DE2634053A1 - (4,5)-Dichloro-imidazole (2)-carboxylic acid derivs. - useful as herbicides, fungicides, bactericides, insecticides etc. - Google Patents

Abstract

Imidazole derivs. of formula (I) and thier salts with bases are new: (where CXYZ represents a C atom with 3 bonds attached to heteroatoms).

Description

4, 5-dichloroimidazole-2-carboxylic acid derivatives,

Process for their production and their use as pesticides The present invention relates to new 4,5-dichloroimidazole-2-carboxylic acid derivatives, Process for their production and their use as pesticides.

Pesticides are understood to mean those agents the control of plant and animal pests in the places where they are undesirable, allow.

It has already become known that derivatives of benzimidazole-2-carboxylic acids, e.g. Behzimidazole-2-carboxonitrile possess herbicidal properties (Dutch Patent application 7 004 376).

However, the effect of these compounds is especially at low levels Concentrations of effort not satisfactory.

It has been found that the new 4,5-dichloroimidazole-2-carboxylic acid derivatives of the formula (I) in which the group stands for a triple hetero-oriented carbon atom, or the salts thereof with bases have a pest-killing effect.

It has also been found that the new 4,5-dichloroimidazole-2-carboxylic acid derivatives of the formula (I) are obtained if 4,5-dichloro-2-dichloromethylene-imidazole of the formula (11) or 4,5-dichloro-2-trichloromethylimidazole of the formula (III) or the dimeric ketene of 4,5-dichloroimidazole-2-carboxylic acid of the formula (IV) with suitable nucleophiles and the resulting reaction products are optionally subjected to further subsequent reactions.

Salts are preferably obtained in which the 4,5-dichloroimidazole derivative as an anion and a metal cation Men 1 / n 'where n is the valence of the metal, or an optionally substituted ammonium cation NR4 +, where R is hydrogen or an organic residue such as

Alkyl, aryl, cycloalkyl, aralkyl, with 2 or 3 of these Remnants can also be connected to one another to form 5- or 6-membered rings, as Cation is present.

Furthermore, compounds of the formula (I) are preferably obtained in where X, Y and Z independently of one another are halogen, in particular chlorine or fluorine or the following groups are: -S-R1 where R1 is saturated or unsaturated aliphatic or cycloaliphatic hydrocarbon radicals, insx # xf, those with 1-12 carbon atoms' optionally substituted by C1-4alkoxy, C1-4-alkylmercapto, Aryl, aryloxy or aryl mercapto, in particular, aryl stands for phenyl or naphthyl which is optionally substituted by Halogen, C14-alkyl, CF3, C14-alkoxy, alkoxycarbonyl, aminocarbonyl, cycloaliphatic radicals, in particular with 5-6 ring carbon atoms, containing O, S or N, in particular 5 or 6-membered heterocyclic Leftovers.

-O-R2 or -S-R2 where R2 is aryl, in particular phenyl or naphthyl, optionally substituted by C1-4-alkyl, C1-4-polyfluoroalkyl, in particular CF3, halogen, C1 4-alkoxy, aryloxy or aryl mercapto, where aryl is in particular Phenyl or naphthyl, which are optionally substituted by halogen, C1-4-alkyl, CF3, C14-alkoxy, NO2, C1-4-alkylmercapto, C1-4-alkylmercapto, C1-4-alkylsulfonyl, Alkoxycarbonyl, aminocarbonyl, CN, NO2, dialkylamino, in particular with 1-4 carbon atoms per alkyl radical, the aryl radicals can also be fused-on cycloaliphatic or contain heterocyclic rings.

Furthermore, compounds of the formula I are preferably obtained in where X and Y together denote oxygen, sulfur or the group = N-R3 where R3 means hydrogen, OH, C1 ~ 12-alkyl, optionally substituted by halogen, OH, C1-4 alkoxy, aryloxy, in particular phenoxy, optionally substituted by C1 4 alkyl or halogen such as chlorine, C1-4 alkyl mercapto, benzyl mercapto, COOH, CONH2, CONH alkyl, CON (alkyl) 2, CONH aryl where aryl especially phenyl or naphthyl and is optionally substituted by halogen, C14-alkyl, in particular methyl, trifluoromethyl, C1-4-alkoxy, nitro, cycloalkyl with 5 or 6 Ring carbon atoms, optionally substituted by C1-4-alkyl containing O, S or N 5 or 6 membered heterocycles C3 8-alkenyl, optionally substituted by Halogen, C1-4-alkoxy, C31-12-alkynyl, optionally substituted by aryl, in particular Phenyl, which is optionally substituted by halogen, C1 4 -alkyl, trifluoromethyl, C1 alkoxy, nitro cycloalkyl with 5 or 6 ring carbon atoms, cycloalkyl with 4-8 ring carbon atoms, optionally substituted by C1-4-alkyl, CF3, or a fused-on phenyl ring containing, aryl, in particular optionally substituted phenyl or naphthyl, O, S or N-eth-containing 5 or 6-membered heterocycles, furthermore R³ stands for one Group O-R where R4 denotes: C1-4-alkyl, aralkyl, in particular benzyl, or the Group -C - R where R means: hydrogen, C1-12-alkyl, C2-8-alkenyl, each can be substituted by halogen, in particular chlorine, nitro C1-4 alkyl mercapto, Aryl mercapto, in particular phenyl mercapto, optionally substituted by halogen or C1-4-alkyl aryl, in particular phenyl, optionally substituted by halogen or C alkyl 1-4 cycloalkyl with 5 or 6 ring carbon atoms.

C2-8-alkynyl, cycloalkyl with 3-6 ring carbon atoms, aryl, in particular Phenyl or naphthyl, optionally substituted by halogen, C1-4-alkyl, C1-4-alkoxy, CF3, NO2, O, S or N-eth-containing 5 or 6-membered heterocycle or a group -O-R26 or -S-R26 where R26 is C1-12-alkyl, C3-12-akenyl, C3-12-alkynyl may optionally be substituted by halogen, C1 4 -alkoxy, optionally by halogen, C1-4-alkyl, substituted phenyl, cycloalkyl, especially cyclohexyl, O, S or N-containing 5 or 6-membered heterocycles, especially furyl, thiz l, pyridyl.

C3-6-cycloalkyl, aryl, preferably optionally by halogen, C1-4 alkyl, C1-4 alkoxy, nitro, substituted phenyl or naphthyl.

a group R27-N-R27 where the radicals R27 are identical or different can be and are hydrogen, C1-12-alkyl, C3-8-alkenyl, which are substituted can be by halogen, C1 4-alkoxy, optionally by halogen, C1-4-alkyl, substituted aryl, especially phenyl, Cycloalkyl with 5 or 6-ring carbon atoms, aryl, especially phenyl, optionally substituted by halogen, C1 4 alkyl, C14 alkoxy, C1-4 alkyl mercapto, CF3, NO2.

R3 also represents the group R5-N-R6, where R5 and R6 can be identical or different and are hydrogen, C1-4-alkyl, optionally substituted by aryl, in particular phenyl, which is optionally substituted by halogen or C1-4-alkyl, in particular Methyl Aryl, in particular phenyl, optionally substituted by halogen, NO2, C1 4 -alkyl, in particular methyl, C1 4 -alkoxy, CF3, O (S) the group -C-R7 where R7 has the meaning given above or the group -S02 -R8 where R8 denotes C1-12-alkyl, optionally substituted by halogen, in particular chlorine or fluorine, aryl, in particular phenyl, optionally substituted by halogen, in particular chlorine, C14-alkyl, C1-4-alkoxy, CF3, NO2, a secondary amino group R5 and R6 can jointly use the mean, where R9 is identical or different and means C1-12-alkyl, optionally substituted by OH, C1-4-alkoxy, COOH, COO (C1-4-alkyl) cycloalkyl with 5 or 6 ring carbon atoms, aralkyl with 1 -4 C atoms in the alkyl part and in the aryl part, in particular phenyl or naphthyl which is optionally substituted by halogen, NO2, C1 4 -alkyl, C1 4-alkoxy, aryl, in particular phenyl or naphthyl, optionally substituted by OH, halogen, NO2, C1- 4-alkyl, C1-4 alkoxy, C14-alkylmercapto, CF3 O, S or N-containing 5 or 6 membered heterocycles, both radicals R9 can also form a carbocyclic or heterocyclic ring together with the adjacent carbon atom, one of the radicals R9 can also mean hydrogen.

R5 and R6 can form a 5 or 6-membered atom with the adjacent nitrogen atom Form a heterocycle which can contain further heteroatoms, such as 0, N or S.

Preference is also given to compounds of the formula I in which Z denotes a group -O-R10 or -S-R10, where R10 denotes: hydrogen, a salt-forming cation, in particular a metal cation or ammonium cation -NR4 where R has the meaning given above, ( In this case, the bond between 0 or S and the radical R10 does not represent a covalent bond, but rather indicates the formation of the salt.) Alkyl and alkenyl, in particular C1-18-alkyl, C3-12-alkenyl optionally substituted by halogen, in particular Chlorine, fluorine or bromine, OH, acyloxy where acyl denotes the remainder of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid or the remainder of a heterocyclic carboxylic acid, in particular the remainder Alkoxy, in particular with 1-4 carbon atoms, alkoxyalkyleneoxy, aryloxy, in particular phenoxy or naphthoxy, optionally substituted by halogen, C1 4 -alkyl, CF3, NO2 alkyl mercapto, in particular with 1-4 carbon atoms, optionally substituted by aryl, in particular phenyl optionally substituted by C1-4-alkyl or halogen, aryl mercapto, arylsulfinyl, arylsulfonyl, each of which is optionally substituted by C1-4-alkyl or halogen; Alkylsulfonyl, in particular with 1-4 carbon atoms, acylamino or diacylamino, where acyl denotes the remainder of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic carboxylic acid or the remainder of a carbonic acid or thiocarbonic acid derivative CN, carboxylic acid ester, cycloalkyl, in particular with 5-6 Ring carbon atoms.

Aryl, in particular optionally by halogen, C14-alkyl, C1-4-alkoxy substituted phenyl, O, S or N-containing 5 or 6-membered heterocycle AW, l in particular with 3-12 carbon atoms cycloalkyl, in particular with 3-6 ring carbon atoms, if appropriate substituted by halogen, C1-4 alkyl, C14 alkoxy or a fused ring containing, aryl, in particular phenyl or naphthyl, optionally substituted by C1 ~ 4-alkyl, polyhalogen (C1 ~ 4-alkyl), in particular CF3, halogen, C1 ~ 4-alkoxy, Aryloxy or aryl mercapto, in particular optionally by halogen, C1 4 -alkyl, CF3, C1 ~ 4-alkoxy, NO2-substituted phenoxy or phenylmercapto, C1-4-alkylmercapto, C1-4-alkylsulfonyl, alkoxycarbonal, aminocarbonyl, CN, NO2, mono- or dialkylamino, in particular with 1-4 carbon atoms per alkyl part, or the fused-on cycloaliphatic or contains heterocyclic radicals.

Z also represents a group R11-N-R12 where R11 and R12 are identical or different and denote hydrogen, alkyl, in particular with 1-12 carbon atoms, alkenyl, in particular with 3-8 carbon atoms, which are optionally substituted by Halogen, especially chlorine, fluorine, bromine, OH, alkoxy, especially C1-4, aryloxy, especially phenoxy, optionally substituted by C1-4-alkyl, halogen, C1-4-alkoxy, acyloxy, where acyl denotes the radical of an aliphatic, cycloaliphatic , araliphatic or aromatic carboxylic acid or the remainder of a heterocyclic carboxylic acid, in particular the remainder Alkyl mercapto, in particular C1 4, optionally substituted by aryl, in particular phenyl, aryl mercapto, in particular phenyl mercapto, optionally substituted by halogen or C1 4 -alkyl CN, COOH, COOR, CONH2, CONH (C1-C4-alkyl), CON t1-C4- Alkyl) 2, CONH-aryl, where aryl is in particular phenyl or naphthyl, cycloalkyl, in particular with 5-12 ring carbon atoms, which is optionally substituted by halogen, C 1-4 -alkyl, CF3, C1 4-alkoxy, NO2 , S or N containing, in particular, 5 or 6-membered heterocycle or a group R11-N-acyl where R11 has the meaning given above and acyl denotes the remainder of an aliphatic, cycloaliphatic, araliphatic, aromatic carboxylic acid or the remainder of a heterocyclic carboxylic acid, in particular the remainder Alkenyl, in particular with 3-12 C atoms, optionally substituted by optionally substituted aryl, in particular phenyl or cycloalkyl, in particular with 5-6 ring C atoms.

