-C2H5 CF3 r=''~
cy~o-Le A 29 089-PCT - 11 Br H CI H H CZHS C2F5 N
~COOC2H5 Br H E3r H H i NHS C2F5 N
~ ~COOC,HS

H CI ~ (:1 H H i ZHs C2F5 N
~ ~COOC=HS

Br H rd02 H H CZHS C2F5 N
~COOCzHt N
~COOCZHS

Cl H lBr H H i ?Hs C2F5 .

/N
~COOCZHs H H N02 H H i NHS C2F5 /N
~COOC2H5 Le A 29 089-PCT - 12 -~~.48~~~

Br H C6H50 H H i ZHS C2F5 N
~COOCZHS
Cl H c' H H CzHs C2F5 cy/ o~ N
ct '/ \COOCzHs E
Cl H c' H H i ?Hs C F

~~\ /~°- N
~COOCZHS
Br H (:1 H H -0-C2H5 C2F5 Br H Etr H H -O-C2H5 C2F5 H Cl (:l H H -O-C2H5 C2F5 Br H NOZ H H -0-CZHS C2F5 C( H C:1 H H -O-C2H5 C2F5 CI H Ear H H -O-C2H5 C2F5 Br H C6H50 H H -O-C2H5 C2F5 Cl H c' H H
_ 0 C2H5 C2H5 c'-~_ / o-c' Cl H c' H H

ct-~_~o-Le A 29 089-PCT - 13 -Br H C! H H i ZHs n-C3F~
N
~COOCZHS
Br H Br H H i zHs n-C3F7 N
~~COOCzHs i H C! ~C! ~~ H i NHS n-C3F7 N
~~COOCzHs Br H N02 H H CzHs n-C3F7 N
~ COOCZHS
Cl H C:l H H i zHs n-C3F7 N
~ ~ COOCZHS
Cl H Br H H i ZHS n-C3F7 N
~COOCZHS
Le A 29 089-PCT - 14 -~~~~~~3 H H N02 H H i zHs n-C3F2 N
~COOCzHs Br H CE;H50 H H j ZHS n-C3F~
/N
~COOCZHS
i CI H ~ H H i zHs n-C3F~
ct~ ~ o- N
ci ~ \COOCzHs CI H c' H H i ZH5 n-C3F7 cy~o- N
~COOC~HS
Br H CI H H -O-CZHS n-C3F~

Br H 13r H H -O-CZHS n-C3F~

H C1 CI H H -O-C2H5 n-C3F~

Br H N02 H H -O-C2H5 n-C3F~

Cl H CI H H -O-C2H5 n-C3F~

Cl H Br H H -O-C2H5 n-C3F~

H H N02 H H -O-C2H5 n-C3F~

Br H C67H50 H H -O-C2H5 n-C3F2 Cl H c~ H H -O-C2H5 n-C3F~

cy 1 0-c~

Le A 29 089-PCT - 15 -,. L
X1 X2 X3 X4 Rl R2 R3 C1 H c~ H H -O-C2H5 n-C3F~
ci ~~o-CI H " H H -O-C2H5 CF3 F,C-~-Cl C1 H " H H -O-C2H5 C2F5 F,C~-~ O-' CI

CI H " H H -O-C2H5 n-C3F~

F,C--CI H _ H H CZHS CF3 F,C ~
~ O

- N
c~ / \COOC2H5 CI H " H H C~HS C2F5 i ~

F,'- /N \
-c~ COOC2H5 CI H " H H CZHS n-C3F~

F,c ~ ~ o-/ \

c~ COOC~HS

Le A 29 089-PCT - 16 -x1 XZ :K3 X4 R1 R2 R3 C1 H CI H H -O-C2H5 n-C7H15 H Cl C1 H H -O-C2H5 n-C7H15 CI H CI H H i ZHS n-C7H15 N
~COOC~ HS
H CI CI H H ~CZHS n-C7H15 N
~ ~COOCzHs i CI H '" H H CZHs n-C7H 15 F~c- / \ o-N
ci ~ ~COOCzHs Using, for example, 5,6-dichl.oro-2-trifluoromethyl-benzimidazole and chloromethyl ethyl ether as starting compownds, the course of the reaction of the process according to the invention can be represented by the following formula scheme:
CI
~~-C F3 + C I-C HZ O-C 2H5 CI
H
- HCI CI ~ N
Base ~ ~ ~ \' CF3 CI
CH2 O-CzHs general definition of the 1 H-benzimidazoles required as starting substances for carrying out the process accordling to the invention is given by the formula (II). In this formula (II), R.3, X~, X2, X.3 .and X4 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds ~of the formula (I) according to the invention.
Le A 29 089-PCT - 17 -The 1 H-benzimidazoles of the; formula (1I) are known or can be obtained by analogy with known processes (cf. e.g. J. Amer. Chem. Soc. 75, 1292 [1953]; US

3,576,818).
A general definition .of the compounds additionally required as starting materials for carrying out the process according to the invention is given by the formula (III). In this formula (III), R~ and R2 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.
A preferably represents a leaviing radical which is usual in alkylating agents, preferably halogen and in particular chlorine, bromine or iodine, or represents in each case optionally substituteid ,alkylsulphonyloxy, alkoxysulphonyloxy or arylsulphonyloxy, such as, in particular, methanesulphonyloxy, trifluoromethanesulphonyloxy, methoxysulphonyloxy, ethoxysulphonyloxy or p-toluenesulphonyloxy.
In addition, A also represents, an alcohol, alkanoyloxy or alkoxy group, such as, for example, a hydroxyl, acetoxy or methoxy group if the intention is to use the process 1 S according to the invention to prepare compounds of the formula (I) in which RI is different from hydrogen.
The compounds of the formula (III) are known or can be obtained by analogy with known processes (c~ e.g. DE 20 40 175; DE 21 19 518; Synthesis 1973, 703).
Suitable diluents for carrying; out the process according to the invention are inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated, hydrocarbons such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dic;hlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; ethers such as diethyl ether, diisopropyl ether, dioaane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether;
ketones such as accaone, butanone or methyl isobutyl ketone; nitrites such as acetonitrile, propionit~rile or benzonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphori~~ triamid,e; esters such as methyl acetate or ethyl acetate, or bases Le A 29 089-I'CT - 18 -such as pyridine, or organic acids such as formic acid or acetic acid.
The process according; to the invention is preferably carried out in the presence of a suitable reaction auxiliary. Suitable such auxiliaries are all conventional inorganic or organic bases. 'they include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, a'.~~coholatea, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, lithium diethylamide, sodium methylate, sodium ethylate, potassium tert-butylate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, organolithium compounds such as n-butyllithium, and tei'ti;~cy amines such as trimethylamine, triethylamine, tributylamine, di-isopropyl-ethylamine, tetramethylguanidine, N,N-dimethylaniline, pyridine, piperidine, N-methylpiperidi:ne, N,N-dimethylaminopyridine, diazobicyclooctane (DABCO), diazobicyclononenf: (DBN) or diazabicycloundecene (DBU).
In cases where the int~:ntion is to use the process according to the invention to prepare compounds of the forrnula (L) in which Rl is different from hydrogen, suitable reaction auxiliaries also include; organic or inorganic acids, such as, for example, sulphuric acid, hydrochloric acid, p-toluenesulphonic acid and perfluorobutanesulphonic acid, or strongly acidic ion exchangers.
:20 The process according to the invention can optionally also be carried out in a two-phase system such as, for example, water/toluene or water/dichloromethame, optionally in the presence of a suitable phase-transfer catalyst. Examples which may be mentioned of such catalysts are: tetrabutylammonium iodide, tetrabutylaunmonium bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C ~
3/C I s-:25 alkylammonium chloride, trimethyl-C~3/C~5-alkylammonium bromide, dibenzyl-dimethyl-ammonium methyl sulphate, dimethyl-C ~ 2/ C 14-alkyl-benzylammonium chloride, dimethyl-C~2/C~4-al'~kyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris-[2-(2-30 methoxyethoxy)-ethyl:-amine.
Le A 29 089-PCT - 19 -~.~~-8~~ 3 When carrying out the process according to the invention, the reaction temperatures can be varied over a relatively wide range. It is in general carried out at temperatures of between -70°C and +;!00°C, preferably at temperatures of between 0°C and 130°C.
The process according to the invention is usually carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.
Carrying out the process according to the invention requires the use, per mole of 1 H-benzimidazole of the formula (II), of in general from 1.0 to 5.0 mol, preferably from 1.0 to 2.5 mol, of compound of the formula (III) and optionally from 0.01 to 5.0 mol, preferably from 1.0 to 3.0 mol, of reaction auxiliary.
In a particular embodiment it is also possible first of all, in a prior reaction step, to silylate the 1H-benzimidazoles of the formula (II) using conventional silylation processes, for example, with hexamethyldisila~zane or trimethylsilyl chloride, optionally in the presence of a suitable cai:alyst such as, for example, sulphuric acid, trifluoroacetic acid, ammonium sulphate, imiidazole or saccharin, at temperatures of between -20°C
and +150°C, and in a subsequent, second step to react the 1-tri-methylsilylbenzimidaz;oles, which are obtainable in this way, with alkylating agents of the formula (II) in accordance with the process according to the invention. In this case it is of advantage to add tin tE;trachloride as a catalyst for the alkylation reaction (cf.
e.g. Chem. Heterocycl'~,. Comp. USSR 24, 514 [1988]).
The implementation o~f the reaction, the working-up and the isolation of the reaction products are carried out by IUnown methods (cf. also in this respect the Preparation Examples).
The purification of the: end products of the formula (I) is carried out using conventional methods, for example by column chromatography or by recrystallization.
Characterization is carried out on the basis of the melting point or, in the case of non-crystallizing compounds - especially in the case of regioisomer mixtures -using proton nuclear magnetic resonance spectroscopy (1H-NMR).
Le A 29 089-PCT - 20 -The active substances are suitable for combating animal pests, preferably arthropods and nematodes, in pau-ticular insects and arachnids, which are encountered in agri-culture, in forests, in 'the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species and against all, or individual, dev~~lopmemtal stages.
The abovementioned bests include:
From the order of the: Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber;
from the order of the Diplopoda, for example, Blaniulus guttulatus;
from the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.; ' from the order of the Symphyla, for example, Scutigerella immaculate;
from the order of the Thysanura, for example, Lepisma saccharine;
from the order of the Collembola, for example, Onychiurus armatus;
from the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, :Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Mel.anoplus differentialis and Schistocerca gregaria;
from the order of the Dermapl:era, for example, Forficula auricularia;
from the order of the Isoptera, .for example, Reticulitermes spp.;
:20 from the order of the Anoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.;
from the order of the lVlallophaga, for example, Trichodectes spp. and Damalinea spp.;
from the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci;
from the order of the Heteropte:ra, for example, Eurigaster spp., Dysdercus intermedius, Piesma quadrate, Cirr~ex lectularius, Rhodnius prolixus and Triatoma spp.;
from the order of the Homoptera, for ex~~nple, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis g;ossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rho;palosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticef~s, Lecanium corm, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, ~,onidiell;~ aurantii, Aspidiotus hederae, Pseudococcus spp. and Le A 29 089-PCT - 21 -Psylla spp.;
from the order of th~~ Lepidoptera, for example, Pectinophora gossypielta, Bupalus piniarius, Cheimatobia brurnata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
Bucculatrix thurberielta, Phylllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia titura, Spodoptera spp., Trichoplusia ni, Caprocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubitalis, Ephestia kuehnietta, Galleria mellonella, Tineola bissellietla, Ti:nea peltionetta, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana;
from the order of 'the Coleoptera, for example, Anobium punctatum, lZhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica atni, Leptinotarsa decemlinea~ta, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephata, Epilaclma varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assiimilis, l~ypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Atta~,enus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio motitor, Agriotes spp., :20 Conoderus spp., Melolontha metotontha, Amphimallon sotstitialis and Costelytra zealandica;
from the order of the: Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.;
from the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., :25 Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephata, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderrr~a spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinetta frit, Phorbia spp., Pc:gomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa;
:30 from the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spP~
from the order of the Araclmida, for example, Scorpio maurus and Latrodectus mactans;
Le A 29 089-PCT - 22 -.
from the order of the ~~carina, l;or example, Acarus Biro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriopllyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomzna spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.
and Tetranychus spp.
The phytoparasitic pematodEa include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., :Longidorus spp, Xiphinema spp. and Trichodorus spp..
The active substances according to the invention are active not only against pests in plants, hygiene and's~tored goods, but also, in the veterinary sector, against animal parasites (ectoparasites and endoparasites) such as ixodic ticks, argasid ticks, scab mites, trombiculid mitEa, flies (piercing and lapping), parasitizing fly larvae, lice, biting lice, feather lice, fleas and wo~:-ms which live as endoparasites.
They are effective against normally sensitive and resistant species and strains, and l5 against all parasitizin;; and non-parasitizing developmental stages of the ecto- and endoparasites.
The active substances according to the invention are notable for a high degree of insecticidal activity.
They can be employed with particularly good success for combating phytopathogenic :Z0 insects, as, for example, against the larvae of the mustard beetle (Phaedon cochleariae) or against the caterpillars of the cabbage moth (Plutella maculipennis) or against the tobacco budworm (Heliothis virescens), and for combating phytopathogenic mites, as, for example, against the red spider mite (Tetranychus urticae) or for combating phytopathogenic nematodes, as, for example, against the nematode species Globodera :ZS rostochiensis.
In addition, the active substances according to the invention can also be employed for combating pests in hygiene and stored goods, as, for example, against the house-fly Le A 29 089-PCT - 23 -~~48~I3 (Musca domestics) or against cockroach species, such as, for example, Periplaneta americana.
Moreover, the active; substances according to the invention can be employed with particularly good success for combating pests which live as parasites of warm-blooded creatures, as, for example, against scab mites (Psoroptes ovis).
In addition, the active substances according to the invention also possess a fungicidal activity in vitro.
Depending on their particular iphysical and/or chemical properties, the active substances can be converted 'into the customary formulations, such as solutions, emulsions, suspensions, powders,, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with aeti~,ve substance, very fine capsules in polymeric substances and in coating compositions for seed, and furthermore in formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and ~ the like, as well as ULV cold mist and warm mist formulations.
These formulations are produced in a known manner, for example by mixing the active substances with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic; solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphrhalenes, chlorinated aromatics or chlorinated aliphatic hydro-carbons, such as chlorobenzc.nes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water;
by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as Le A 29 089-PCT - 24 -~14~~~~
solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, at~tapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are: suitable: for example crushed and fractionated natural rocks such as calcite, marble:, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic: and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite wash liquors and methylcellulose.
Adhesives such as carboxymeahylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can bf: used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal plzthalocy;mine dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and tin.
The formulations in general contain between 0.1 and 95 per cent by weight of active substance, preferably between 0.5 and 90%.
The active substances according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations, as a mixture with other active substances such as insecticides, attractants, sterilizers, aca.ricides, nematicide~s, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by Le A 29 089-PCT - 25 -microorganisms, etc.
Furthermore, the acti~re substances according to the invention can be present in their commercially availal;~le formulations and in the use forms prepared from these formulations as a miraure with synergists. Synergists are compounds which raise the activity of the active substances without the synergist which is added necessarily being active itself.
The active substance,content oiFthe use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.00000(11 up to 95 per cent by weight of active substance, preferably between U.~D001 and 1 per cent by weight.
Application is effected in a customary manner appropriate to the use forms.
When used against pests in hygiene and stored goods, the active substances are notable for an outstanding residual action on wood and clay and for a good alkali stability on limed substrates.
The active substances which can be used in accordance with the invention are also suitable for combating insects, mites, ticks etc. in the sector of animal husbandry and cattle rearing, the combating of the pests enabling better results to be achieved, e.g.
higher milk yields, greater weiight, more attractive coats, longer lifespan etc.
In this sector, the application of the active substances which can be used in accordance :20 with the invention is c,~rried out in a known manner, for example by oral administration in the form of tablela, capsules, drinking formulations or granules, by dermal or external application in the forms of, for example, dipping, spraying, pouring on (pour-on or spot-on) and powdering, and by parenteral administration in the form, for example, of injection, and, furthermore, by the feed-through method. In addition, application as :25 a shaped article (collar, ear-tal;) is also possible.
The preparation and the use .of the active substances according to the invention is evident from the following examples.
Le A 29 089-PCT - 26 -..
Preparation Exam~~s:
Example 1:
CI~ ~ N
~~ ~~--CF3 CI~ '~ N
v A solution of 14.1 g (0.15 mol) of chloromethyl ethyl ether in 40 ml of ethyl acetate is added dropwise to ;a mixture of 36 g (0.12 mol) of 5,6-dichloro-2-trifluoromethyl-I H-benzimidazole, 33 g (0.24 mol) of powdered potassium carbonate and 300 ml of ethyl acetate at room t~cmperah~re, and, after addition is complete, the mixture is heated for a further 4 hours .at boiling temperature. For working up, the reaction mixture is cooled and washed twice with 150 ml of water each time, dried over sodium sulphate and concentrated in vacuo. The residue is purified by chromatography on silica gel (eluent: dichloromethane).
32.4 g(83%oftheory)of5,6-dichloro-1-ethoxymethyl-2-trifluoromethyl-benzimidazole are obtained with a melting point of 89-92°C.
In a corresponding manner and in accordance with the general instructions for the preparation, the following substituted benzimidazoles of the general formula (I) are 'L 5 obtained:
i X

X. ~ N
3 ~ / ~~ R3 X _' N
\C H-RZ
X
R
Le A 29 089-PCT - 27 . . ~ (~
Ex. X1 X2 X 3 X4 R~ R2 R3 physical No. properties 2 H CI CI H 1(-3 CHj CF3 m.p.120-121°C
I
N
~ ~COOCH3 3 H CI Cl H H CH3 CF3 m.p. 9S-97°C
N
~ ~COOC~HS

4 H CI CI H H j ZHS CF3 m.p. 104-106°C
/N
~COOCzHs S H CI CI H H i ?Hs CF3 m.p. 88-89°C
/N
~COOCH3 6 H Cl CI H H n-C~,H~ CF3 m.p.102-103°C
N
'~ ~COOCH3 7 CI H CI H H -O-C2HS CF3 m~P~ 57-61°C
(H) (CI) (H) (CI) (87:13) 8 CI H CI H Hf CH3 CF3 m.p. 95-100°C
(H) (C1) (H) (CI) I (92:8) /N
~COOCH3 9 H Cl H H H -O-CH(CH3)2 CF3 1 H_~ *):
(H) (~'() 5.63; S.6S; 7.35;
' 7.40; 7.57; 7.78 ;
7.63; 7.85 Le A 29 089-PCT - 28 -Ex. X1 X2 ~i'3 X4 Rl R2 R3 physical No. properties H CI I-f H H CN CF3 IH-NMR*):

5.15; 5.18; 7.45;
(H) (CI) 7.55; 7.83; 7.90 I 1 H CI H H H -0-C2H5 CF3 I H-NMR*):
(H) (C11) 5.43; 5.48; 7.28-8.01 12 H CI 'H H H -O-C2H5 CF3 m.p.75°C
13 H H Cl H H -O-C2H5 CF3 m.p.73°C
14 H CI Hi H H CH3 CF3 1H-NMR*):
5.88; 5.92; 7.35;
(H) (C1) ~N~COOCzHs 7.67; 7.92 I S H CI H H H i ZHS CF3 1H-NMR*):
(H) (C1) N 5.88; 5.90; 7.41;
~COOCzHs 7.79; 7.81 16 H CI H H H n-C3H, CF3 1H-NMR*):
5.89; 5.96; 7.37;
~N~COOC2H5 7.78; 7.78; 7.81 17 H Cl H: H H OH CF3 18 H N02 H H H -O-C2H5 CF3 IH-NMR*) (H) ~~~2) 7.79-8.78;