Cycloalkyl, in particular with 4-8 ring carbon atoms, optionally substituted by C1 ~ 4-alkyl, CF3, C1-4-alkenyl, C1 ~ 4-alkynyl, or optionally condensed, containing aromatic or cycloaliphatic rings, S, 0 or N-containing, in particular 5 or 6-membered heterocycle, which is also cycloaliphatic, may contain aromatic or other heterocyclic rings fused, as well as may optionally be substituted, furthermore R11 or R12 stand for aryl, here Aryl stands in particular for optionally substituted phenyl or naphthyl.

Possible substituents are C1-C4-alkyl, C1-4-haloalkyl in particular CF3, halogen, C14-alkoxy and haloalkoxy with 1 - 4 carbon atoms, acetyl, Aryloxy or aryl mercapto, where aryl is in particular phenyl or naphthyl, which can optionally be substituted by halogen, C 1-4 -alkyl, CF3, C1-4-alkoxy, NO2, C14 alkyl mercapto; further substituents are C1-4-alkyl mercapto and haloalkyl mercapto with 1 - 4 carbon atoms, C1-4-alkylsulfonyl, alkoxycarbonyl, aminocarbonyl, CN, NO2, Mono- and dialkylamino in particular with 1 - 4 carbon atoms per alkyl radical. The aryl residues can also contain fused-on cycloaliphatic or heterocyclic rings.

R11 and R12 can also be one together with the adjacent N atom 3-7 membered heterocyclic ring, which has additional 0, S or N heteroatoms may contain, may optionally be substituted as well as optionally condensed, may contain aromatic or heterocyclic rings.

R12 can also denote OH, alkoxy, in particular C1 4, optionally substituted by aryl, in particular phenyl, which may optionally be substituted, O an acyl group -C-R13 where R13 denotes hydrogen, alkyl, in particular C112, alkenyl, in particular C2 ~8 which are each optionally substituted by halogen, C1 ~ 4-alkoxy, aryloxy, in particular optionally halogen, methyl, NO2 substituted phenoxy, alkyl mercapto, in particular C14, aryl mercapto, in particular phenyl mercapto optionally substituted by halogen or methyl, aryl, in particular by halogen or C1 -4-alkyl-substituted phenyl alkynyl, in particular C2 ~ 8, cycloalkyl, in particular with 3-6 ring carbon atoms, aryl, in particular phenyl or naphthyl, optionally substituted by halogen, C1-4 alkoxy, C1-4 alkyl, Cf3, NO2 O, S or N-containing, in particular 5 or 6-membered heterocycles, which optionally are fused-on, cycloaliphatic, cycloaromatic or heterocyclic radicals thalten, a carboxylic acid ester group where R14 denotes alkyl, in particular C112, alkenyl, in particular C3-12, alkynyl, in particular C3-12, which are optionally substituted by halogen, C1-4 alkoxy, aryl, in particular phenyl cycloalkyl optionally substituted by halogen or C1 4 alkyl, in particular with 5-6 ring carbon atoms, a 0, S or N-containing, in particular 5-6 membered heterocycle, cycloalkyl, in particular with 5-6 ring carbon atoms, optionally substituted by C14-alkyl aryl, in particular phenyl or naphthyl, optionally substituted by halogen, C1-4 alkyl, CF3, C14 alkoxy, C1-4 alkyl mercapto, NO2, CN.

a carboxamide group where R15 is the same or different and means @ hydrogen, alkyl, especially C1-12, alkenyl, especially C3-12, which are optionally substituted by halogen, NO2, C1-4-alkyl, CF3, C14-alkoxy, aryl, especially phenyl , optionally substituted by halogen, C1-4-alkyl, CF3, C1-4-alkoxy, C1-4-alkylmercapto, NO2-cycloalkyl, in particular with 5-6 ring carbon atoms; a sulfonyl group -SO2-R8, where has the meaning given above, The group R5-N-R6 where R5 and R6 have the meaning given above.

if X and Y together represent the group = N-R3, then R3 together with Z and the adjacent carbon atom can form heterocycles of the following type R16 where R16 is the same or different and is hydrogen, C1-4-alkyl, C1-4-halogen- (especially Cl or Br) -alkyl, C1-4-alkoxy, aryloxy, especially phenyl, optionally substituted by halogen, C1- 4-alkyl, C1 ~ 4-alkoxy, NO2, where Q is O, S or the group -N-R18 where R18 is Hydrogen, C1-6-alkyl, cycloalkyl, benzyl, aryl, in particular phenyl optionally substituted by C1, C1-4-alkoxy, C1-4-alkyl, NO2, where R19 is Hydrogen, alkyl, in particular C1-12 'optionally substituted by C1-4-alkoxy, aryloxy, in particular phenoxy optionally substituted by methyl or halogen, C1-4-alkylmercapto. Aryl mercapto, in particular optionally methyl or halogen-substituted phenyl mercapto, aryl, in particular optionally phenyl or naphthyl substituted by C1 1-4 alkyl, C14 alkoxy, halogen-substituted phenyl or naphthyl, cycloalkyl, in particular with 5-6 ring carbon atoms, optionally substituted by C1- 4-Alkyl or halogen aryl, in particular phenyl or naphthyl 'optionally substituted by C1-4-alkoxy, C1-4-alkylmercapto, NO2, 0, S or N-containing, in particular 5 or 6-membered heterocycle, the optionally condensed cycloaliphatic, cycloaromatic or contains heterocyclic radicals and can optionally be substituted, in particular by halogen alkoxy, in particular C112, aryloxy, in particular phenoxy, optionally substituted by halogen, C1 4 alkyl, CF3 C1-4 alkoxy, C1 4 alkyl mercapto, C14 alkylsulfonyl, NO2, CN, COO (C14-alkyl), CONH2, N (C1-4-alkyl) 2; Alkylmercapto, in particular C1-12, optionally substituted by C1 4-alkoxy, cycloalkyl, in particular cyclohexyl, aryl, in particular optionally phenyl substituted with chlorine, nitro, methoxy or methyl.

Amino optionally substituted by C1-12-alkyl, cycloalkyl, Aralkyl, aryl, in particular optionally by halogen, alkyl, CF3, NO2, C1-4-alkyl mercapto substituted benzyl or phenyl, if appropriate, two radicals R19 can also be used together a ring fused to the stated heterocycle, preferably an aromatic ring Ring, form.

P denotes 0 or S Z can furthermore denote the azide group X, Y and Z, together with the adjacent carbon atom, can furthermore denote a nitrile group.

Furthermore, compounds are preferably obtained in which Z, when X and Y stands for the radical = N-aryl, for halogen, alkoxy, alkylmercapto, aryloxy, Arylmercapto, the radical -NH-aryl or the radical R11-N-R12, where R11 and R12 are identical or different and have the meaning given above.

Particularly preferred are compounds in which X, Y, Z are independent one another fluorine, chlorine, optionally Cl-substituted phenoxy or methyl mercapto mean.

Also particularly preferred are compounds in which X and Y together denote oxygen and 10 Z denotes: OH, N3 or OR, where R10 denotes: alkyl having 1-12 carbon atoms, optionally substituted by chlorine, OH, CN, C 1-4 4-alkoxy, C1 2-alkoxy-C1 2-alkyleneoxy or phenyl is substituted, cyclohexyl, alkenyl or alkynyl having 3 carbon atoms; furthermore the rest in which R11 and R12 are independently hydrogen, optionally C1-12 alkyl, cyclohexyl, alkenyl or alkynyl having 3-6 carbon atoms which is substituted by CN, OH, CONH2, COOH, phenyl or N-4,5-dichloroimidazole-2-carboxamide , Aryl, especially optionally substituted phenyl or naphthyl.

Possible substituents are C14-alkyl, C1 4-haloalkyl, in particular CF3, halogen, C1-4-alkoxy and C1 4-haloalkoxy, acetyl, aryloxy or aryl mercapto, where aryl stands in particular for phenyl or naphthyl, which may optionally be substituted by halogen, C1-4 alkyl, CF3, C1-4 alkoxy, NO2, C1-4 alkyl mercapto; further substituents are C1-4-alkylmercapto and C1-4-haloalokylmercapto, C1-4-alkylsulfonyl, alkoxycarbonyl, aminocarbonyl, CN, NO2, mono- and dialkylamino, in particular with 1-4 carbon atoms per alkoxy radical. The aryl radicals can also contain fused-on cycloaliphatic or heterocyclic rings. R11 and R12, together with the adjacent nitrogen atom, can also form a 5- to 7-membered heterocyclic ring, which can optionally contain a further N or O atom, Ril and R12 can also represent the radical CHO or in which R14 is C1 4-alkyl, the remainder in which R15 each independently of one another denotes hydrogen, C14-alkyl or phenyl, the remainder wherein R5 and R6 independently of one another are hydrogen, phenyl, COCC13, COOC2H5, or together with the adjacent nitrogen atom the remainder form, in which R9 are each independently hydrogen, C 1-4 -alkyl, or phenyl which is optionally substituted by OH.

Compounds in which X and Y are common are also particularly preferred Denotes oxygen and Z denotes S-R10, in which R10 denotes C1-4-alkyl, in particular Methyl.

Compounds in which X and Y are common are also particularly preferred Mean sulfur and Z means methyl mercapto and amino.

Compounds in which X and Y are common are also particularly preferred the remainder = N-R3, in which R3 means: hydrogen, OH, C14-alkyl 'benzoyloxy, Pyridyl or aryl, in particular optionally substituted phenyl or naphthyl, whereby Possible substituents are C1-4-alkyl, C14-haloalkyl in particular CF3, halogen, C1-4-alkoxy and C14-haloalkoxy, acetyl, aryloxy or Aryl mercapto, where aryl is in particular phenyl or naphthyl, which optionally can be substituted by halogen, alkyl, CF3, C1 4 alkoxy, NO2, C1-4 alkyl mercapto, further substituents are C14-alkylmercapto and C1-4-haloalkylmercapto, C1-4 Alkylsulfonyl, alkoxycarbonyl, aminocarbonyl, CN, NO2, mono- and dialkylamino in particular with 1-4 carbon atoms per alkyl radical. The aryl radicals can also be fused-on cycloaliphatic ones or contain heterocyclic rings.

In these cases, Z preferably denotes alkoxy having 1-4 C atoms, chlorine, aryl mercapto, in particular phenyl mercapto or phenyl mercapto which is optionally substituted by Cl, C1-4-alkyl in which R11 and R12 independently of one another denote hydrogen, C1 4 -alkyl, pyridyl or aryl, where aryl is optionally substituted by C1 4 -alkyl, halogen, C1 4-haloalkyl, C1 4-alkoxy, C1 4-alkyl mercapto, C1 4-haloalkyl mercapto, C1 4-haloalkoxy substituted phenyl.

Compounds in which X, Y and Z together are also particularly preferred with the adjacent carbon atom an oxazole, thiazole, imidazole, oxadiazole, Means thiadiazole or 1,2,4-triazolone radical. A benzene ring can be attached to these residues be condensed, they can also by amino, C1 4-alkyl, optionally by NO2-substituted phenyl or phenoxy, by furyl, pyridyl or optionally be substituted by chlorine-substituted thiazole.