A: 5.73 B: 5.74 19 H N02 H: H H -O-C2H5 CF3 m.p.:48C

Le A 29 089-PCT - 29 -~~.4~~~
Ex. X1 X2 I~'3 X4 Rl R2 R3 physical No. properties ~0 H H N02 H H -O-CZHS CF3 m.p. ; 90°C
2l H N02 H Ei I-I -O-n-C3H~ CF; 1H-NMR*) 7.so-s.7o;
(H) (N02) A:5.80 B: 5.85 22 H N02 H H H CH3 CF3 1H-~*).
7.95-8.80; .
~~02) /N~ A: 5.96 COOCZHS
B: 5.99 23 H N02 H H H CZHs CF3 1H-NMR*):
7.90-8.75;
(H) (Td02) /N~ A:5.97 B: 5:38 24 H N02 H H H n~3H~ CF3 1H-NMR*)-7.91-8.80; .
(H) (h(O2) /Ny A:5.97 COOCZHS
B: 5.99 25 H N02 H H H OH CF3 1H-NMR~~
7.85-8.9;
(H) (I~f02) A:5.85 B: 5.89 26 H F H H H -O-C2H5 CF3 1H-NMRfi):
(H) (F) A: 5.63; 7.10-7.90 B: 5.69 Le A 29 089-PCT - 30 -~~ 4~~~ 3 Ex. X1 X2 X 3 X4 Rl R2 R3 physical No. properties 27 H c~ H H: H -O-C2Hg CF3 1H-NMR*):
cF,- ~~~ o-- 5.61; 5.68; 6.91-7.85 ci (H) cF~~ o_ ci 28 H c~ , H H H -O-n-C3H7 CF3 1H-NMR*):
cF, ~-~ o__ c~ 5.63; 5.79;
o_ 6.82-7.86 H ct ~- c~
( ) 29 H c~ H H H ~H, CF3 1H-NMR*):
CF, ~-~ O- c1 N 5.84; $.86;
~ ~COOCzH, 6.86-7.90 cl ~ --(j''_ (H) ct 3 0 H c~ H H H ~H, CF3 1 H-NMR*):
CF,- ~-~ O-- c1 N 5.80; $.84;
~ ~c~~Hs 6.88-7.89 a (~ c' 31 H c~ H H H n-pH, CF3 1H-NMR*):
CF, ~-~ O-- ~~ N 5.78 (S), -~( ~ ~cooc,x, 5.88 (s), c~ ~a~~o._ (H) ci 6.88-7.95 (m) 32 H c~ H H H CN CF3 1H-NMR*):
cF, ~-~ o-- c~ 5.11; 6.95; 7.04;
_ 7.74 ; 7.93 ci (H) Le A 29 089-PCT - 31 -Ex. X~ X2 X3 X4 R~ Rz R3 physical No, properties 33 Br Cl C:1 H H ~~H~ CF3 m.p.100-103°C
-N
COOCzH, The ~H-NM:EZ spectra were recorded in deuterochloroform (CDCl3) or hexadeutero-dimethyl sulphoxide (DMSO-d6) using tetramethylsilane (TMS) as the internal standard. The value given is the chemical shift as d in ppm.
Le A 29 089-PCT - 32 -~~.4~~~3 Preparation of the sta~-tin~ compound:
Example II-1:
CI ~ ,N
~~-CFa CI ~ N
H
35.4 g (0.2 mol) of 4,5-dichlorophenylene-diamine are heated with 150 ml of trifluoroacetic acid for 3 hours at reflux temperature. For working up, excess trifluoro-S acetic acid is distilled off and the residue is partitioned between 100 ml of water and 300 ml of ethyl acetate. The organic phase is separated off and washed successively with in each case 100 ml of aqueous sodium hydrogen carbonate solution and water, dried over sodium s~~lphate and concentrated in vacuo. The residue is purified by chromatography on silica gel (eluent: cyclohexane/ethyl acetate 1:1 ).
42.1 g (81% of theory) of 5,6-dichloro-2-trifluoromethyl-1H-benzimidazole are obtained with a melting point of 225-230°C.
In a corresponding manner, the following 1 H-benzimidazoles of the formula (II) are obtained:
X

X. ~ N
yR3 (i1) a H
X
Le A 29 089-PCT - 33 -Ex. No. X~ X1 X3 X4 R3 physical properties II-2 H ~I H H CF3 m.p.227°C
CF~~~U-~~CI ~' /-\
(H) ci II-3 H F H H CF3 m.p.213C

(F) II-4 H N02 H H CF3 m.p.151C

(N02) II-5 H CI H H CF3 m.p.193C

(H) (CI) II-6 Cl ' H Cl H CF3 m.p.165-170C

(~ (CI) (~ (C1) II-7 Br (CI) CI H CF3 m.p.195-149C

*> The ~H-NMR spectra were recorded in deuterochloroform (CDC13) or hexade utero-dimethyl sulphoxide (DlvISO-d6) using tetramethylsilane (TMS) as the internal standard. The value given is the chemical shift as d in ppm.
Chloro-(2-halogeno-l~~fluoromethyl-ethoxy)-urethanes of the formula /CHzX
CI--CHz-O-O-C\H

in which X represents fluorine or chlorine [the individual compounds concerned are chloro-(2-fluoro-1-fluoromethyl-ethoxy) methane (formula (I), X = fluorine) and chloro-(2-chloro-1-fluoromethyl-ethoxy) methane (formula (I), X = chlorine)]
are obtainable by reacting halogenated isopropanols of the formula Le A 29 089-PCT - 34 -~CHZX
HO--Cue/ H
\CF-i1F
in which X represents fluorine or chlorine at -20 to +20°C with :formalde:hyde and hydrogen chloride.
They are used for tl'se preparation of substituted benzimidazoles of the formula X
z X ~ N
X/ ~ / N~--C F3 C H2X

X CHZ-O-C/\ H
\C H2F
S in which X represents fluorine or chlorine and Xt, X2, X3 and X4, independently of one another, in each case represent hydrogen, halogen, cyano, nitro, iin each case optionally substituted alkyl, alkoxy, alkyl-thio, alkylsulphinyl, alk:ylsulphonyl or cycloalkyl, optionally substituted, fused-on dioxyalkylene, or represent hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkoxycarbonyl, in each case optionally substituted amino or aminocarbonyl or in each case optionally substituted aryl, aryloxy, arylthio, arylsulphinyl, ;~rylsulpl-~onyl, arylsulphonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylo:hiomethylsulphonyl, but with at least one of the substituents X~, 1 S X2, X3 or x:4 representing a halogenoalkyl with the exception of the chlorometh~~l radical, halogenoalkoxy, halogenoalkylthio, Le A 29 089-PCT - 35 -~14~6~
halogenoalkylsulphinyl., halogenoalkylsulphonyl, alkylsulphonyl, optionally substituted fused-on dioxyalkylene, hydroxycarbonyl, alkylcarbom~l, alkoxycarbonyl, cycloa.lkoxycarbonyl, in each case optionally substituted amino or aminocarbonyl or in each case optionally substituted aryl, arylthio, arylsulphinyl, arylsulplhonyl, arylsulphonyloxy, arylcarbonyl, aryloxycarbonU, arylazo or ary:lthiomethylsulphonyl, from benzimidazoles of the formula X
z X ~ N
X3 ~ / N>--C F3 X H
Example 192 g of 1,3-difluoro-2-propanol were admixed with 66 g of paraformaldehyde (finely powdered). Then, at -10°C, a vigorous stream of hydrogen chloride gas was passed in with stirring until a cllear 2-phase mixture had been formed. Subsequently the organic phase was separated off, dried with calcium chloride and subjected to fractional distillation in vacuo. 183 g (6f% of theory) of chloro-(2-fluoro-1-fluoromethyl-etho~~-)-methane were obtained with a boiling point of 50 to 54°C at 20 mbar.
The cha.rac-teristic absorptions in the NMR spectra were as follows:
IH-NMR: 5.6 ppm arid 4.55 ppm.
~9F-NMR: -233 ppm.
Fluorinated 1,3-benzo-dioxoles of the formula Le A 29 089-PCT - 36 -R
z R. 4 ~ p z C F3 5I \
R3' s ~ 0 CHXCF3 R
in which X represents hydrogen, fluorine, chlorine or bromine, and R1 and R4 may be idc;ntical to or different from one another and in each case denote hydrogen, halogen, C~-C6-alkyl, C~-C6-alkoxy, halogeno-C~-C6-alkyl, C6-Clo-aryl, COOH,'' C:N, NCC), COO-CI-C6-alkyl, NH-C~-C6-alkyl, N(C~-C6-alkyl)2, and R2 and R3 represent I'd02 or NH2, are obtainable by reacting 1,2-~dihydroxybenzenes , R
z R ~ OH
R3 \ OH

R
in which R~ to R4 have the meaning given above, but R1 to R3 do not represent OH, COCI
or S02C1, in the presence of a base and a diluent at -20 to +200°C with a hexafluorobutene of the formula cis-trans Le A 29 089-PCT - 37 -~.~4~~~3 in which X ~ represents hydrogen or halogen and X2 represents halogen, or by reacting 1,2-dihydroxybe:nzenes which are provided with a protective group and are of the formula R
z 5 R ~ OR
R3 \ OH

R
in which R~ to R4 have the me~ming given above and RS represents a protective group or R5, together with R:~, represents a -C(CH3)2-O- radical first with a hexafluorobutene of the formula z cis-trans in which X ~ represents hydrogen or halogen and Le A 29 089-PC'T - 38 -X2 represents halogen, to obtain an intermediiate of the formula R

F~, ~ OR
CF
F~ ~ 4 O-C
R

in which XI and R~ to RS have: the meaning given above, S then eliminating the protective; group RS from the intermediate of the above formula, and then reacting the OH compound thus obtainable with a base, to obtain 1,3-benzo-dioxoles of the above formula.
1,3-Benzo-dioxoles which contain two adjacent amino groups can be converted with trifluoroacetic acid into the corresponding benzimidazole, e.g. of the following formula R
F C-~N / ~ ~~~CF3 H R
in which R~, R4 and X have the meaning given above.
From these compounds it is possible to obtain, by alkylation, benzimidazole derivatives Le A 29 089-PCT - 39 -/R
CH

which are substituted on the nitrogen atom with a R radical.
Le A 29 089-PCT - 40 -2.~4~~~3 Examples Example 1 a 2-(2,2,2-Trifluoroethy l)-2-trifleroromethyl-1,3-benzodioxole 11 g of pyrocatechol vvere dissolved in 200 ml of dimethylfomamide, and 18 g of 45%
S strength by weight aqueous sodium hydroxide solution were added. 20 g of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise at 75°C to the mixture. Stirring was continued at 75°C for 30 minutes. The mixture was then poured into 500 ml of ice-water and extracte~3 with diethyl ether. The organic phase was washed with water, dried with magnesium sulphate and concentrated. Finally, the product was distilled l0 under a high vacuum. The yielLd was 1 S g (= 56%) and the boiling point was 60°C at mbar. The NMR spectra showed the following characteristic absorptions: ~ 9F-NMR:
-59.0 and -84.6 ppm; ~ H-NMR: 3.02 ppm.
Example 2 a 2-( 1-Chloro-2,2,2-triflvuoroethyl)-2-trifluoromethyl-1,3-benzodioxo1e l5 110 g of pyrocatechol were dissolved in 1,500 ml of acetonitrile, and 200 g of triethylamine were added. 235 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise at 75"C to thf: mixture. Stirring was continued at 75°C
for 2 hours.
1,200 ml of the solvent were then distilled off in vacuo and the residue was taken up in 1,500 ml of water. The product was extracted with diethyl ether and the organic :?0 phase was washed twice with 10% strength by weight aqueous sodium hydroxide solution and once with water. After drying with magnesium sulphate the product was concentrated and subjected to :fractional distillation in vacuo. The yield was 258 g (_ 84% of theory). The broiling point was 63°C at 12 mbar. The NMR spectra showed the following characteristic abso~ptions: 19P-NMR: -66.8 and -79.7 ppm; 1H-NMR:
~'.5 4.71 ppm.
Le A 29 089-PCT - 41 -~~_~8~~~
Examples 3a 2-( 1,1,1,4,4,4-Hexafluoro-2-butenoxy)-methoxybenzene 260 g of 2-methoxyyhenol were dissolved in 1 I of dimethylformamide (technical grade), and 220 g of 45% sodium hydroxide solution were added. Then 400 g of 2-chloro-1,1,1,4,4,4-hex~afluoro-2-butene were added dropwise with stirring at 22°C.
Stirring was continued at 22°C' for 2 hours. Then 1.5 1 of ice-water was added and the mixture was extracted with me;thylene chloride.
The combined organic phases were washed twice with 10% strength sodium hydroxide solution and once with saturated NaCI solution, dried with MgS04 and distilled. The yield was 329 g (58% of theory) and the boiling point was 68-70°C at 12 mbar. The NMR spectra showed the following chau~acteristic absorptions: ~9F-NMR: -57.6 and -67.9 ppm; 1 H-NMR: 5.92 ppm.
Example 4a 2-( 1,1,1,4,4,4-hexafluoro-2-bul:enoxy)-phenal IS 286.1 g of 2-(1,1,1,4,4,4-hexa~fluoro-2-butenoxy)-methoxybenzene from Example 3a were dissolved in a mixture of 500 ml of glacial acetic acid and 500 ml of 48%
strength hydrobromic acid, and 5 g of triethylbenzylammonium chloride were added.
The mixture was stirred at a. bath temperature of 150°C until, according to gas-chromatographic monitoring, complete reaction had been achieved. The mixture was :~0 then allowed to cool, and 2 kg of ice-water were added. The aqueous phase was extracted thoroughly vVith Cl-12C:12. After drying with MgS04 the solvent was stripped off and the residue was distilled in vacuo. The yield was 200 g (50% of theory) and the boiling point was 81)°C at 16 mbar. The NMR spectra showed the following characteristic absorptions: ~9F-NMR: -59.6 and -69.6 ppm; ~H-NMR: 6.1 ppm.
Le A 29 089-PCT - 42 -~a.4~~~~
Example Sa 2-(2,2,2-Trifluoroethyl )-2-trifluoromethyl-1,3-benzodioxole 200 g of 2-(1,1,1,4,4,4-hexafluo~ro-2-butenoxy)-phenol from Example 4a were dissolved in 400 ml of acetonitril~e, and 5 g of triethylamine were added. The mixture was stirred at 70°C for 4 h. Distillation wa.s then carried out in vacuo. The yield was 162 g (81 of theory) and the boiling point was 60°C at 10 mbar. The NMR spectra showed the following characteristic absorptions: 19F-NMR: -59.0 and -84.6 ppm; ~H-NMR:
3.02 ppm.
Example 6a 2-(2-Chloro-1,1,1,4,4,4~-hexaflu.oro-2-butenoxy)-1-benzyloxybenzene g of 2-benzyloxyphenol were dissolved in 100 ml of dimethylformamide, and 9 g of 45% strength sodium hydroxide solution were added. 23 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene: were then added dropwise at room temperature.
After the exothermic reaction had sulbsided the mixture was stirred at room temperature for 15 a further 1 hour and then added to water and extracted with tert-butyl methyl ether. The mixture was dried with MgSO,t and the solvent was then stripped off. The yield was 29 g (74% of theor~r). The NMR spectra showed the following characteristic absorptions: ~ 9F-NMR: -59.5, -60.5, -61.7 and -62.8 ppm.
Example 7a 20 2-(2-Chloro-1,1,1,4,4,4E-hexaflu.oro-2-butenoxy)-phenol 24.4 g of 2-(2-chloro-1,1,1,4,,4,4-hexafluoro-2-butenoxy)-1-benzyloxybenzene from Example 6a were dissolved in 150 ml of tetrahydrofuran and treated at room temperature for 4 hours with 3 bar of hydrogen in the presence of 2 g of Pd/C
( 10%).
The mixture was then filtered and the filtrate concentrated and distilled in vacuo. The 5 yield was 13.2 g (69°/ of theory) and the boiling point was 56°C at 0.15 mbar.
Le A 29 089-PCT - 43 21~~~~~
Example 8a 2-( 1-Chloro-2,2,2-trif luoroeth:yl)-2-trifluoromethyl-1,3-benzodioxole 11.7 g of 2-(2-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy)-phenol from Example 7a were dissolved in 40 ml of tert-butyl methyl ether, and 40 ml of 1 N sodium hydroxide solution were added. After stirring at room temperature for 30 minutes, the organic phase was separated off, dried with MgS04 and distilled. The yield was 10 g (88% of theory) and the boiling point was 63°C at 12 mbar. The NMR spectra showed the following characteristic abscrrptions: ~9F-NMR: -66.8 and -79.7 ppm; IH-NMR:
4.71 ppm.
Example 9a 2,2-Dimethyl-4-(1,1,1,4,4,4-he;xafluoro-2-butenoxy)-1,3-benzodioxole (formula V, RS
together with R1 = -C',(CH3)2-O- radical) 46 g of 2,2-dimethyl-4-hydro~;y-1,3-benzodioxole (formula IV, RS together with R3 =
-C(CH3)2-O- radical) were dissolved in 200 ml of N-methylpyrrolidone, and 31 g of 40% strength by weight aqueous sodium hydroxide solution were added. 54.8 g of chloro-1,1,1,4,4,4-hex.afluoro-2-butene were then added dropwise while stirring at room temperature. After stirring further for 1 hour, the batch was poured into water and extracted with tert-butyl methyl ether. The organic phase was washed with 10%
strength by weight aqueous sodium hydroxide solution and dried with magnesium sulphate, and the readily volatiile fractions were removed on a rotary evaporator. There remained 73.8 g (= 80% of theory) of a product which was 95% pure according to gas chromatography. The characteristic absorptions in the NMR spectra were: ~9F-NMR:
-58.1 and -68.5 ppm; ~H-NMR: 6.73, 6.55, 6.03 and 1.70 ppm.
Le A 29 089-PCT - 44 .a Example 10a 1,2-Dihydroxy-3-( 1,1,1,4,4,4-hexafluoro-2-butenoxy)-benzene 65 g of the product from Example 9a were heated to boiling, at reflux, with 200 ml of concentrated aqueous hydrochloric acid for 4 hours, while stirring. The mixture was S then diluted with 300 ml of water and extracted with methylene chloride.
After drying the extract with magnesium sulphate, the solvent was stripped off from the organic phase to give 54 g of a 90% pure product. Recrystallization from cyclohexane gave colourless crystals with a melting point of 105°C. The characteristic absorptions in the NMR spectra were as~ follows: t9F-NMR: -57.7 and -67.7 ppm; 1H-NMR: 6.77, 6.50, 6.21 and 5.42 ppm.' Example 11 a 2-(2,2,2-Trifluoroethyl)-2-(trifluoromethyl)-4-hydroxy-1,3-benzodioxole (formula (I), R~ = OH, X = H, X == CI-I, R2 and R3 = H).
43.5 g of the product from Example 10a were dissolved in 300 ml of acetonitrile, and 1.5 g of triethylamine was added at room temperature. After stirring at room temperature for 2 hours, the solvent was stripped off and the residue distilled in vacuo.
The yield was 17 g (-= 39% of theory), the boiling point was 85°C at 0.1 S mbar, and the melting point was 65°C. T:he characteristic absorptions in the NMR
spectra were as follows: ~9F-NMR: -~~9.0 and -84.5 ppm; ~H-NMR: 6.80, 6.55, 6.2 and 3.01 ppm.
Example 12a 2,2-Dimethyl-4-(3-chloro-1,1, :l ,4,4,4-hexafluoro-2-butenoxy)-1,3-benzodioxol~formula (V), R~ and RS together are -C(CH3)Z-O-, X~ = C1, R2 + R3 = H, A = CH).
33.2 g of 2,2-dimethyl-4-hydroxy-1,3-benzodioxole were reacted in analogy to Example 9a with 47 g of 2,3-dic;hloro-1,1,1,4,4,4-hexafluoro-2-butene. The product obtained was distilled in vacuo, and a 1:1 molar mixture of cis/trans isomers was obtained.
The yield Le A 29 089-PC'r - 45 -was 51 g (= 70% of '.theory) amd the boiling point was 70°C at 0.15 mbar. The charac-teristic absorptions in the NM:R spectra were as follows: 19F-NMR: -60.0, -61.6, -62.2 and -63.4 ppm; ~ H-I'f MR: 6. i'9, 6.65 to 6.48 and 1.7 ppm.
Example 13a 1,2-Dihydroxy-3-(3-r.hloro-1,1,1,4,4,4-hexafluoro-2-butenoxy)-benzene(formula( V ),R ~
=OH, R2+R3=H, A=C'H:, RS=H, Xt =Cl) 18 g of the product from Ex~unple 12a were reacted in analogy to Example 10a with SO ml of concentrated hydroclhloric acid. 15.7 g of a 97% pure product were obtained.
The product was ~ 1:1 molar mixture of the cis/trans isomers. The characteristic absorptions in the NIVIR specara were, as follows: t9F-NMR: -60.2, -61.3, -62.2 and -63.3 ppm; 1H-NMR: 6.80, 6.45 and 6.25 ppm.
Example 14a 2-( 1-Chloro-2,2,2-trifluoroeth;yl)-2-trifluoromethyl-4-hydroxy-1,3-benzodioxole g of the product from Example 13a were dissolved in 50 ml of acetonitrile, and 15 1 ml of triethylamine was added. After stirring for 15 minutes, the solvent was stripped off and the residue w~~s distilled in vacuo. For purification the product was taken up in diethyl ether and filtered through silica. After stripping off the diethyl ether there remained 10.5 g of the product (= 70% of theory). The melting point was 139 to 141 °C. The characteristic absorptions in the NMR spectra were as follows: ~ 9F-NMR:
-66.6 and -79.3 ppm; tH-NM:R.: 8.4, 6.76, 6.60, 6.50 and 4.70 ppm.
Example 15a 5-Nitro-2-(2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole A solution of 54.4 g of 2-(2,:Z,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole in 75 ml of methylene chloride was added dropwise at 10°C to a mixture of 40 ml of Le A 29 089-f CT' - 46 -~~~8~~~
65% strength by weight nitric acid and 40 ml of concentrated sulphuric acid.
The mixture was stirred at room temperature for a further I hour and then poured into ice-water, the organic phase was then separated off and the aqueous phase was extracted with methylene chloride. The combined organic phases were washed with water, dried, and freed from readily volatil'~e constituents. There remained 95 g of the product (_ 86% of theory) with a melting point of 87 to 88°C.
The NMR spectra showed the i:ollowing characteristic absorptions: ~9F-NMR: -59.0 and -69.4 ppm; ~ H-NMR: 3.10 pp:m.
Example 16a 5-Nitro-2-(1-chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole 613 g of 2-(1-chloro-2,2,2-l:rifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole from Example 2a were dissolved in 1.2 1 of methylene chloride, and the solution was added dropwise at 0 to 10°C' to a mixture of 400 ml of 65% strength nitric acid and 400 ml of concentrated sulphuric acid. The mixture was stirred at room temperature for a further 2 hours. It w;as then .added carefully to 2 1 of ice-water and extracted with methylene chloride. The combined organic phases were washed 2 times with water, dried and concentrated. The yield was 652 g (93% of theory). The NMR spectra showed the following characteristic absorptions: 19F-NMR: -66.4 and -79.2 ppm;