Salts with the following cations are also particularly preferred: sodium or NR4, where R independently of one another is hydrogen, optionally represented by hydroxy substituted alkyl having 1 to 4 carbon atoms or benzyl, or two of the R to a morpholine ring or three of the R interconnected to form a pyridine ring are.

Furthermore, the connection in is particularly preferred forms the CN group. 4,5-dichloroimidazole-2-carboxylic acid derivatives of the formula XVI are also preferred in which W stands for 0, S or the radical = N-aryl and Z when W stands for the radical = N-aryl, for halogen, alkoxy, alkyl mercapto, aryloxy, aryl mercapto, the radical -NH-aryl or the radical R11- N-R12, where R11 or R12 are identical or different and have the meaning given above, and Z furthermore, when W stands for 0 or S, stands for the radical -NH-aryl.

The compounds according to the invention are prepared by adding 4,5-dichloro-2-dichloromethylene-imidazole of the formula (II) or 4,5-dichloro-2-trichloromethyl-imidazole of the formula (III or the dimeric ketene of the 4,5- Dichloro-imidazole-2-cgboxylic acid of the formula (IV) with nucleophiles of the general formula HZ, where Z has the meaning given above, optionally reacting in the presence of acid-binding agents and / or in the presence of water, or treating such reaction products subsequently with water, and optionally converting them into their salts with the aid of bases or by making compounds of the formulas wherein R10 has the meaning given above and Alk is a lower alkyl radical, with nucleophiles of the formula (XV) reacted, where Ril and R12 have the meaning given above or by reacting 4,5-dichloroimidazole-2-carboxylic aurenitrile with nucleophiles of the general formula HZ, where Z has the meaning given above or by 4,5-dichloro-imidazole-2 -thiocarboxamide is reacted with alkalizing agents and the reaction products are subsequently hydrolyzed or cyclized or by using the imide chloride of the formula (XIV) in which aryl stands for an aryl radical, with compounds of the general formula ZH, where Z has the meaning given above, if appropriate in the presence of thinning agents and acid binders, or by hydrolyzing the imide chloride of the formula (xIM if appropriate in the presence of diluents or by adding 4, 5-dichloro-2-dichloromethyleneimidazole of the formula (II) is reacted with equimolar amounts of an amine of the formula (XV), optionally in the presence of diluents, at temperatures below about 90.degree.

All processes for the preparation of the 4,5-dichloro-imidazole-2-carboxylic acid derivatives according to the invention take their starting point from the 4,5-dichloro - 2-dichloromethylene-imidazole of the formula (II) or 4,5-dichloro-2-trichloromethyl-imidazole of the formula (III). These connections have not yet been described in the literature. 4,5-dichloro-2-dichloromethyleneimidazole (II) is obtained by adding 2,4,5-trichloro-2-trichloromethyl-2H-imidazole (V) (available e.g.

by chlorination of 2-methyl-imidazole) with red phosphorus or other reducing agents such as copper (I) chloride, heated: This process is the subject of an earlier patent application that has not yet been published.

The 4,5-dichloro-2-trichloromethyl-imidazole of the formula (III), which can also be used as starting material, is obtained from 4,5-dichloro-2-dichloromethylene-imidazole of the formula II by allowing this dry hydrogen chloride to act: This reaction is preferably carried out in inert solvents, such as aliphatic or aromatic hydrocarbons or halogenated hydrocarbons, for example gasoline, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, chlorobenzene, or in ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane dimeric ketene of 4,5-dichloro-imidazole-2-carboxylic acid of formula (IV) can be obtained a) by targeted hydrolysis of compound II according to the following reaction scheme: (IV) can be obtained particularly advantageously if b) the 1: 1 addition compound of II and the dialkylamide of a lower aliphatic carboxylic acid, preferably N, N-dimethylformamide, of the presumed formula at elevated temperatures, preferably 50 to 1000C, subject to cleavage. Preference is given to working in inert, non-polar solvents such as petroleum ether or carbon tetrachloride.

The addition compound produced in situ is advantageous here directly subjected to cleavage, resulting in (1V).

Another process for the preparation of (IV) consists in reacting c) 4,5-dichloro-imidazole-2-carboxylic acid of the formula (XI) with inorganic acid halides, preferably thionyl chloride: It is preferred to work in excess acid chloride as solvent at temperatures between OOC and the boiling point of the acid chloride and IV is isolated by distilling off excess acid chloride.

To prepare the compounds of the formula I in which X, Y and Z are chlorine or fluorine, but at least one of them is fluorine (formula III a, b, c), the procedure is that the compounds of the formulas II or III allows dry hydrogen fluoride and / or optionally metal fluoride to act. The reaction can be carried out in stages: The reactions are preferably carried out in hydrocarbons as a solvent or in excess hydrofluoric acid. The reaction temperatures are 0 to 2000C for the compound of the formula IIIa, preferably 0-500C, for the compounds of the formulas IIIb and IIIc preferably 20-150 ° C.

To prepare the compounds of the formula I in which the X, Y and Z are the groups -S-R¹, -O-R², -S-R², 2-trichloromethyl-4,5-dichloro-imidazole (III) with phenols, mercaptans or thiophenols in the presence of acid-binding agents.

With phenol or methyl mercaptan as the reaction partner, the reaction takes the following course, for example: Here you work in inert solvents such as hydrocarbons, ethers, ketones or the like. Alkali metal and alkaline earth metal oxides, hydroxides or carbonates or even tertiary amines are preferably used as acid-binding agents. But one can also use previously prepared alkali metal or alkaline earth metal phenolates, mercaptides or thiophenolates for the reaction and then work without the further addition of acid-binding agents. The reactions can also be carried out in the presence of water by, for example

aqueous alkalis used as acid scavengers, both in with Water-miscible solvents or in a two-phase system with water immiscible solvents can work. The reaction temperatures can can be varied over a wide range, e.g. between -200C and 1500C. Preferably one works between 0 and 1000C.

The meaning of R1 and R2 in formulas IX and X is already above have been defined, very particularly preferred are compounds in which R1 is methyl and compounds in which R2 is optionally Cl-substituted phenyl stands.

The compound of the formula I in which X and Y together denote an oxygen atom and Z denotes the OH group, that is to say the 4,5+ dichloro-imidazole-2-carboxylic acid, can be prepared by using the compounds of the formula II or III subject to acid hydrolysis. The reaction proceeds in the following formula-wise way: Mineral acids diluted with water, for example 5- to 90% strength sulfuric acid or phosphoric acid or 5- to 35% strength hydrochloric acid, or anhydrous or water-containing organic carboxylic acids, for example formic acid, acetic acid, oxalic acid, benzoic acid and the like, can be used as the water-supplying reaction medium If anhydrous organic carboxylic acids are used as the hydrolyzing agent, the reaction can also be carried out in the presence of salts of these acids, for example with mixtures of acetic acid and sodium acetate.

The reactions are carried out in the temperature range between 0 and 150 ° C, preferably between 20 and 120 ° C.

However, it is most convenient to hydrolyze oil with water alone Brief heating of compounds of the formulas II or III in excess is sufficient Water at its boiling point until a clear solution is obtained. When cooling down the carboxylic acid of the formula XI crystallizes out.

To convert the 4,5-dichloro-imidazole-2-carboxylic acid into its salts of the formulas XII or XIII, in which A has the meaning given above, if the methods customary for converting organic carboxylic acids or NH-acidic compounds into their salts are used, ie the carboxylic acid is reacted with corresponding metal oxides or hydroxides in the desired stoichiometric ratio or with the single or double stoichiometric amount of ammonia, or a primary, secondary or tertiary amine implemented. Or the procedure is that metal salts of the carboxylic acid are reacted with inorganic salts of those anions which form a sparingly soluble salt with the cation originally bonded to the carboxylic acid. These reactions are preferably carried out in water or alcohols or mixtures of these. The reactions with ammonia and amines can also be carried out in organic solvents which are inert towards amines.

Amine salts of carboxylic acid are obtained from the verb bonds of the Formula II and III directly also in that one with at least three or four Reacting moles of a tertiary amine in the presence of water, e.g.

according to the following formula scheme: This reaction is carried out at 0-100 ° C, preferably at 20-70 ° C. Amine hydrochloride which is formed at the same time can generally be separated off because the amine salts of the carboxylic acid are more difficult to remove in water.

Also leave salts of the formula XII with primary aliphatic amines conveniently from compounds of the formulas II or IIt in the one-pot process in the aqueous Produce medium. To do this, the amine-water mixture is first made acidic (preferably with hydrochloric acid) and then briefly heated with compounds of the formula II or III, preferably to 80-1100C. After setting a weakly alkaline reaction medium, preferably with bicarbonate, the desired salt precipitates.

To prepare the compounds of the formula I in which X and Y together denote an oxygen atom and Z denotes the radical OR10 (formula VI), in which R10 denotes optionally substituted alkyl or cycloalkyl, alkenyl or alkynyl, the procedure is to use the compounds of the formulas II, III or IV reacts with the corresponding aliphatic or cycloaliphatic alcohols.

With methanol and compounds of the formulas II or III as reaction components, the course of the reaction can be shown in the following way: As can be seen from the reaction scheme, at least two moles of the respective alcohol per mole of compound II or III are required for complete conversion. The reaction can be carried out in an excess of this alcohol as solvent or else in inert solvents, such as aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, e.g. gasoline, carbon tetrachloride, toluene, chlorobenzene, in ethers, e.g. diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc. The reactions can be carried out over a wide temperature range, for example between 0 and 125.degree.

It is preferable to work at 15-100C. Isolation of the reaction products generally takes place by simply removing the excess by distillation Solvent and the alkyl chloride formed in the reaction.

To bind the hydrogen chloride released during the reaction can acid-binding agents can also be added in up to a stoichiometric amount, e.g. Alkali and alkaline earth oxides, hydroxides and carbonates as well as tertiary amines.

With glycol and the dimeric ketene of the formula IV as starting products, the reaction takes the following formula: The reactions between the dimeric ketene of the formula IV and aBcholic reaction components are carried out in inert solvents such as aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, open-chain and cyclic ethers, ketones, dimethylformamide, dimethyl sulfoxide or the like. Or else in the alcohol used as the reaction component as a solvent. At least twice the molar amount of alcohol is required per mole of compound IV for complete conversion. The reaction temperatures are 0-2000 ° C., preferably 15 ° C. up to the boiling point of the solvent or alcohol used.

In the cases described, the radical R10 in formula VI denotes: alkyl with 1 to 18 carbon atoms or alkenyl with 3 to 12 carbon atoms, which can be substituted by halogen, in particular chlorine and bromine, hydroxy, acyloxy (where acyl is the radical of an aliphatic , cycloaliphatic, araliphatic, aromatic or heterocyclic carboxylic acid, including the rest means), alkoxy (C1-C4), alkoxyalkyleneoxy (especially with a C2 chain between the oxygen atoms), aryloxy (optionally substituted by halogen, methyl or nitro), alkyl mercapto (C1-C4), benzyl mercapto (optionally substituted in the aryl radical by chlorine ), Aryl mercapto, in particular phenyl mercapto (optionally substituted in the phenyl radical by chlorine or methyl), acylamino (where acyl is the radical of an aliphatic, araliphatic, cycloaliphatic, aromatic or heterocyclic carboxylic acid, including the radical means)) CN, residues of carbonic acid esters, cycloalkyl with 5-6. Ring carbon atoms, aryl, in particular phenyl or naphthyl optionally substituted by Cl, CH3, C1 4-alkoxy, 1 5-6 membered heterocycles which may contain N, O or S as heteroatoms, in particular furyl, thienyl or pyridyl; furthermore R10 denotes C3-12 alkynyl or cycloalkyl with 5-6 ring carbon atoms, optionally substituted by C1-4 alkyl or containing fused rings.

Carboxylic acid esters of the formula VI with tertiary alcohols can be prepared from the carboxylic acid of the formula XI and alkenes, in particular isobutylene and isoamylene, under the catalvtic influence of strong acids such as. B. sulfuric acid. Perchloric acid. Boron trifluoroether, optionally in the presence of solvents such as. B. dioxane, win (see. "Houben-Weyl", 4th edition 1952, Volume VIII, page 534 and "Methodicum Chimicum", 1975, Volume V, page 652.) For the preparation of the compounds of formula I in which X and Y together denotes an oxygen atom and Z denotes the radical OR10 (formula VI) in which R10 denotes optionally substituted aryl, the procedure is as follows: a) the compounds of the formulas II or III with at least an equimolar amount of a phenol in the presence of at least brings two or three molar equivalents of an acid-binding agent and water to the reaction. With phenol as the reaction component, the reaction takes the following course: The reactions can be carried out in water as the reaction medium, in water-miscible solvents such as alcohols, for example

Methanol or ethanol, ketones, e.g. acetone, ethers, e.g. tetrahydrofuran or dioxane or else in a two-phase system with aliphatic or aromatic Hydrocarbons or halogenated hydrocarbons carried out as solvents will. As can be seen from the reaction scheme, at least one or two Moles of water and two or three moles of an acid-binding agent are required. As an acid-binding Alkali and alkaline earth hydroxides and carbonates are preferably used. The reaction temperatures are between -10 and 1000C, preferably between 5 and 600C.

b) 2-Triaryloxymethyl-4,5-dichloro-imidazoles of the formula X of the partial Subjects to saponification in a basic medium.

For the production of the phenyl ester, the reaction takes the following formula according to the formula: The reaction is carried out in the presence of at least one mol of water and at least two molar equivalents of a strong base, preferably alkali and alkaline earth hydroxides or carbonates, using water-miscible solvents such as alcohols, acetone, dioxane, tetrahydrofuran and the like as solubilizers can be present at the same time. The reaction temperatures are between 0 and 100 ° C., preferably between 15 and 750 ° C.

In these cases, R10 is preferably phenyl- or naphthyl, the is optionally substituted by halogen, alkyl (C1-C4), CF3, alkoxy (C1-C4), Alkylmercapto (C1-C4), alkylsulfonyl (C1-C4), alkoxycarbonyl, cyano or nitro.

Particularly preferred are compounds in which R10 is phenyl or Means nitrophenyl.

To prepare the compounds of the formula I in which X and Y together represent an oxygen atom and Z denotes the radical S-R10 (formula VII), the procedure is that 4,5-dichloroimidazole-2-thiocarboxamide (XLI II) (the preparation of the 4,5-dichloroimidazole-thiocarboxamide required as the starting product is described further below), converted into the salt of a corresponding imino-thioether with an alkylating agent and subjected to hydrolysis in a neutral or acidic medium. With methyl iodide as the reaction component, the reaction takes the following course, for example: The alkyl halides, dialkyl sulfates, sulfonic acid alkyl esters, etc., which are customarily known for this purpose, are used as alkylating agents. The first reaction stage is carried out in a largely anhydrous solvent.

Aromatic hydrocarbons, nitromethane, Alcohols, ketones, open-chain and cyclic ethers etc .. The reaction temperatures are between 0 and 1200C, preferably between 20 and 1000C.

The second stage of the reaction is carried out using the at least equimolar Amount of water carried out, preferably in excess water as the reaction medium, mineral acids up to pH 1 can be added. The addition of a A water-miscible solvent is possible, but generally not required.

10 In formula VII, R preferably denotes an alkyl radical with 1 to 12 carbon atoms, which can be substituted by one or more groups of the type: Hydroxy, (C1-C4) -alkoxy, (C1-C4) -alkyl mercapto, cyano, carboxylic acid ester, Carboxamide or optionally substituted by chlorine, nitro, methoxy or methyl Phenyl, also an alkenyl or an alkynyl radical having 3 to 12 carbon atoms.

However, the compound in which R10 is methyl is particularly preferred.

To prepare the compounds of the formula I in which X and Y together denote an oxygen atom and Z denote an optionally substituted amino group (formula XVII), one proceeds in such a way that a) the compounds of the formulas II or III are reacted with the hydrohalide of a primary or secondary amine and the resulting imide chloride-like compounds are subsequently subjected to hydrolysis.

With dimethylamine hydrochloride, the reaction takes the following course: The first stage of the reaction is carried out in aprotic solvents. Cyclic ethers such as tetrahydrofuran and dioxane are particularly suitable. The reaction temperatures are 50 to 200 ° C, preferably 70-120 ° C.

The subsequent hydrolysis reaction can be carried out with or without prior isolation of the intermediate stages are carried out by bringing water to act on them. One Binding of the released hydrogen chloride is not necessary, but it is whose neutralization the presence of equivalent amounts, acid binders, e.g. alkali or alkaline earth oxides, hydroxides or carbonates or tertiary amines are not harmful. The reaction temperatures in the hydrolysis reaction are 0-100 ° C., preferably 10-700C.

For the preparation of 4,5-dichloro-imidazole-2-carboxamides sterically highly hindered secondary amines, e.g.

Diisopropylamine, the first stage of the reaction can take place with the hydrohalides can also be carried out with the free amines themselves.

The procedure is to use the compounds of the formulas II or III in inert solvents such as hydrocarbons, chlorinated hydrocarbons, open-chain or cyclic ethers, ketones etc. or in lower alcohols with at least twice the molar amount of a sterically strongly hindered secondary Amine or with at least one mole of this amine with the addition of the at least equimolar Amount of an acid-binding agent, such as alkali or Erdal) jali carbonates or tertiary amines, in the temperature range between -10 and + 120 ° C, preferably reacted at 0-75 ° C and immediately thereafter or after removal of the Solvent the at least equimolar amount of water and optionally the amount of water Neutralization necessary amount of an inorganic or organic acid-binding agent Means to act.

When reacting with aromatic amines, it is preferred to work above 90.degree. The course of the reaction can be represented as follows: The reaction can be carried out using suitable diluents. Water is preferred as such. The reaction is preferably carried out in the presence of at least 1 mole of hydrochloric acid per mole of the aniline.

The reaction temperatures can be varied within a relatively wide range but generally above about 900C, preferably between 900C and 1500C.

The reaction can also be carried out under normal pressure and under increased pressure will.

Furthermore, compounds of the formula XVII can be obtained by the reaction between the amine and the subsequent hydrolysis in two stages, d. H. carries out with intermediate isolation of an imide chloride of the formula XIV.

If 4,5-dichloroimidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -imide chloride is used as the imide chloride of the formula (XIV) and this is hydrolyzed, the course of the reaction can be shown as follows: Concentrated sulfuric acid is preferably used as the hydrolysing agent, but the hydrolysis can also be carried out with other conventional hydrolysis agents, such as: formic acid, concentrated hydrochloric acid, etc.

The reaction temperatures can be varied over a wide range, generally one works at room temperature.

The reaction can be carried out under normal pressure, but also under increased pressure will.

Imide chlorides of the formula XIV are obtained by adding 4,5-dichloro-2-dichloromethyleneimidazole of the formula II with equimolar amounts of an amine of the formula XV at temperatures converts below approx. 900C.

If 4,5-dichloro-2-dichloromethylene-imidazole of the formula (II) and an equimolar amount of an amine of the formula (xv), for example 2,6-dichloroaniline, are used, the course of the reaction at reaction temperatures below 90 ° C. can be represented by the following reaction scheme : The reaction can be carried out using suitable diluents. Water in particular comes into consideration as such.

The reaction is also preferred in the presence of at least 1 Moles of hydrochloric acid carried out per mole of aniline.

The reaction temperatures can be varied within a relatively wide range are, but is generally worked below 90 0C, preferably between 40 and 700 The reaction can be carried out at normal pressure but also at elevated pressure will.

The imide chlorides of the formula (xIv) obtained in this reaction can as starting materials for the preparation of further compounds according to the invention to serve.

b) In addition, compounds of the formula XVII can be obtained by deacylating 4,5-dichloro-imidazole-2-carboxylic acid-N-formylamides of the formula XX.

With the 4, 5-dichloro-imidazole-2-carboxylic acid-N-formyl-isopropylamide, the reaction takes the following formula, for example: The hydrolyzing agent used is aqueous mineral acids, or else organic carboxylic acids, such as formic acid or oxalic acid, or else concentrated mineral acids, such as, for example, concentrated sulfuric acid. The reaction temperatures are 10-1500C, preferably 20-1000C, depending on the hydrolyzing agent.

The 4,5-dichloro-imidazole-2-carboxylic acid N-formyl-amides required as precursors (According to formula XIX are preferably obtained in such a way that the compound of formula II with at least two moles of a formic acid amide. This reaction can be done in the presence or absence of solvents. As a solvent for example: aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, open-chain and cyclic ethers or aliphatic nitriles such as acetonitrile, water can also be present. The reaction temperatures are -10 to 110 ° C in the event that the work is carried out in an anhydrous manner. If water is present, is the reaction temperature -10 to + 100C.

With compound II and the N-isopropylformamide, the reaction takes the following formula: If at least 1 mole of water is added per mole of the compound of the formula II in this reaction, the corresponding amide is obtained directly in a one-pot process at a reaction temperature of 50 to 150 ° C., preferably 80 to 120 ° C.

In an analogous way, 4,5-dichloroimidazole-2-carboxylic acid-N-acyl-amides of the formula XXI which contain no hydrogen atom on the carbon atom of the acyl group can be prepared.

The first stage of the reaction is in the same solvents and carried out in the same temperature range as specified above. For the second reaction stage the at least equivalent amount of water is added to the unisolated intermediate product in the temperature range between 0 and 1000C, preferably at 10 to 500C, added.

In formula XXI, R13 in this case denotes a radical bonded to CO via carbon which does not contain a hydrogen atom on the α-carbon atom, namely a tertiary alkyl group with 4 to 12 carbon atoms, an α-alkyl-substituted vinyl group with 3 to 8 carbon atoms, an alkynyl group with 2 to 8 carbon atoms, a -substituted cycloalkyl group with 3 to 6 ring carbon atoms, an aryl group, preferably phenyl and naphthyl, optionally substituted by halogen, alkyl (C1-C4), 0-alkyl (C1-C4), S- Alkyl (C1-C4), CF3 or NO2 or a 5- or 6-membered heterocyclic radical with oxygen, sulfur and / or nitrogen in the ring, which can also contain fused carbocyclic or other heterocyclic rings c) Compounds of the formula XVII can also be obtained by converting the cyclic reaction products from the compound of formula II and aliphatic, araliphatic or cycloaliphatic carboxamides, which are carbonylg on the d-atom rgruppe contain at least one hydrogen atom, the formula XXIII is subjected to hydrolysis.

In formula XXII, R20 and R21 are hydrogen, an alkyl radical (C1-C12), an aryl radical or R20 and R21 together represent a tetramethylene or pentamethyl radical.

With the reaction product from the compound of the formula II and acetic acid ethylamide, the reaction takes the following course, for example: The hydrolysis reaction can be carried out with concentrated mineral acids, for example concentrated sulfuric acid, phosphoric acid, hydrochloric acid or with dilute mineral acids, for example

3 to 15% strength hydrochloric acid or 3 to 45% strength sulfuric acid carried out or with organic acids such as formic acid or oxalic acid. The reaction temperatures are 0 to 1500C, preferably 20-1000C.

The cyclic precursors corresponding to formula XXII can be prepared in a simple manner from the compound of formula II by reaction with carboxamides.

Suitable carboxamides are all those derived from primary amines are derived from aliphatic, araliphatic, cycloaliphatic and aromatic Amines. The carboxylic acid portion of these carboxamides must be on the carbon atom contain at least one hydrogen atom in the $ position to the carbonyl group. Consequently e.g. the amides of acetic acid, propionic acid, Butyric acid, isobutyric acid, phenylacetic acid, cyclohexanecarboxylic acid etc.

At least equimolar amounts of the reactants are used, but the carboxamide can also be used in excess as the reaction medium. The reactions can be carried out in inert diluents, but work is preferably carried out without a solvent. The reaction temperatures are 0-1500C, preferably 20-1000C.