NMR: 4.81 ppm.
Example 17a 5,6-Dinitro-2-(2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole A mixture of 250 ml of 100% strength by weight nitric acid and 350 ml of concentrated sulphuric; acid w;as added dropwise to an initial charge of 317 g of the product from Example; I Sa. The mixture was stirred at 55°C for 2 hours. The mixture was then cooled and poured into ice-water. The product was extracted with methylene chloride, washed until neutral with sodium hydrogen carbonate solution, dried, and Le A 29 089-PC'T - 47 -freed on a rotary evaporator from readily volatile constituents. The yield was 339 g (_ 94% of theory) and t:he melting point was 101 to 103°C.
The NMR spectra showed the following characteristic absorptions: t9F-NMR: -60.9 and -86.5 ppm; 1 H-NMR: 3.18 pp~m.
Example 18a 5,6-Dinitro-2-( I -chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole A mixture of 250 rnl of 100% strength by weight nitric acid and 350 ml of concentrated sulphuric acid eras added to an initial charge of 352 g of S-nitro-2-( 1-chloro-2,2,2-trifluorocahyl)-2-trifluoromethyl-1,3-benzodioxole from Example 16a. The mixture was stirred at 60°C for 2 hours. It was cooled, poured into ice-water and extracted with methyl~ene chloride. After washing the mixture with sodium hydrogen carbonate solution, and drying, it was concentrated on a rotary evaporator.
The yield was 392 g (91% of theory) and the melting point was 125°C. The NMR
spectra showed the following characteristic absorptions: I9F-NMR: -68.5 and -81.0 ppm;

NMR: 4.86 ppm.
Example 19a 5-Amino-2-(2,2,2-trifl,uoroethyl)-2-trifluoromethyl-1,3-benzodioxole 57.4 g of the product from E~;:ample 15a were dissolved in 400 ml of tetrahydrofuran and hydrogenated with hydrogen in the presence of 4 g of catalyst (palladium on carbon, 10% by weight) at 3'0°C for 5 hours and at 50 bar. The mixture was then filtered, the solvent removed, and the remaining filtrate distilled under a high vacuum.
37 g of product (= 63% of theory) were obtained with a boiling point of 83°C at 0.07 mbar. '9F-NMR: -59.0 and -84.6 ppm; ~H-NMR: 2.98 ppm.
Le A 29 089-PCT - 48 Example 20a 5-Amino-2-( I -chloro-2,2,2-tri fluoroethyl)-2-trifluoromethyl-1,3-benzodioxole 72 g of 5-nitro-2-1;1-chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole from Example 16a were dissolved in 500 ml of tetrahydrofuran, and hydrogenated on 5 g of palladium on carbon (5%) at room temperature for 5 hours with 15 to 20 bar of hydrogen. The mixture was then filtered and the solvent stripped off in vacuo.
The yield was 60 g (93% of theory) and the boiling point was 80 to 82°C at 0.1 mbar. The NMR spectra showed the folllowing characteristic absorptions: 19F-NMR: -66.5 and -79.4 ppm; ~ H-NMR: 4.68 ppm.
Example 21 a 5,6-Diamino-2-(2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole 339 g of the product from Ex~unple 17a were dissolved in 2,000 ml of tetrahydrofuran, and 20 g of catalyst (palladiwm on carbon, 5% by weight) were added.
Hydrogenation was carried out with hydrogen at 25 to 30 bar and at room temperature for 13 hours.
The mixture was then filtered and the solvent stripped off in vacuo. A solid remained.
The yield was 274 g (= 96%. of theory). 19F-NMR: -61.2 and -86.6 ppm; ~H-NMR:
3.02 ppm.
Example 22a 2-(2,2,2-Trifluoroeth~rl)-2-trifluoromethyl-1,3-benzodioxole 306.5 g of 2-(1-chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole from Example 2a were dissolved in 500 ml of THF, and 101 g of triethylamine and 30 g of palladium on carbon (5% by weight) were added. Hydrogenation was then carried out with 100 bar of hydrogen at 110°C for 48 h. The mixture was then filtered, the solvent stripped off in vacuo and the residue subjected to fractional distillation in vacuo. The yield was 126 g (46°/. of theory) and the boiling point was 60°C
at 10 mbar. The NMR
Le A 29 089-PCT - 49 __ spectra showed the following .characteristic absorption: ~9F-NMR: -59.0 and -84.6 ppm;
~ H-NMR: 3.02 ppm.
o-Phenylenediamines containiing fluoroalkyl(ene) groups and of the formula NHR
Rz NH2 in which S R1 represents C',F3, OCF3., SCF3, S02-Ct-C6-alkyl, which can be straight-chain or branched and may be substituted wholly or partially by fluorine, N(CF3)2, a phenyl or phc~.noxy radical with CF3 or CN in the 4 position and optionally further substituents, 1,1,2,3,3,3-hexafluoropropoxy, 1,1,2-trifluoro-2-chloro-ethoxy, 1,1,2,2-tetr;afluoroethoxy, 1,1,2-trifluoro-2-chloro-ethylthio or 1,1,2,3,3,3-heatafluorolpropylthio, and, independently thereof, R2 represents F, Cl, Br, C;N, CH3, OCF3, S02-Ct-C6-alkyl which can be straight-chain or branched and may be substituted wholly or partially by fluorine, COO-C~-C6-alkyl, COC>C6H5, 1,1,2,2-tetrafluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy or 1,1,2-trifluoro-2-chloro-ethoxy, and R3 represents hydrogen, C:OCH3 or COCF3, where R~ and R2 can together represent a -O-CFCI-CFCI-O- radical, with the exception of the compounds described in EP-A 251 013 and EP-A 487 286, are obtainable by dinitrating a benzene derivative of the formula D
i D
Le A 29 089-PCT - 50 -.. ~~l~~~l~
in which D~ represents CF;;O, CF3;i, CHF2CFz0, CHFCI-CF20, CF3CHFCF20, CF3CF20, CF3CF2CF20, CF3CF,,S or CF3CHFCF20, and D2 represents CF:~O, CF3S, CHF2CF20, CHFCI-CF20, CF3CHF-CF20, CF3CF20, S CF3CF2CF20, CF3CF; S or CF3CHFCF20, fluorine, chlorine, bromine, C1-C6-alkyl or C~-C~~-alkoxy., and subsequently reducing the; nitro groups to obtain compounds in which R1 and R2 are in the 4 and S po:~itions with respect to the amino groups and have the meaning of D ~ and D2. ' If it is intended to prepare compounds in which Rl has the meaning given above and is in the 4 position with respect to the amino groups, and R2 represents Cl or Br and is in the 5 position with respect to the amino groups, then, for example, a nitrobenzene derivative of the forrrrula CI or B ~ Hal in which R~ has the meaning given and Hal represents fluorine, chllorine or bromine, can be reacted with ammonia, the Hal group thus being exchanged for an amino group, and the resulting nitroaniline can be reduced.
If it is intended to prepare compounds in which R~ has the meaning given above and is in the 4 position with respeca to the amina groups, R2 represents chlorine or bromine and is in the 6 position with respect to the amino groups and R3 denotes hydrogen, then, for example, a nitroaniline of the formula Le A 29 089-PCT - 51 ~1~~~~3 R ~ N02 in which R~ has the meaning given. above can be reacted with a chlorinating or brominating agent, a chlorine or bromine atom thus being introduced into the position meta to the vitro group, and the vitro group can subsequently be reduced.
If it is intended to prepare compounds in which R1 represents a donor group in the 4 position with respect to the two amino groups, R2 represents an acceptor group, e.g.
COO-C~-C6-alkyl, C1~1, CF.3 or S02-C~-C6-alkyl, and R3 is not hydrogen, a benzene derivative of the formula , D
i A
in which D I has the meaining given above and A represents CF_s, S02-C1-C6-alkyl which is straight-chain or branched and may be substituted wholly or partially by fluorine, COO-C~-C6-alkyl or CN, for example, can then be manonitrated (introduction of the N02 group into the position para to D 1 ), the N02 group c,an be reduced to the NH2 group, the NH2 group can be acylated with, for example, acetic acid or trifluoroacetic acid, the product cam again be mononitrated (introduction of this N02 group into the position ortho to the NHCOR
group where R = e.g. CH3 or (:F3), this NOZ group can be reduced to the NH2 group and, optionally, if it is desiredl to prepare a compound of the above formula where R3 = hydrogen, the acyl group cam be eliminated by hydrolysis.
Le A 29 089-PCT - 52 -2~4~~~3 The o-phenylenediamines containing fluoroalkyl(ene) groups, in which R3 denotes hydrogen, can initially be reacted with trifluoroacetic acid to give 2-trifluoro-methylbenzimidazoles, of the formula i R
N
~~.-CF3 ~N
2 ~
R H
and then further reacted with compounds of the formula R
A-C H
Ra 5 where R~ and RZ adopt the above scope of meaning, R4 represents hydrogen, alkyl, alkoxy or optionally substituted aryl, RS represents hydlroxyl, cyano or in each case optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, amino, aminocarbonyl, alkylcarbonyl. alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphonyl, (hetero)ary l, (he;tero)arylcarbonyl, (hetero)aryloxycarbonyl, (hetero)arylcarbonylox:y or (hetero)arylaminocarbonylaminocarbonyloxy, and A denotes a suitable leaving group.
Leaving groups are known to those skilled in the art and are, for example, halogen, alkyl(alkoxy, aryl)sulphonyloxy, hydroxyl or alkoxy.
Le A 29 089-PCT - 53 -Examples Examples 1 to 6 b (Dinitration and reduction) Example 1 b 320 g of 1,2-bis-(2-chloro-1,1,;?-trifluoroethoxy)-benzene were added dropwise to 500 g of a mixed acid containing 3a% by weight of HN03 and 67% by weight of H2S04.
After one hour at 40°C, 250 ml of 20% strength by weight oleum were added dropwise. The mixture was thf;n heated to 80°C and stirred for 15 hours. Subsequently a further 120 ml of 20% strength by weight oleum and 250 g of the abovementioned mixed acid were adfied dropwise. After 6 hours at 80 to 82°C, the mixture was cooled and poured onto ice. The organic phase was separated off and washed with water. After azeotropic drying ~Nith 1,;Z-dichloroethane, 350 g of 96% by weight pure 1,2-dinitro-4,5-bis-(2-chloro-1,1,2-trifluoroethoxy)-benzene were obtained (oil, nDO:
1.4832, GC 99.1 %).
350 g of this dinitro c:ompoun.d were added dropwise to a mixture of 1.5 1 of ethanol, 1 S 50 ml of water, 30 ml of concentrated aqueous hydrochloric acid and 470 g of iron filings, and heated tn boiling; at reflux for a total of 15 hours. The solution was subsequently cooled and then filtered, the filtrate concentrated, and the residue recrystallized from cyclohe:xane. 216 g of 1,2-diamino-4,5-bis-(2-chloro-1,1,2-trifluoroethoxy)-benzene having a melting point of 58 to 60°C were obtained.
Example 2 b In analogy to Example l, the: corresponding 4,5-dinitro compound (oil, no :
1.4852) and the corresponding; 4,5-diamino compound (oil, 87% by weight pure) were prepared from 1,2-bis-(1,1,2,3.3,3-hexaifluoropropoxy)-benzene.
Example 3 b In analogy to Example 1, the corresponding 4,5-dinitro compound (melting point 56 to Le A 29 089-PCT - 54 -2~.~~~~3 57°C) and the corresponding 4,5-diamino compound (melting point 67 to 68°C) were prepared from 1-( 1,1,:Z-trifluoro-2-chloroethoxy)-2-chlorobenzene.
ExamQle 4 b In analogy to Example 1, the corresponding 4,5-dinitro compound (melting point 73 to S 75°C) and the corresponding 4,5-diamino compound (oil, 98% by weight pure, npo:
1.5485) were prepared from 1-trifluoromethoxy-2-bromobenzene.
Example 5 b In analogy to Exam~l~e 1, the corresponding 4,5-dinitro compound (melting point 55 to 56°C) and the corresponding 4,5-diamino compound (melting point 56 -57°C) were prepared from 1-trifluorometh.oxy-2-chlorobenzene.
Example 6 b The corresponding 4,5-dinitro compound (oil) and the corresponding 4,5-diamino compound (oil) were prepared from 1-(1,1,2,3,3,3-hexafluoropropoxy)-2-chloro-benzene.
Examples 7 to 12 b Pressurization with ammonia and reduction Example 7 b 260 g of 3-nitro- 2,5-dichlorobenzotrifluoride, 130 ml of water and 10 g of tetraethylammonium chloride were initially introduced into an autoclave, and 120 ml of liquid ammonia w~:re injecl;ed. The mixture was then heated to 130°C
and stirred for 10 hours at this tennperaturc:. The mixture was cooled and then filtered, and the precipitate which was separated off was washed with water and dried. 194 g of amino-3-nitro-5-chlo~ro-benzotrifluoride with a melting point of 67°C
resulted.
Le A 29 089-PCT - 55 -~~4~~~~
134 g of the nitroaniline obtained as described above were dissolved in 800 ml of ethanol, and then 20 ml of wate:r, 10 ml of concentrated aqueous hydrochloric acid and 160 g of iron filings were added. The mixture was heated for 15 hours to boiling at reflux, then cooled and filtered with suction and the filter residue washed with S dichloromethane; the organic phases were subsequently freed from the solvent under reduced pressure. 171 g of :S-chloro-3-trifluoromethyl-1,2-diaminobenzene with a melting point of 53°C resulted.
Example 8 b In analogy to Example 7, first 3-nitro-4-amino-6-chloro-difluorochloromethoxybenzene (melting point 73°e) and from this 3,4-diamino-6-chloro-difluorochloromethoxy-benzene (oil) were obl:ained from 3-nitro-4,6-dichloro-difluorochloromethoxybenzene.
Example 9 b In analogy to Example 7, first ?.-bromo-S-nitro-6-amino-benzotrifluoride (melting point 80 to 82°C) and from this 3-b:romo-5,6-diamino-benzotrifluoride (melting point 52 to I S 54°C) were prepared from 3-bromo-5-nitro-6-chlorobenzotrifluoride.
Example 10 b In analogy to Example; 7, first 3-cyano-4-amino-5-nitro-benzotrifluoride (melting point 99 to 100°C) and from this 3-cyano-4,5-diamino-benzotrifluoride were prepared from 3-cyano-4-chloro-5-nitro-benzotrifluoride.
Example 11 b In analogy to Example: 7, first :3-chloro-5-nitro-6-amino-benzotrifluoride (melting point 53 to 54°C) and from this 3-c;hloro-5,6-diamino-benzotrifluoride were prepared from 3,6-dichloro-5-nitro-b~~nzotriflnoride.
Le A 29 089-PCT - 56 -~14~~1~
Example 12 b First 2-bromo-4-amino-5-nitro-( 1,1,2-trifluoro-2-chloro-ethoxy)-benzene (melting point 90°C) and from this 2-bromo-4,5-diamino-(1,1,2-trifluoro-2-chloro)-ethoxybenzene were prepared from 2-'bromo-4-fluoro-5-nitro-( I,1,2-trifluoro-2-chloro)-ethoxybenzene.
Example 13 b (Halogenation of a nitroaniline and reduction) 24 g of finely powdered 2-nitro-4-trifluoromethylmercaptoaniline were dissolved in 50 ml of trifluoroaCetic acid, and 18 g of bromine were metered in at 20°C. The mixture was then stirred at 20"C for 3 hours and at 40°C for a further 30 minutes. The mixture was added to water and the product was taken up in dichloromethane.
Following removal of the solvent, 31 g of 6-bromo-2-nitro-4-trifluoromethyl-mercapto-aniline resulted.
155 g of the nitroanil:ine thus ;prepared were heated to boiling at reflux for 1 S hours in 700 ml of ethanol tngether with 15 ml of water, 10 ml of concentrated aqueous hydrochloric acid an<i 70 g of iron filings; the mixture was then filtered, the filtrate freed from solvent under reduced pressure, and the crude solid product recrystallized from cyclohexane. 11.2 g of fi-bromo-4-trifluoromethyl-mercapto-1,2-diaminobenzene with a melting point of 60 to 61 °C were obtained.
Example 14 b In analogy to Example 13, 27 g of 2-nitro-4-trifluoromethyl-sulphonylaniline in 100 ml of acetic acid were brominated with 18 g of bromine.
After work-up, 32 g of 2-nit:ro-6-bromo-4-trifluoro-methylsulphonyl-aniline resulted:
melting point 147°C.
32 g of the nitroamine thus prepared were reduced with iron filings in alcohol and Le A 29 089-PCT - 57 -~1~.~~13 aqueous hydrochloric acid. 24 g of 3-bromo-5-trifluoromethylsulphonyl-phenylene-1,2-diamine resulted; melting point 155 - 157°C.
Example 15 b In analogy to Example 14, 27 g of 2-nitro-4-trifluoromethylsulphonyl-aniline in 100 ml of acetic acid were chlorinated with 10 g of chlorine. 29 g of 2-nitro-4-trifluoromethylsulphonyl-6-ch.loro-aniline resulted; melting point 138 -139°C.
13 g of 3-chloro-5-trifluoromethylsulphonyl-1,2-phenylenediamine (melting point:
143 - 145°C) were obtained by reduction.
Example 16 to 20 b (Nitration and reduction in 2 stages) Example 16 b 263 g of 4-(2,6-dichloro-4-trifluoromethyl)-phenoxy-acetanilide were dissolved in 1,100 ml of dichloromethane, and taken as initial charge at 10°C. 88 g of 98% strength by weight nitric acid were then added dropwise at this temperature. The mixture was subsequently stirred at 10°C for 1 hour and at 30°C for 2 further hours. After the addition of 300 ml 01~ water, the phases were separated and the organic phase was freed from dichloromethane under reduced pressure. There remained 253 g of 2-nitro-4-(2,6-dichloro-4-trifluoroir~ethyl-phenoxy)acetanilide with a melting point of 138 -140°C.
91 g of the acetaniliide thus prepared were dissolved in 800 ml of dioxane, 10 g of Raney nickel were added, and hydrogenation was carried out at 25 to 45°C in a hydro-genation apparatus with a maximum of 50 bar hydrogen pressure. The apparatus was let down, the mixture was filtered, and the dioxane was distilled off under a slight vacuum. There remained 65 ~; of 2-amino-4-(2,6-dichloro-4-trifluoromethyl-phenoxy)-acetanilide with a melting point of 222 - 223°C.
Le A 29 089-PCT - 58 -~~4-813 Example 17 b In analogy to Example 16.. first 3-trifluoromethyl-4-methoxy-6-nitro-acetanilide (melting point 143 - 144°C) and from this 3-trifluoromethyl-4-methoxy-6-amino-acetanilide (melting point 164 - 165°C) were prepared from 3-trifluoromethyl-4-methoxy-acetanilide.
Example 18 b In analogy to Example 16, first 3-trifluoromethyl-4-fluoro-6-nitro trifluoromethylacetanilide (meslting point 78°C) and from this 3-trifluoromethyl-4 fluoro-6-amino-trifluoromethy'.lacetanilide (melting point 92 - 93°C) were prepared from 3-trifluoromethyl-4-fluoro-trifluoromethyl-acetanilide.
Example 19 b In analogy to Example 16, first 3-trifluoromethyl-4-bromo-6-nitro-trifluoromethylacetanilide (me:lting point I 10 - 112°C) and from this 3-trifluoromethyl-4-bromo-6-amino-trifluoromethylacetanilide (melting point 63 - 65°C) were prepared from 3-trifluoromethyl-4-bromo-trifluoromethylacetanilide.
Example 20 b In analogy to Example; 16, first 3-trifluoromethylthio-4-chloro-6-nitro-trifluoromethylacetaniilide (melting point 99 - 100°C) and from this 3-trifluoro-methylthio-4-chloro-6.-amino-t:rifluoromethylacetanilide (melting point 88 -90°C) were prepared from 3-trifluorometh.ylthio-4-chloro-trifluoromethylacetanilide.
Example 21 b 0.2 mol of 3-bromo-_'>-trifluoromethyl-phenylene-diamine were heated with 150 ml of trifluoroacetic acid ;at reflua; temperature for 3 hours. For working up, excess trifluoroacetic acid w:as distilled off and the residue was partitioned between 100 ml of Le A 29 089-PCT - 59 water and 300 ml of ethyl acetate. The organic phase was separated off, washed successively with in each case 100 ml of aqueous sodium hydrogen carbonate solution and water, dried over sodium sulphate, and concentrated in vacuo. The residue was purified by chromatol;raphy on silica gel (eluent: cyclohexane/ethyl acetate 1:1).
S 4-Bromo-6-trifluorom.ethyl-2-l:rifluoromethyl-1 H-benzimidazole with a melting point of 149 - 1 S 1 °C was obtained.
Example 22 b 0.03 mol of 4-bromo-6-trifluoromethyl-2-trifluoromethyl-1H-benzimidazole and 0.06 mot of powdered potassium carbonate were heated in 70 ml of ethyl acetate at reflux temperature for 15 minutes; 3.9 g (0.04 mol) of chloromethyl methyl thioether in 20 ml of ethyl acetate were: then added, and the mixture was heated with stirring at reflux temperature for a further 4 hours. For working up, the reaction mixture was cooled and then washed twice with in each case 40 ml of water, dried over sodium sulphate and concentrated in vacuo, and the residue was purified by chromatography on silica gel (eluent: dic:hloromet:hane).
1-Methylthiomethyl-4-bromo-6-trifluoromethyl-2-trifluoromethyl-benzimidazole with a melting point of 56 - 60°C was obtained.
Use Examples:
In the Use Examples which follow, the compounds listed below were employed as comparison substancca:
O
ii C
0-i-C3H~
N-Methyl-O-(2-isopropoxyphenyl)-carbamate (cf. e.g. DE 11 08 202) Le A 29 089-PCT - 60 O
I I