This reaction can also be carried out with such compounds, in which carboxylic acid and amine radicals are linked to one another to form a ring, i.e. with lactams.

In these cases, the hydrolysis of the intermediates XXIII leads to carboxamides of 4,5-dichloroimidazole-2-carboxylic acid of the formula XXIV in which the alkyl radical of the amide group is substituted by a carboxy group.

Possible lactams are, for example: pyrrolidone, valerolactam and caprolactam. The reaction conditions correspond to those described above.

d) Compounds of the formula XVII can also be obtained by subjecting 4,5-dichloroimidazol-2-oylureas of the formula XXVI to the cleavage. This cleavage can take place thermally or hydrolytically.

With 4,5-dichloro-imidazoloyl-1,3-dimethyl urea, the reaction takes the following formula, for example: The thermal cleavage can be carried out in the melt, without a diluent or in sufficiently high-boiling solvents, for example chlorobenzene, dichlorobenzene, mesitylene, tetralin, etc. The reaction temperatures are 100-2500C.

The hydrolysis reaction is preferably carried out with concentrated mineral acids, e.g. concentrated sulfuric acid or phosphoric acid or also with concentrated Formic acid made. The reaction temperature is 50-1500C.

The 4,5-dichloro-imidazoloylureas according to formula XXV (or XXVI) required as precursors are obtained from the compounds of the formulas II and III by reaction with urea or with mono- or 1,3-disubstituted ureas. With monosubstituted ureas, the reaction takes the following course, for example: and with 1,3-disubstituted ureas: The preparation is carried out in such a way that the compounds of the formula II or III are reacted with at least twice the molar amount of the corresponding urea. This can be done without a solvent or in inert organic solvents, such as, for example, dioxane, or else in water. The reaction temperatures are from 0 to 1200C, preferably from 20 to 1000C.

In formula XXVI and XXVII, R15 has the meaning already defined above. R preferably represents hydrogen, an alkyl radical with 1 to 12 carbon atoms or an alkenyl radical with 3 to 8 carbon atoms, which can be substituted by O-alkyl (C1-C4), phenyl (optionally substituted by halogen, or C1-C4-alkyl ), Cyclophenyl or cyclohexyl or a phenyl radical (optionally substituted by halogen, C1-C4-alkyl, CF3, O-alkyl and S-alkyl (C1-C4) or Nu2); or e) Compounds of the formula XVII can also be obtained by adding 4,5-dichloro-imidazole-2-thiocarboxylic acid S-ester (corresponding to formula VII) or 4,5-dichloro-imidazolecarboxylic acid aryl ester (corresponding to formula VI ) with ammonia, primary or secondary amines.

With the 4,5-dichloro-imidazole-2-thio-carboxylic acid S-methyl ester or the 4,5-dichloro-imidazole-2-carboxylic acid phenyl ester and dimethylamine, the reaction takes, for example, the following formula: The reactions are preferably carried out in solvents. Suitable as such are water, alcohols, open-chain and cyclic ethers, ketones, aliphatic and aromatic hydrocarbons, dimethylformamide, dimethyl sulfoxide and the like. The alkyl esters and the benzyl esters are suitable as 4,5-dichloro-imidazole-2-thiocarboxylic acid S-alkyl esters, and as 4,5-dichloro-imidazolecarboxylic acid aryl esters, esters with any aryl ester radicals are suitable. Since the phenol part is removed again in these compounds, the unsubstituted phenyl ester is preferably used. The primary or secondary amine is used in at least an equimolar amount, but it can be advantageous (for example in the case of volatile amines) to use an excess of up to a further mol. The reaction temperatures are -20 to + 1200C, preferably 20 to 750C. The preparation of the 4,5-dichloroimidazole-2-thiocarboxylic acid alkyl ester and the 4,5-dichloroimidazole-2-carboxylic acid aryl ester has already been described above; f) Compounds of the formula XVII can also be obtained by reacting the dimeric ketene of 4,5-dichloro-imidazole-2-carboxylic acid of the formula IV with ammonia, primary or secondary amines.

With dimethylamine, the reaction takes, for example, the following formula: The reactions are preferably carried out in solvents. Hydrocarbons, alcohols, open-chain and cyclic ethers, ketones, dimethylformamide, dimethyl sulfoxide, etc. are suitable as such.

The reaction temperatures are -10 to + 150 ° C, preferably works one at 0 to 100 ° C.

In formulas XVII, XIX, XX, XXI, XXII and XXV, R11 and R12 have the meaning already defined in more detail above. These formulas preferably contain R11 and R12 for hydrogen, for an alkyl radical having 1 to 12 carbon atoms or an alkenyl radical with 3 to 8 carbon atoms which can be substituted by halogen (fluorine, chlorine, bromine), hydroxy, alkyl (C1-C4), O-aryl (in the aryl radical optionally substituted by C1-C4-alkyl, halogen, C1-C4-alkoxy), S-alkyl (C1-C4), S-benzyl, S-aryl (optionally substituted in the aryl radical by chlorine or methyl), carboxyl, carboxamide, Cyano, aryl (preferably phenyl and naphthyl, optionally substituted by halogen, methyl, CF3, O-alkyl (C1-C4), NO2), cycloalkyl (with 5 or 6 ring carbon atoms) or by a 5- or 6-membered heterocyclic radical with oxygen, sulfur and / or nitrogen as heteroatomewfor an alkynyl radical with 3 to 12 carbon atoms, optionally substituted by (substituted) phenyl or cycloalkyl (C5-C6); for a cycloalkyl radical with 4 to 8 ring carbon atoms, optionally substituted by alkyl (C1-C4), which can also contain fused-on carbocyclic rings; for a 5- or 6-membered heterocyclic radical with oxygen, sulfur and / or Nitrogen as heteroatoms, which also condenses carbocyclic or heterocyclic rings may contain, where R11 and R12 together with the nitrogen atom connecting them can also form a 3 to 7-membered ring which, in addition to this nitrogen atom also other heteroatoms such as oxygen, sulfur or nitrogen as well as condensed may contain carbocyclic rings, and also aryl, especially substituted or unsubstituted Phenyl or naphthyl.

The preparation of compounds of the general formula XXVII and XXVII a, in which R13 is hydrogen or an optionally substituted organic The radical or R15 denote alkyl or aryl has already been described above (cf. the processes for the preparation of 4,5-dichloro-imidazole-2-carboxamides, formula XIX, XXI, XXV and -XXVI).

Compounds in which R12 is a group can also be prepared in an analogous manner denotes, where R14 denotes alkyl or aryl. To this end, carbamic acid esters are reacted with the compounds of the formula II or III.

If N-monosubstituted carbamic acid esters are used, amide chloride-like compounds are obtained in the first stage, which are then hydrolyzed.

With N-methyl-carbamic acid phenyl ester as the starting product, the reaction proceeds, for example, according to the following equation: The first stage of the reaction is carried out in aprotic solvents, preferably cyclic ethers such as dioxane or tetrahydrofuran, at temperatures between 50 and 150.degree. The subsequent second stage is carried out with at least an equimolar amount of water, it being possible for diluents such as alcohols, ketones, cyclic ethers, etc., to be present. The hydrogen chloride released in the hydrolysis reaction can be bound by adding equimolar amounts of a base, for example alkali and alkaline earth oxides, hydroxides or carbonates or tertiary amines, but this is generally not necessary. The reaction temperatures are 0-1000C, preferably 20-700C.

If N-unsubstituted carbamic acid esters are used, the course of the reaction can be controlled in such a way that N- (4,5-dichloro-imidazoloyl- (2) -carbamic acid esters XXXI are formed in a one-step reaction. In this case, the "hydrolyzing agent" is used for the intermediate products according to formula XXIX a second mole of the carbamic acid ester: With the carbamic acid ethyl ester as the starting product, the reaction proceeds as follows: According to this reaction scheme, at least two moles, preferably 2-3 moles, of a carbamic acid ester are allowed to act on the compound of the formula II. Cyclic ethers such as dioxane and tetrahydrofuran are preferred as the reaction medium. The reaction temperatures are 200C to the boiling point of the respective solvent.

For formula XXX, R11 has already been defined in more detail above. Of the R14 radical denotes an alkyl radical with 1 to 12 carbon atoms, an alkenyl radical with 3 to 12 carbon atoms or an alkynyl radical with 3 to 12 carbon atoms, each of which can also be substituted by halogen, alkoxy (C1-C4), aryl, preferably Phenyl (optionally substituted by halogen or C1-C4-alkyl) or cyclohexyl as well as a cycloalkyl radical with 5 to 6 Ring carbon atoms or an aryl radical, preferably phenyl and naphthyl, optionally substituted by Halogen, alkyl (C1-C4), CF3, O-alkyl (C1-C4), S-alkyl (C1-C4), NO2 or cyano.

To prepare the compounds of the formula XVII in which R11 denotes hydrogen and R12 denotes a sulfonyl group 502-R8 (formula XXXI), the procedure is that 4,5-dichloro-2-dichloromethylene-imidazole (II) is mixed with the alkali metal salt of an N. -unsubstituted sulfonic acid amide R8-S02-NH2 and water.

The reactions take place in water alone or in the simultaneous presence a water-miscible solvent such as acetone, dioxane, tetrahydrofuran and the like, optionally in the presence of an acid-binding agent, such as alkali and alkaline earth oxide, hydroxide or carbonate or tertiary amine. The reaction temperature is O-1000C, preferably 20-100 ° C.

R8 has the meaning already mentioned above and preferably represents represents an alkyl group with 1-4 C atoms, optionally substituted by chlorine or Fluorine or phenyl, optionally substituted by halogen, methyl, C1-C4-alkoxy, CF3 or nitro or a secondary amino group.

To prepare the compounds of the formula I in which X and Y together represent an oxygen atom and Z represent an optionally substituted hydroxylamino group (formula XXXII), a number of processes can be used which are used for the preparation of 4,5-dichloroimidazole 2-carboxamides of the formula XVII were given. For example, according to process e), the 4,5-dichloro-imidazole-2-carboxylic acid phenyl ester or the -S-methyl thioester can be reacted with hydroxylamine or its O-alkyl or N, O-dialkyl derivatives: With hydroxylamine itself, for example, 4,5-dichloroimidazole-2-hydroxamic acid is obtained. The reaction conditions are the same as described in process e) for corresponding carboxamides.

In formula XXXII, R11 and R23 are preferably hydrogen or lower (C1-C4) -alkyl radicals, a benzyl radical or the cyclohexyl radical.

Alkyl and aralkyl radicals corresponding to R11 and R23 can be in the molecule can also be introduced subsequently by adding the 4,5-dichloro-imidazole-2-hydroxamic acid (R11 and R23 = according to known methods, preferably in an alkaline medium, with Reacts alkylating agents.

For the preparation of the compounds of the formula I in which X and Y together is an oxygen atom and Z is an optionally substituted hydrazino group (formula XXXIII), you can also use a number of those for the preparation of 4,5-dichloroimidazole-2-carboxamides apply the specified procedure.

The process in which a 4,5-dichloro-imidazole-2-carboxylic acid alkyl ester is reacted with a corresponding hydrazine has proven to be particularly suitable: With the 4,5-dichloro-imidazole-2-carboxylic acid methyl ester and unsubstituted hydrazine (as hydrate), for example, 4,5-dichloro-imidazole-2-carboxylic acid hydrazide (XXXIIIa) is obtained: The reaction is generally carried out by reacting an alkyl 4,5-dichloro-imidazole-2-carboxylate in a solvent with at least the equimolar amount of hydrazine or a substituted hydrazine. Suitable solvents are aliphatic and aromatic hydrocarbons, open-chain and cyclic ethers, alcohols and the like. Water can also be present. As a result of the strong basicity of the hydrazines, the reaction products are obtained in the form of their hydrazinium salts (salt formation on the acidic ring nitrogen of the imidazole radical) if more than the equimolar amount of the respective hydrazine is used.

The free hydrazides can be obtained from this by acidification. The reaction temperatures are 0-1200C, preferably 20-1000C.