O,S-Dimethyl-thiolo-phosphoric acid amide (c~ e.g. DE 12 10 835) Le A 29 089-PCT - 61 -Example A:
Phaedon larvae test:
Solvent: 7 harts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active substance, 1 part by weight of active substance is mixed with the stated amount of solvent and the stated amount of emulsi-fier, and the concentrate is dilluted with water to the desired concentration.
Cabbage leaves (Br~ssica oleracea) are treated by being dipped into the preparation of the active substance of the desired concentration and are infested with mustard beetle larvae (Phaedon cochleariae), as long as the leaves are still moist.
After the desired time, the destruction in per cent is determined. 100% means that all the beetle larvae have been kiilled; 0% means that none of the beetle larvae has been killed.
In this test the following compound, for example, from the Preparation Examples exhibits superior activity over the prior art: 7.
Le A 29 089-PCT - 62 -Table A:
Phaedon larvae test Active substances Concentration Degree of of active destruction substance in % after in % 3 days O (A) 0.1 I 00 II 0.01 70 \ 0.001 0 O-i~:3H~
(known) CI (7) 0.1 100 0.01 100 \ N ~ 0.001 100 \~--CF3 CHI-OC21-i~

\ -CF3 / N
Cl Cf~-OC2Hs Le A 29 089-PCT - 63 ~~ 4-8~~.~
Example B
Plutella test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active substance, 1 part by weight of active substance is mixed with the stated amount of solvent and the stated amount of emulsi-Pier, and the concentrate is diluted with water to the desired concentration.
Cabbage leaves (Bra;aica oleracea) are treated by being dipped into the preparation of active substance of t:he desired concentration and are infested with caterpillars of the diamond-back moth yPlutella maculipennis) while the leaves are still moist.
After the specified periods o:f time, the destruction in % is determined. 100%
means that all the caterpillars have been killed; 0% means that none of the caterpillars has been killed.
In this test the following compound, for example, from the Preparation Examples exhibits superior activity over the prior art: 1 and 7.
Le A 29 089-PCT - 64 -Table B:
Plutella test Active substances Concentration Degree of of active destruction substance in % after in % 3 days O (A) 0.1 100 0.01 100 O-C-NFi-CH, 0.001 10 O-i-C, H~
(known) C ~ N (1) 0.1 100 \~CF3 0.01 100 0_001 100 C1 ~
CH2 O--C;ZHS
Cl (7) 0.1 100 0.01 100 N 0.001 100 \~-_CF3 CI / N
Cl~-OCzHs CI N
\ -CF3 N
Cl Cl Le A 29 089-PCT - 65 -Example C:
Heliothis virescens test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether S To produce a suitable preparation of active substance, I part by weight of active substance is mixed with the stated amount of solvent and the stated amount of emulsi-fier, and the concentrate is diluted with water to the desired concentration.
Soya shoots (Glycirie max) are treated by being dipped into the preparation of active substance of the desired concentration and are infested with the tobacco bud worm (Heliothis virescens) while the; leaves are still moist.
After the desired time;, the de:>truction in per cent is determined. 100%
means that all the caterpillars have been killed; 0% means that none of the caterpillars has been killed.
In this test the following compounds, for example, from the Preparation Examples exhibit superior activity over the prior art: 1, 2, 6, 7, 9, 18, 22 and 27.
Le A 29 089-PCT - 66 -. , ~148~~~
Table C:
Heliothis virescens test Active substances Concentration Degree of of active destruction S substance in % after in % 3 days O (A) 0.1 10 i1 O-C-~-1~H3 O-_;.~3 H~
(knownl) C ~ N ~ (1) 0.1 100 ~~---CF3 \CHZ O--CZHs Cl ~ N (2) 0.1 100 ~~--CF3 C;H3 ~C--OCH3 y O
CI ~ N (6) 0.1 100 ~~---CF3 ,n-C3H~
CH2 __N
\C--OCI~
O
Le A 29 089-PCT - ('7 Table C: yContinued) Heliothis virescens test Active substances Concentration Degree of of active destruction substance in % after in % 3 days C1 (7) 0.1 100 \ N
\~--CF3 Cl ~ N
C> h-OC2lHs CI N
j,--CF3 N
Cl C~~-OC~ Hs N (9) 0.1 100 \~--CF3 Cl / N
v CIA, -O-i-C:~ H~

\ -CF3 N
CH2 ~'1-~.3~
Le A 29 089-PCT _ bg _ -Table C: (Continued) Heliothis virescens test Active substances Concentration Degree of of active destruction substance in % after in % 3 days CHz--OCZHS
,N (18) 0.1 100 \~--.CF3 'N
OzN