In formula XXXIII, R11, R5 and R6 are hydrogen or an alkyl radical with 1 to 4 carbon atoms, one optionally substituted by halogen or methyl Benzyl radical or an optionally substituted by halogen, nitro, methyl, alkoxy (C1-C4) or CF3 substituted phenyl radical.

R5 and R6 can together with the nitrogen atom connecting them and optionally further heteroatoms such as oxygen, sulfur or nitrogen be closed to form a 5- or 6-membered ring.

The carboxylic acid hydrazides of the formula XXXIII, in which at least one of R5 and R6 is a hydrogen atom, can be subjected to further reactions by known processes. Some of these possible reactions are explained below using the example of 4,5-dichloroimidazole-2-carboxylic acid hydrazide: a) Reaction with aldehydes or ketones, preferably in organic solvents, optionally with acid catalysis: In formula XXXIV, R9 denotes alkyl radicals (C1-C12), optionally substituted by OH, O-alkyl (C1-C4), COOH or COO-alkyl (C1-C4), cycloalkyl radicals with 5 or 6 carbon atoms in the ring, aralkyl radicals with 1- 4 carbon atoms in the alkyl chain and optionally substituted in the aryl radical by halogen, nitro, alkyl (C1-C4) or alkoxy (C1-C4), aryl radicals, preferably phenyl or naphthyl, optionally substituted by OH-halogen, nitro, alkyl (C1-C4 ), Alkoxy C1-C4), alkylmercapto (C1-C4), CF3, heterocyclic radicals with 5 or 6 ring members with oxygen, sulfur or nitrogen in the ring, where both radicals R9 can be closed with one another to form a carbocyclic or heterocyclic ring. One of the radicals R9 can also mean hydrogen.

b) Reaction with carboxylic acid chlorides in the presence of acid-binding agents in water or organic solvents or with carboxylic acid anhydrides in the presence or absence of inert solvents: In formula XXXV, R7 preferably denotes hydrogen, an alkyl radical with 1-12 carbon atoms or an alkenyl radical with 2-8 carbon atoms, optionally substituted by halogen, O-alkyl (C1-C4), O-aryl, in particular optionally by halogen, methyl or nitro substituted phenyl, S-alkyl (C1-C4), S-aryl (optionally substituted by chlorine or methyl), phenyl (optionally substituted by halogen or alkyl (C1-C4); an alkynyl radical with 2 to 8 carbon atoms, a cycloalkyl radical with 3 up to 6 ring carbon atoms, an aryl radical, preferably phenyl and naphthyl, optionally substituted by halogen, O-alkyl (C1-C4), S-alkyl (C1-C4), alkyl (C1-C4), CF3, NO2, a 5th - Or 6-membered heterocyclic radical with oxygen, sulfur and / or nitrogen in the ring, which can also contain fused carbocyclic or other heterocyclic rings.

c) Reaction with (thio) carbonic acid ester chlorides in organic solvents in the presence of acid-binding agents: In formula XXXVI, R26 preferably denotes an alkyl radical having 1 to 12 carbon atoms, an alkenyl radical having 3 to 12 carbon atoms or an alkynyl radical having 3 to 12 carbon atoms, which can optionally be substituted by halogen, alkoxy (C1-C4), phenyl (optionally substituted by C1-C4-alkyl or halogen), cyclohexyl, furyl, thienyl or pyridyl, a cycloalkyl radical with 5 to 6 ring carbon atoms, or an aryl radical, preferably phenyl or naphthyl, optionally substituted by halogen, alkyl (C1-C4), alkyl ( C1-C4) or nitro.

d) Reaction with (thio) carbamic acid chlorides, preferably in organic solvents in the presence of acid-binding agents: or with isocyanates or isothiocyanates, preferably in organic solvents: In formulas XXXVII and XXXVIII, R27 denotes hydrogen, an alkyl radical with 1-12 carbon atoms or an alkenyl radical with 3-8 carbon atoms, which can be substituted by halogen, O-alkyl (C1-C4) or phenyl (optionally substituted by halogen or alkyl (C1-C4), a cycloalkyl radical with 5 or 6 ring carbon atoms or a phenyl radical, optionally substituted by halogen, alkyl (C1-C4), O-alkyl (C1-C4), S-alkyl (C1-C4), CF3 or NO2.

e) Reaction with sulfonic acid chlorides and sulfamic acid chlorides, preferably in organic solvents in the presence of acid-binding agents: In formula XXXIX, R8 denotes an alkyl radical with 1 to 12 carbon atoms, optionally substituted by chlorine or fluorine, phenyl or naphthyl, which are optionally substituted by chlorine, alkyl (C1-C4), alkyl (C1-C4), CF3 or NO2); or a secondary amino group.

The compound of the formula I in which X and Y together represent an oxygen atom and Z an azide group, the 4,5-dichloroimidazole-2-carboxylic acid azide (formula XL) can be prepared by a) on the 4 , 5-dichloro-imidazole-2-carboxylic acid hydrazide (XXXIIIa) allows alpine acid or one of its lower alkyl esters to act. With nitrous acid itself, the reaction takes the following course, for example: The reaction is carried out in water or lower alcohols at temperatures between -20 and + 50 ° C., preferably at 0-200 ° C. or b) 4,5-dichloro-2-dichloromethylene-imidazole (II) is reacted with aqueous solutions of salts of hydrazoic acid: The reaction can be carried out in water alone or in the simultaneous presence of a water-miscible solvent, for example

Dioxane, tetrahydrofuran or acetone can be made.

The reaction temperature is 0-100 ° C, preferably 0-50 ° C.

For the preparation of the compounds of the formula I in which X and Y together represent a sulfur atom and Z represent a group S-R10 (formula XLI) where R1O preferably represents an alkyl radical with 1 to 6 carbon atoms, an alkenyl radical or an alinyl radical with 3-5 carbon atoms, a cyclohexyl radical or a benzyl radical which is optionally substituted by chlorine or methyl, the compounds II or III are first set with salts of hydrogen sulfide to form a salt of 4,5-dichloroimidazole-2-dithiocarboxylic acid (XLII) and allows this to react with an alkylating agent. With sodium hydrogen sulfide and methyl iodide as reactants, the reaction takes the following course, for example: Alkali metal or alkaline earth metal hydrogen sulfides are preferably used for the first stage of the reaction. Water or lower alcohols or mixtures of these are used as solvents.

The reaction temperatures are -20 to + 100 ° C, preferably 0-70 ° C. The salts corresponding to formula XLII can be isolated by evaporating the solvent will. As a rule, however, they are carried out without cleaning as described above in second stage with an alkylating agent in a dithiocarboxylic acid ester, accordingly Formula XLI, over.

The commonly known alkyl, Alkenyl, alkynyl, cycloalkyl or aralkyl halides, or corresponding dialkyl sulfates or sulfonic acid alkyl esters. In general, one works in the same reaction medium, in which the salts of the formula XLII are obtained, preferably in lower alcohols or their mixtures with water, optionally after prior separation of the resulting in reaction leading to XLI alkali or alkaline earth chloride. The reaction temperatures are 0-100 ° C.

To prepare the compound of the formula I in which X and Y together denote a sulfur atom and Z denotes the amino group (formula XLIII), the 4,5-dichloroimidazole-2-carboxylic acid nitrile (L) is reacted with hydrogen sulfide.

For this purpose, all processes known in the literature can be used for the Apply conversion of a carboxylic acid nitrile into a corresponding thioamide. For example one can proceed in such a way that one uses the nitrile L in pyridine as solvent in the presence the equimolar amount of a strongly basic amine (e.g. triethylamine) at 20-50 ° C treated with excess hydrogen sulfide.

Compounds of the formula I in which X and Y together denote a sulfur atom and Z denotes a substituted amino group, an optionally substituted hydrazino group or hydroxylamino group (formula XLIV) can be derived from the 4,5-dichloroimidazole-2-dithiocarboxylic acid alkyl esters, corresponding to formula VIII , by reaction with primary or secondary amines, with hydroxylamines or hydrazines.

In formula XLIV, R11 and R12 are those for the compounds of the formulas XVII, XXXII and XXXIII radicals indicated. The reactions are preferably in made equimolar ratio. Hydrocarbons are used as solvents, Alcohols, open-chain and cyclic ethers and water or mixtures thereof and the organic solvents mentioned. The reaction temperatures are 0-1500C, preferably 15-1000C.

Compounds of the formula I in which X and Y together represent an imino group and Z an alkoxy group are 4,5-dichloro-imidazole-2-imino-carboxylic acid esters of the formula XLV which, like customary iminocarboxylic acid esters, are only stable in the form of their salts. This is obtained by the action of alcohols on 4,5-dichloro-imidazole-2-carboxylic acid nitrile of the formula (L) in the presence of strong mineral acids: The alcohols used are saturated or unsaturated aliphatic, cycloaliphatic or araliphatic alcohols, and the mineral acid used is preferably hydrohalic acids, preferably hydrochloric acid.

The reactions can take place in the respective alcohol as a solvent be carried out or with stoichiometric amounts of alcohol in solvents such as hydrocarbons or open-chain or cyclic ethers. The reaction temperatures are -20 to 1000C, preferably 0-500C.

Compounds of the formula I in which X and Y together are substituted Imino group mean are obtained by adding an imide chloride of the formula XIV with a compound of the general formula Z-H.

If the imide chloride of the formula (XIV) used is 4,5-dichloroimidazole-2-carboxylic acid N- (2,6-dichlorophenyl) imide chloride and the compound of the formula (ZH) 4-chlorothiophenol, the course of the reaction can be as follows represent: The reaction can be carried out using suitable solvents. Water in particular is suitable as such.

The reaction is also carried out in the presence of suitable acid binders, as such come into question z. B. alkali hydroxides, e.g. B. sodium or potassium hydroxide.

The reaction temperatures can vary within a relatively wide range. Generally one works between 10 and 1000C.

The reaction components are generally used in equimolar amounts used with the exception of the cases in which the compound Z-H due to its basic Properties also serves as an acid binder. In these cases you can use a Excess of a compound of the formula Z-H can be worked.

In general, normal pressure is used.

Compounds of the formula I in which X and Y together denote a substituted imino group and Z denote a monosubstituted amino group (formula XLVI), are prepared by allowing primary amines to act on the compounds II or III: In formula XLVI, R11 has the meaning already defined above, but does not mean hydrogen.

Two moles (from II) or three moles (from III) Bound hydrogen chloride. This can be done by going from the to the Amine used in the reaction instead of the two necessary moles of which four or

five applies. However, the corresponding acid-binding agent can also be used Amount of an alkali or alkaline earth carbonate or a tert. Amines are used. The reactions are usually carried out in solvents. As such are suitable: Hydrocarbons, alcohols, open-chain and cyclic Aether as well as water. If water and alcohols are used as solvents, To avoid side reactions, it is advisable to proceed in such a way that during the amine is always present in excess during the reaction. The reaction temperatures are -20 to + 1500C, preferably 0 to 1000C.

The compound of formula I in which X and Y together represent the hydroximino group and z denotes the amino group, the 4,5-dichloro-imidazole-2-carboxylic acid amide-oxime (Formula XLVII).

is produced by adding hydroxylamine to 4,5-dichloro-imidazole-2-carboxylic acid nitrile (L): This reaction is preferably carried out in water or lower alcohols or in mixtures of these. The hydroxylamine is used in at least an equimolar amount. The reaction temperatures are 0-1000C, preferably 15 to 750C.

Derivatives on the -NOH or on the -NH 2 group can also be derived from XLVII of the amidoxime residue. E.g.

the alkylation in an alkaline medium to O-alkyl-amidoximes (XLVIII), the acylation e.g. with carboxylic acid halides or halocarbonic acid derivatives to O-acyl-amidoximes (IL): where in the formulas XLVIII and IL the radicals R4 and R7 have the meaning already given above.