OZN ~ ' ,N
~N
N (22) 0.1 100 ~~-CF3 N
02N v ; C~
(:Hz-N
\C-OCzHs OzN ~ N y \~CF:3 N
~CH3 CHz-N
\C-OC21-i~
O
Le A 29 089-PCT - 69 -~.
Table C: (Continued) Heliothis virescens tf~st Active substances Concentration Degree of of active destruction substance in % after in % 3 days CI (27) 0.1 100 \ O w. N
~>--CF3 F3C ~(.I
CFii-OC2H5 F3C / C;1 ~' N
\ ~ ~ /~ ~~~3 \,/ N
Cl CF'Zz-OC21'is Le A 29 089-PCT - 70 -Example D
Tetranychus test (OlP-resistant) Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active substance, I part by weight of active substance is mixed with the stated amount of solvent and the stated amount of emulsi-fier, and the concenorate is diluted with emulsifier-containing water to the desired concentrations.
Bean plants (Phaseolus vulg~~ris) which are heavily infested with all developmental stages of the red spider mite (Tetranychus urticae) are dipped in a preparation of the active substance of the desired concentration.
After the desired time, the destruction in per cent is determined. 100% means that all the spider mites ham: been killed; 0% means that none of the spider mites has been killed.
1 S In this test the following compounds, for example, from the Preparation Examples exhibit superior activity over the prior art: 8, 21, 22, 23, 24 and 25.
Le A 29 089-PCT - 71 -Table D:
Tetranychus test (OP-resistant) Active substances Concentration Degree of of active destruction substance in % after in % 7 days O (B) 0.01 60 CH30- i ~-NHZ
S~~H3 (known) Cl . (8) 0.01 100 N
~~~--CF3 / /
Cl N ,CH3 CE-~-N
\C;-OCR
O
Cl N
~>---CF3, N

CI f'~ N
\C-OCH3 O
Le A 29 089-PCT - 72 -2~4.~~~~
Table D: (Continued) Tetranychus test (OP-resistant) Active substances Concentration Degree of of active destruction substance in % after in % 7 days ,N (21) 0.01 98 \ -CF3 'N

~z-_O-n-~~
OZN ~ ; ,N
\/ CF3 / 'N
CHi--O-n-C3I-h (22) 0.01 100 \~Cl' 3 02N / td CIA-rf OzN .~ lV Cp ~~--CF3 ~CI-T3 v C-OC21-i~
O
Le A 29 089-PCT - 73 -~~.~~~~3 Table D: (Continued Tetranychus test (OI'-resistant) Active substances Concentration Degree of of active destruction substance in % after in % 7 days (23 ) 0.01 100 \~Cl'3 r~
OZN \ /CZHs CHz--N
~C--OCzHs OzN ~ 1~T
\~-CIF
1~1 \ /C2H5 CHZ-td \C-OC2H5 O
(24) 0.01 100 \~---CF3 OZN ~ 1V /n-C3~
C~-_rJ
\C-OC2Hs OzN \ N (),, \~--_C,F3 N
\ /n_C3H.r CHZ--lV
~C--OCZHS
O
Le A 29 089-PCT _ ~4 _ Table D: (Continued Tetranychus test (OlP-resistant) Active substances Concentration Degree of of active destruction substance in % after in % 7 days (25) 0.01 98 \~_ C,.F3 lV
OzN ~
CHz-OH
OzN ~ N
\~--C;F3 N
CI-~w-OH
Le A 29 089-PCT - 75 -~.. ~~~.$~~~
Example E
Nematodes: Critical concentration test Test nematode: Globodera ros,tochiensis Solvent: 31 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active substance, 1 part by weight of active substance is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
The preparation of active substance is intimately mixed with the soil which is heavily contaminated with thc: test nematodes. The concentration of the active substance in the preparation is of practically no importance here, only the amount by weight of active substance per unit volume of soil, which is given in ppm (= mg/1), being decisive. The treated soil is transferred into pots, potatoes are planted in it, and the pots are maintained at a greenhouse temperature of 20°C.
After six weeks the potato roots are examined for cysts and the degree of effectiveness of the active substance is determined in %. The degree of effectiveness is 100% if infestation has been 'totally avoided, and is 0% if infestation is just as high as in the control plants in soil which is untreated but contaminated in the same way.
In this test the folle~wing compound, for example, from the Preparation Examples exhibits superior activity over the prior art: I and 7.
Le A 29 089-PCT - 76 -Table E:
Nematodes test (Glolbodera rostochiensis) Active substances Degree of destruction in at an active substance concentration of 20 ppm O (B) 0 SCFi3 (known) C ~ N (1) 100 ~~--CF3 CI
O--CzHs Cl (7) 100 \ N
~~--CF3 Cl / N

C~ _.O~~zHs CI N
N
1CH2=-OC2H5 Cl Le A 29 089-PCT - '7'7 ..
Example F:
Psoroptes ovis test:
Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable preparation of active substance, 3 parts by weight of active substance are mixed v~rith 7 parts of the solventlemulsifier mixture indicated above, and the emulsion concentrate thus obtained is diluted with water to the desired concentra-tion.
1 ml of this active substance preparation is pipetted into suitably sized PP
blister packs.
About 25 mites are then transferred into the active substance preparation.
After 24 hours the effectiveness of the active substance preparation is determined in %.
100% means that all i:he mites have been killed; 0% means that none of the mites has been killed.
In this test, the following compounds, for example, of the Preparation Examples display superior action comp~ued to the prior art: 3, 4, 5 and 18.
Le A 29 089-PCT - 78 -Table F:
Psoroptes ovis test Active substances Concentration Degree of of active destruction S substance in in ppm of a.i.
C ~ N (3) 10 100 \~CF3 Cl / ~N~ /CHf3 CHfz N
\COOCZHs ~~--CF, 'CHZ O___Cz~~S
C ~ N (4) 10 100 \~---CF3 Cl / N~' /CzHs CFi2 N~
COC~zHs C ~ N (5) 10 100 \~---CF3 Cl / N~ /C;~HS
CI~Z N~

N (18) l0 loo \>-CF3 OzN / N
\~CH2 O--CzHS
OzN ~ N
/ N
Le A 29 089-PCT - 79 -Example G:
Periplaneta americana test:
Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether To produce a suitable preparation of active substance, 3 parts by weight of active substance are mixed with 7 pans of the abovementioned solvent/emulsifier mixture, and the resulting emulsion concentrate is diluted with water to the desired concentration.
2 ml of this active substance preparation are pipetted onto filter paper discs (diameter:
9.5 cm) which are located in suitably sized Petri dishes. After drying the filter discs, five cockroaches (Periplaneta ~unericana) are transferred to the Petri dishes and covered.
After 3 days the effectiveness of the active substance preparation is determined in %.
100% means that all the cockroaches have been killed; 0% means that none of the cockroaches has been killed.
In this test the follo~Ning compounds, for example, from the Preparation Examples exhibit superior activity over the prior art: 7, 8, 18, 19, 20 and 25.
Le A 29 089-PCT - 80 -.-Table G:
Periplaneta americana test Active substances Concentration Degree of of active destruction substance in in ppm of a.i.
CI (7) 1000 100 N
~~---CF3 \CHZ O--CZHs C ~ N
~~----CF3 N
C1 \Ciii O-C ZHs C1 (8) 1000 100 N
~~--CF3 Cl / ~N\ %
CF(i N
\COUCH3 C ~ N
~~--CF3 N\ ~CH3 Cl C~;~ N\

Le A 29 089-PCT - 81 -~. ~.8 ~ ~.~
Table G: (Continued) Periplaneta americana test Active substances Concentration Degree of of active destruction substance in in ppm of a.i.
OzN ~ N (18) 1000 l00 ~~-CF3 / N
\~CHZ O--CzHs N
~~,--CFA
/ /
OzN N\
~CHZ O--CzHs OzN .~ N (19) 1000 100 ~>-CF3 / N
'CHZ O--CzHs N (20) 1000 100 ~~~--CFi OzN Nv \Cli2 O--CzHs Le A 29 089-PCT - 82 -Table G: (Continued) Periplaneta americana test Active substances Concentration Degree of of active destruction substance in in ppm of a.i.
OZN ~ N (25) 1000 100 \~..Ch3 / 'N
\CHZ -OH
~ ~N
\~---.-CF3 OzN / . _N
\CHZ -OH
Le A 29 089-PCT - 83 -~~4~~~3 Example H_ Musca domestica test:
Solvent: 35 parts by weight of ethylene glycol monomethyl ether Emulsifier: 35 part: by weight of nonylphenol polyglycol ether To produce a suitable preparation of active substance, 3 parts by weight of active substance are mixed with 7 parts of the abovementioned solvent/emulsifier mixture, and the resulting emulsion. concentrate is diluted with water to the desired concentration.
2 ml of this active substance preparation are pipetted onto filter paper discs (diameter:
9.5 cm) which are located in suitably sized Petri dishes. After drying the filter discs, 25 test organisms (Musca domestica; strain WHO [N]) are transferred to the Petri dishes and covered.
After 3 days the effectiveness of the active substance preparation is determined in %.
100% means that all the flies have been killed; 0% means that none of the flies has been killed.
In this test the following compounds, for example, from the Preparation Examples exhibit superior activity over the prior art: 7, I1, 18, 19, 20 and 25.
Le A 29 089-PCT - 84 -Table H:
Musca domestica test Active substances Concentration Degree of of active destruction substance in in ppm of a.i.
C1 (7) 1000 100 100 >50 N
~~--CF3 CI ~ N
\CH.t O--CzHs C ~ N
~~--CF3 N
Cl \CHZ O-C'.ZHs C1 ~ N (11) 1000 100 ~~--CF3 N
CH2 OCZHs ~ ,N
~~---CF3 C1 ~ N
\C:Hz OCZl3s Le A 29 089-PCT - 85 -~~.~.8~13 Table H: (Continued) Musca domestica test Active substances Concentration Degree of of active destruction substance in in ppm of a.i.
02N ~ N (18) 1000 100 \~,-CF; 100 >50 N
~CHZ O--CZHs N
~~---CF3 OzN ~ N
\~CH2 O.-CzHs OZN ~ N ( I 9) 1000 I 00 \~-CFA 100 100 N
y ~CHz 0--CZHs N (20) 1000 100 \~~-CF 100 >5O

OzN ~ Nv \CHZ O--CzHs Le A 29 089-PCT - 86 -Z~ 4.~61~
Table H: (Continued) Musca domestica test Active substances Concentration Degree of of active destruction substance in in ppm of a.i.
OZN ~ tJ (25) 1000 100 \CHz ~OH
~ N
OzN / , N
\CHZ ~OH
Le A 29 089-PCT - 87 -

Claims (5)

CLAIMS:

1. A substituted benzimidazole of the general formula (I):
wherein:
R1 represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, or phenyl which is optionally substituted once or more than once by identical or different substituents selected from the group consisting of:
halogen; cyano; nitro; straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl each having 1 to 6 carbon atoms; straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms; straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl, alkoxycarbonyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl moieties; divalent dioxyalkylene having 1 to 5 carbon atoms which is optionally substituted once or more than once by identical or different substituents selected from the group consisting of halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms and straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms; and phenyl which is optionally substituted once or more than once by identical or different substituents selected from the group consisting of halogen, straight-chain or branched alkyl having 1 to 6 carbon atoms and straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
R2 represents hydroxyl, cyano, alkoxy having 1 to 8 carbon atoms or amino which is optionally substituted once or twice by identical or different substituents selected from the group consisting of: straight-chain or branched alkyl having 1 to 8 carbon atoms; straight-chain or branched alkenyl having 2 to 8 carbon atoms; cycloalkyl having 3 to 8 carbon atoms; alkoxycarbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-thiocarbonyl each having 1 to 8 carbon atoms in the individual straight-chain or branched alkyl moieties; a divalent closed alkanediyloxycarbonyl ring having 2 to 6 carbon atoms in the alkanediyl moiety; and arylalkyl or aryl each having 6 to 10 carbon atoms in the aryl moiety and 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, each of which is optionally substituted once or more than once by identical or different substituents, wherein the substituents for each aryl are as defined for R1;
R3 represents straight-chain or branched perhalogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms; and X1, X2, X3 and X4, independently of one another, represent hydrogen, fluorine, chlorine, bromine, iodine, nitro or aryloxy having 6 to 10 carbon atoms in the aryl moiety which is optionally substituted in the aryl moiety once or more than once by identical or different substituents, wherein the substituents in the aryl are as defined for R1, with the proviso that at least one of X1, X2, X3 or X4 is other than hydrogen;
with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-dichlorbenzimidazole.

2. A process for the preparation of a substituted benzimidazole of the general formula (I) according to claim 1, comprising:
reacting a 1H-benzimidazole of the general formula (II):
wherein R3, X1, X2, X3 and X4 are as defined in claim 1, with a compound of the general formula (III):
wherein R1 and R2 are as defined in claim 1, and A represents a suitable leaving group, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary.

3. An agent for combating pests, comprising at least one substituted benzimidazole of the general formula (I) according to claim 1, and an extender therefor.

4. Use of a substituted benzimidazole of the general formula (I) according to claim 1 for combating pests.

5. A process for the preparation of an agent for combating pests, comprising mixing a substituted benzimidazole of the general formula (I) according to claim 1 with an extender, a surface-active agent or a mixture thereof.