The compound of the formula I in which S, Y and Z together represent a triple bonded nitrogen atom, the 4,5-dichloro-imidazole-2-carboxylic acid nitrile of the formula (L), is produced by clicking on the Allow at least three or 4 mol of ammonia to act on compounds of the formulas II or III: The compound of the formula L is preferably obtained in good yield without significant side reactions if ammonia is always present in excess during the reaction, ie the procedure is preferably such that the compounds of the formulas II or III are introduced into the ammonia initially charged.

Ammonia itself can serve as a solvent, which means that one works in liquid ammonia. Or one uses solutions of ammonia in cyclic Xethers, such as dioxane or tetrahydrofuran or in lower alcohols or water or in mixtures of these. When working in lower alcohols, water or mixtures these become reaction temperatures of -200 to + 500C, preferably 0-250C applied. The nitrile of the formula L falls during production in the form of its water-soluble Ammonium salt from which you can get it by adding sufficient quantities can win mineral acids in free form.

Compounds of the formula I in which two or three of the radicals X, Y and Z via at least one heteroatom each, preferably oxygen, sulfur or Nitrogen, linked together to form a 5-membered ring, are produced by acting on the compounds of the formulas II or III reactants leaves the 1,4-position to one another two hydrogen atoms which can be substituted by acyl groups contain.

Examples of compounds that can be prepared in this way are: a) 5 rings with one oxygen and one nitrogen atom: R16 preferably denotes hydrogen, (C1-C4) alkyl and (C1-C4) alkoxy.

2-aminophenols In formula LII, T denotes identical or different radicals halogen, alkyl (C1-C4), O-alkyl (C1-C4), NO2, CF3 and n is a total number from 1-4.

b) 5 rings with one sulfur and one nitrogen atom: 2-mercapto-alkylamines R 6 has the preferred meaning given above; 2-Amino-thiophenols T and n preferably have the meanings mentioned above. e) 5 rings with two nitrogen atoms: 1,2-diaminoalkanes R16 has the meaning given above, R18 denotes hydrogen, (C1-C6) alkyl, (C5-C6) cycloalkyl, benzyl or phenyl (optionally substituted by chlorine, (C1-C4) alkoxy, (C1 -C4) alkyl or NO2.

1,2-Phenylenediamine T and n have the meaning given above.

d) 5 rings with one oxygen and two nitrogen atoms: Carboxylic acid hydrazides Carbazic acid ester thiocarbazic acid S-ester e) 5 rings with one sulfur and two nitrogen atoms: Thiocarboxylic acid hydrazides Dithiocarbazic acid ester thiosemicarbazide f) 5-rings with three nitrogen atoms: Amidrazones O-alkyl-semicarbazide S-alkyl-thiosemicarbaz ide aminoguanidines Semicarbazides In the formulas LVII, LVIII, LIX and LX, R18 has the meaning given above.

R19 preferably denotes hydrogen, alkyl (C1-C12), if appropriate substituted by (C1-C4) alkoxy, phenoxy (optionally substituted by methyl or halogen), (C1-C4) alkyl mercapto, phenyl mercapto (optionally substituted by methyl or halogen), phenyl or naphthyl (which may be substituted are through methyl, (C1-C4) alkoxy or halogen); Cycloalkyl with 5 or 6 ring carbon atoms, optionally substituted by (C1-C4) -alkyl; Phenyl or naphthyl, which optionally are substituted by halogen, (C1-C4) alkyl, CF3, (C1-C4) alkoxy, (C1-C4) alkylmercapto or NO2; a 5- or 6-membered heterocyclic radical with oxygen, sulfur and / or nitrogen as heteroatoms, which are also fused-on carbocyclic or may contain further heterocyclic rings; Alkoxy with 1 to 12 carbon atoms, Phenoxy, optionally substituted by halogen, (C1-C4) alkyl, CF3, (C1-C4) alkoxy, (C-C4) alkyl mercapto (C14 alkylsulfonyl, NO2, CN; Alkyl mercapto, saturated or unsaturated, with 1 to 12 carbon atoms, optionally substituted by (C1-C) alkoxy, phenyl (optionally substituted by chlorine, nitro, methyl or methoxy); Amino, optionally substituted by (C1-C12) alkyl, (C5-C6> -cycloalkyl, Benzyl, phenyl (optionally substituted by halogen, (C1-C4) alkyl, CF3, NO2, (C1-C4) alkoxy or (C1-C4) -alkyl mercapto.

The reactions according to a) to g) are carried out in the manner that the compounds II or III with at least the equimolar amount of the specified Reacting partner. You can do without the addition of other substances and e.g. the reaction mixtures in the absence of solvents or in organic Solvents such as hydrocarbons (toluene, chlorobenzene), cyclic ethers (Dioxane, tetrahydrofuran), dimethyl sulfoxide and the like until the end of the Let the evolution of hydrogen chloride act on each other. This leads to reactions one in the temperature range between 0 and 2500C, preferably between 20 and 2200C, by.

However, you can also work with the addition of acid-binding agents, which one in twice (when using compound II) or three times the molar amount (when using compound III) applies. Suitable acid-binding agents are: Alkali and Alkaline earth oxides, hydroxides and carbonates as well as tertiary ones Amines such as pyridine, triethylamine, N, N-dimethylaniline and the like. The working temperatures are then -20 to + 1200C, preferably 0 to 700C.

4,5-dichloro-imidazoles substituted in the 2-position by heterocyclic radicals However, by further implementation of secondary products from II and III to win.

One example is: the reaction of 4,5-dichloro-imidazole-2-thiocarboxamide (XLIII) with i-halo-carbonyl compounds, which leads to 2-thiazolo-4, 5-dichloro-imidazoles (LXI): The procedure is the same as for other thiazole derivatives - already described in the literature, by bringing the reaction components into reaction in water or organic solvents, such as hydrocarbons, alcohols, Xther, dimethylformamide, acetonitrile or the like, preferably in an equimolar ratio. To accelerate the reaction, bases which bind hydrogen halide can be added, such as alkali and alkaline earth oxides, hydroxides and carbonates or tertiary amines such as triethylamine, N, N-dimethylaniline or pyridine. The reaction temperatures are 0-1500C, preferably 15-1000C.

In formula LXI, R17 preferably denotes hydrogen, alkyl (C1-C12), Cycloalkyl with 5 or 6 ring carbon atoms, aralkyl and aryl, which are in the aryl part are optionally substituted by halogen, methyl, OH, O-alkyl (C1-C4), S-alkyl (C1-C4) or N02. Both radicals R17 can also form a 5- or 6-membered structure with one another carbocyclic or heterocyclic ring be closed.

The active compounds according to the invention are characterized by a broad herbicidal quality Spectrum of activity, they are the previously known benzimidazole-2-carboxylic acid derivatives clearly superior and thus represent an enrichment of the technology. The active ingredients can be used in both pre-emergence and post-emergence procedures. They are suitable for weed control in grain, cotton and corn as selective Herbicides and can also be used as total herbicides in higher application rates Find.

The possible uses for selective weed control and as Total herbicides are essentially dependent on the application rate.

The active ingredients according to the invention are highly fungitoxic and bacteriotoxic effects. They damage crops in the control concentrations of fungi and bacteria are not necessary. From these greens are them for use as crop protection products to fight fungi and bacteria suitable. Fungitoxic agents in crop protection are used for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The active ingredients according to the invention have a broad spectrum of activity and can be used against parasitic fungi that affect parts of plants above ground infested or attacking the plants from the ground, as well as against seed-borne ones Pathogens.

The active ingredients according to the invention are particularly effective against parasitic fungi that attack above-ground parts of plants, such as rust diseases on cereals caused by Puccinia species, bean rust (Uromyces phaseolie), furthermore against powdery mildew caused by Erysiphe species, apple powdery mildew (Podosphaera leucotricha), in rice against Pyricularia oryzae and Pellicularia sasakii. At above ground Plant parts, the compounds also act against Botrytis species, Septoria species, Helminthosphorium species and Cercospora species. Effective and particularly practical The active compounds according to the invention are important when they are used as seed dressings or soil treatment agents used against phytopathogenic fungi that adhere to the seed and occur in the soil, and seedling diseases on cultivated plants, Cause root rot, tracheomycosis and seed diseases, such as Fusarium species, Thizoctonia species, Verticillium alboatrum, Phialophora cinerescens.

The substances according to the invention are in those for combating fungal and bacterial pathogens, the required application rates are well tolerated by plants.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, sprout inhibitors and especially used as weed killers. Under weeds in In the broadest sense, all plants are to be understood that grow in places where they are are undesirable. Whether the substances according to the invention as total or selective herbicides act depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in the following plants are used: dicot weeds of the genera: mustard (Sinapis), cress (Lepidium), Bedstraw (Galium), chickweed (Stellaria), chamomile (Matricaria), dog chamomile (Anthemis), Button herb (Galinsoga), goose foot (Chenopodium), nettle (Urtica), ragwort (Senecio), foxtail (Amaranthus), purslane (Portulaca), pointed burdock (Xanthium), Morning glory (Convolvulus), morning glory (Ipomoea), knotweed (Polygonum), sesbania (Sesbania), Ambrosia (Ambrosia), scrub thistle (Cirsium), thistle (Carduus), goose thistle (Sonchus), Nightshade (Solanum), pond cress (Rorippa), Rotala, boxweed (Lindernia), Dead nettle (Lamium), speedwell (Veronica), beautiful mallow (Abutilon), Emex, thorn apple (Datura), violets (Viola), hemp nettle, hollow tooth (Galeopsis), poppy seeds (Papaver), knapweed (Centaurea).

Dicot cultures of the genera: Cotton (Gossypium), soa bean (Glycine), turnip (Beta), carrot (Daucus), kidney bean (Phaseolus), pea (Pisum), Potato (Solanum), flax (Linum), morning glory (Ipomoea), bean (Vicia), tobacco (Nicotiana), Tomato (Lycopersicon), peanut (Arachis), cabbage (Brassica), lettuce (Lactuca), cucumber (Cucumis), Pumpkin (Cuburbita).

Monocotweed weeds of the genera: barn milletX (Echinochloa), bristle millet (Setaria), millet (Panicum), fingergrass (Digitaria), timothy grass (Phleum), bluegrass (Poa), fescue (Festuca), Eleusine, Brachiaria, Lolch (Lolium), Trespe (bromus), oats (Avena), sedge grass (Cyperus), black millet (sorghum), couch grass (Agropyron), dog tooth grass (Cynodon), monocharia, fimbristylis, arrowhead (Sagittaria), Sumpfried (Eleocharis), cornices (Scirpus), Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Ostrich grass (Agrostis), foxtail grass (Alopecurus), wind stalk (Apera).

Monocot cultures of the genera: rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), black millet (sorghum), Millet (Panicum), sugar cane (Saccharum), pineapple (pineapple), asparagus (Asparagus), leek (Allium).

However, the use of the active ingredients according to the invention is by no means limited to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control e.g. on industrial and rail systems and on paths and Places with and without trees. Likewise, the compounds for weed control in permanent crops e.g. forest, ornamental wood, fruit, wine, CitFus, nut, banana, Coffee, tea, rubber, oil palm, cocoa, berry fruit and hops plants and for selective weed control can be used in annual crops.

The active compounds according to the invention can be used as such or in their formulations to reinforce and supplement their spectrum of activity depending on the intended use can be combined with other herbicidal active ingredients, with finished formulation or Tank mixing is possible. The following are also particularly suitable for this Active ingredients and other representatives of the groups of active ingredients characterized by these active ingredients.

2,3,6-trichlorobenzoic acid and its salts, 2,3,5,6-tetrachlorobenzoic acid and their salts, 3-nitro-2,5-dichlorobenzoic acid and their salts, 3-amino-2,5-dichlorobenzoic acid and their salts, 2-methoxy-3,6-dichlorobenzoic acid and their salts, 2-methoxy-3,5,6-trichlorobenzoic acid and their salts, 2,6-dichloro-thiobenzamide, 2,6-dichlorobenzonitrile, 2,4-dichlorophenoxyacetic acid and their salts and esters, 2,4,5-trichlorophenoxyacetic acid and their salts and Esters, (2-methyl-4-chlorophenoxy) acetic acid and its salts and esters, 2- (2,4-dichlorophenoxy1-propionic acid, 2- (2-methyl-4-chlorophenoxy) propionic acid and 2- (2,4,5-trichlorophenoxy) propionic acid and their salts and esters, 4- (2,4-dichlorophenoxy) butyric acid and their salts and esters, 4- (2-methyl-4-chlorophenoxy) -butyric acid and its salts and esters, 2,3,6-trichlorophenylacetic acid and their salts, 4-amino-3,5,6-trichloropicolinic acid.

Trichloroacetic acid and its salts, 2,2-dichloropropionic acid and their salts, 2-chloro-N, N-diallylacetic aureamide, dinitrocresol, dinitro-sec.-butylphenol as well as its salts.

3-phenyl-1, 1-dimethylurea, 3- (4'-chlorophenyl) -1,1-dimethylurea, 3- (3 ', 4'-dichlorophenyl) -1,1-dimethyl-urea, 3- (3', 4'-dichlorophenyl) -1-n-butyl-1-methyl-urea, 3- (3 ', 4'-dichlorophenyl) -1,1,3-trimethyl-urea, 3- (4'-chlorophenyl) -1-methoxy-1-methyl-urea, 3- (3'-trifluoromethyl-phenyl) -1, 1-dimethyl-urea, 3- (3 ', 4'-dichlorophenyl) -1-methoxy-1-methylurea, 3- (4'-bromophenyl) -1-methoxy-1-methyl-urea, 3- (3 ', 4'-dichlorophenyl) -3-methoxy-1,1-dimethyl urea, 3- (4'-chlorophenoxyphenyl) -l, l-dimethyl-urea, N-cyclooctyl-N, N-dimethyl-urea, 3- (Benzthiazol-2-yl) -1,3-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea.

N, N-di- (n-propyl) -S-n-propyl-thiocarbamic acid ester, N-ethyl-N- (n-butyl) -S-n-propyl-thiocarbamic acid ester, N, N-di- (n-propyl) -S-ethyl-thiocarbamic acid ester, N-phenyl-O-isopropyl-carbamine acid ester, N- (m-chlorophenyl) -O-siopropyl-carbamic acid ester, N- (3 ', 4'-dichlorophenyl) -O-methyl-carbamic acid ester, N- (m-chlorophenyl) -O- (4-chloro-butyn- (2) -yl) -carbamic acid ester, N- (3'-methylphenyl) -0- (3-z.ethoxycarbonylaminophenyl) -carbamic acid ester, 2,3,3-trichloroallyl N, N-Diisopropyl-thiocarbamic acid.

3-cyclohexyl-5,6-trimethylene-uracil, 5-bromo-3-sec.-butyl-6-methyl-uracil, 3,6-Dioxo-1,2,3,6-tetrahydropyridazine, 4-amino-5-chloro-1-phenyl-pyridazon- (6).

2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4, 6-bis (methoxypropylamino) -s-triazine, 2-methoxy-4,6-bis (isopropylamino) -s-triazine, 2-diethylamino-4-isopropylacetamido-6-methoxys-triazine, 2-isopropylamino-4-methoxypropylamino-6-methylthio-striazine, 2-methylthio-4,6-bis- (iso-propylamino) -s-triazine, 2-chloro-4,6-bis- (ethylamino) -s-triazine, 2-methylthio-4,6-bis- (ethylamino) -5-triazine, 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine, 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine, 2-methoxy-4,6-bis- (ethylamino) -s-triazine, 2-chloro-4,6-bis- (isopropylamino) -s-triazine.

N, N-dietyl-2,4-dinitro-6-trifluoromethyl-1,3-phenylenediamine, N, N-di-n-propyl-2, 6-dinitro-4-trifluoromethyl-aniline, 4-nitro-2,4-dichloro-diphenyl ether, 3,4-dichlorophenyl propionamide, 2 ', 6'-Diethyl-N- (methoxymethyl) -2-chloroacetanilide.

The active ingredients are also suitable for combating animal pests, in particular insects, arachnids and nematodes, which are found in agriculture, in Forests, in the protection of stored products and materials as well as in the hygiene sector. she are against normally sensitive and resistant species as well as against all or individual stages of development effective. The pests mentioned above include: From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scsber.

From the order of the Diplopoda 2. B. Blaniulus guttulatus.

From the order of the Chilopoda, for. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola, for. B. Onychiurus armatus.

From the order of the Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderas, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, for. B. Foriicula auricularia.

From the order of the Isoptera, for. B. Reticulitermes spp ..

From the order of the Anoplura, e.g. B. Phylloxera vast trix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp, Linognathus spp.

From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, e.g. Hercinothrips femoralls, Thrips tabaci.

From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma langierum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvats lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp.

Psylla spp ..

From the order of the Lepidoptera, for. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeute padella, Plutella macutipennia, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Esrias insulana, Heliothis spp., Laphygma exigus, Mamestra brassicae, Panolis flammea, Prodenia litura, spodoptera spp., Tricholpulsia ni, Carpocaps pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Christoneura fumiferana, Clysia ambuguellas, Homona magnanima, tortrix viridana.

From the order of the Coleoptera, for. B. Anobium punctatum, Rhizopertha dominica, bruchidius obtectus, Acanthoscelides obtecus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decelmineata, Phaedon cochleariae, Diabrotica spp., Paylliodes crysocephala, Epilachna verivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonosus spp., Sitophilus spp., Othiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes meneus, Ptinus spp., Niptus hololeucus, Gibbium psaylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimnallon solstitialis, Costelytra zsalandica.

From the order of the Hymenoptera, for. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia sop., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, e.g. Xenopsylla cheopis, Ceratophyllus spp ..

From the order of the Arachnida, e.g. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae ,. Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

The plant-parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..

The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are made in a known manner, e.g. B. by mixing the active ingredients liquefied pressurized liquids with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. In the case of the use of water as an extender, z. B. also organic Solvents can be used as co-solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. B. Aeroaol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock powder, such as kaolins, clays, talc, Chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as finely divided silica, aluminum oxide and silicates; as an emulsifier; non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolysates; as a dispersant: e.g. B. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients, such as fungicides, insecticides and acaricides.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90 percent by weight.

The herbicidal application is both after the post-emergence method as well as possible after the pre-emergence procedure; it becomes when the active ingredients are applied as total herbicides, preferably made after emergence of the plants the use for selective weed control, however, before emergence.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general the application rates are between 0.1 and 25 kg / ha, preferably between 0.25 and 10 kg / ha.

The active compounds according to the invention are used in the form of them commercial formulations and / or those prepared from these formulations Application forms.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges.

The active ingredient concentration of the use forms can range from 0.0000001 up to 100% by weight of active ingredient, preferably between 0.01 and 10% by weight.

They are used in a customary manner adapted to the use forms Way.

When used against hygiene and storage pests stand out the active ingredients through. an excellent residual effect on wood and clay as well as through good alkali stability on limed substrates.

When used as foliar fungicides, the drug concentrations can be varied in the application forms over a wide range. You are in generally between 0.1 and 0.00001 percent by weight, preferably between 0.05 and 0.0001%.

In the treatment of seeds, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.

For soil treatment, amounts of active ingredients from 1 to 1000 g per cbm of soil are required, preferably from 10 to 200 g.

The versatile uses of the active ingredients according to the invention can be seen from the following examples.

Example A Post emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Test plants which have a Height of 5-15 cm have such that the amounts of active ingredient given in the table can be applied per unit area. The concentration of the spray liquor will be like this chosen that the amounts of active ingredient given in the table in 2000 1 water / ha be applied.

After three weeks, the degree of damage to the plants is rated in% damage in comparison to the development of the untreated control. The figures mean: O% = no effect (like untreated control) 100% = total destruction Active ingredients, application rates and results are shown in the table below: Table A Post-emergence test Example- active ingredient- Echnio- Cheno- Gallin- Stella- Urtica Matri- Dau- Sina- oat tree- wheat No effort chloa podium soga ria caria cus pis wool kg / ha #N 1 3 2 1 4 2 1 0 3 3 2 3 CN 0.5 1 0 1 2 1 1 0 3 2 0 1 N H 1 5 5 5 5 5 5 5 5 4 2 3 13 0.5 5 5 5 4-5 4 5 5 5 2 2 2 1 5 5 5 5 5 5 5 5 4 4 3 14 0.5 5 5 5 5 5 5 5 5 4 4 2 1 5 5 5 5 4-5 5 5 5 2 1 3 10 0.5 5 4 5 3 3 5 5 5 2 0 2 1 5 5 5 5 5 5 5 5 3 3 2 28 0.5 5 4-5 5 5 4 5 5 4-5 3 1 2 1 5 5 5 5 5 - 5 5 4 3 4 54 0.5 4 5 5 3 4 - 5 5 4 1 3 1 5 5 5 5 5 - 5 5 4 2 3 51 0.5 5 5 5 3 3 - 5 5 4 1 3 1 4-5 5 5 4 - 5 5 5 1 4 2 62 0.5 3 5 5 3 - 5 5 5 0 1 1 1 3 5 5 2 - 5 5 5 4 4 2 65 0.5 2 4 - 5 5 1 - 5 5 3 1 2 1 1 4-5 5 5 5 - 5 5 5 2 3 2 71 0.5 2 5 5 5 - 4 2 4 0 3 2 Table A (continued) Post-emergence test Example- Active ingredient- Echnio- Cheno- Gallin- Stella- Urtica Matri- Dau- Sina- Oat Tree- Wheat No. Expenditure chloa podium soga ria caria cus pis wool kg / ha 1 5 5 5 5 5 5 5 5 4 5 4 70 0.5 5 5 5 5 5 5 5 5 3 5 4 128 1 4 5 5 5 5 5 5 5 5 5 4-5 0.5 3 5 5 5 5 5 5 5 4-5 5 4 1 5 5 5 5 5 5 5 5 5 5 5 3 0.5 5 5 5 5 5 5 5 5 5 5 5 Table A (continuation) Post-emergence test active ingredient on echino- Cheno- Galin- Stella- Urtica Matri- Dau- Sina- oat tree- Webeispiel wall chloa podium soga ria caria cus pis wool no. Kg / ha 90 1 5 5 5 5 4 5 5 5 4 3 5 0.5 5 5 5 5 3 5 5 5 3 1 5 89 1 3 5 5 2 3 5 5 5 2 1 3 0.5 1 5 4 2 3 5 5 5 1 0 3 41 1 4 5 5 5 5 5 5 5 4-5 4 5 0.5 4 5 5 5 5 5 5 5 4 1 5 142 1 3 4-5 5 3 5 3 5 5 3 2 4 0.5 0 3 3 1 4 1 4 5 2 1 2 237 1 4 4-5 5 4 5 3 5 5 3 1 3 0.5 1 4 3 2 3 2 3 5 3 0 2 238 1 3 5 5 5 5 5 5 5 3 4-5 3 0.5 2 5 5 5 5 5 5 5 2 2 2 239 1 4 5 5 5 5 5 5 5 2 3 4 0.5 3 5 5 4 5 5 5 5 2 2 3 244 1 2 5 5 5 3 5 - 4 3 1 3 0.5 0 5 4 5 3 5 - 4 3 1 2 I9example bire emergence test solvent: 5 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after Doused with the active ingredient preparation for 24 hours.

The amount of water per unit area is expediently kept constant. The concentration of active ingredient in the preparation is irrelevant, only the amount of active ingredient applied per unit area is decisive. After three weeks, the degree of damage to the plants is rated in% damage in comparison to the development of the untreated control. The figures mean: O% = no effect (like untreated control) 100% = total destruction Active ingredients, application rates and results are shown in the table below: Table B Pre-emergence test Example- active ingredient- Echino- Cheno- Galin- Stella- Lolium Matri- Sina- corn oat cotton No effort chloa podium soga ria caria pis 5 3 0 - 1 0 4 0 0 0 0 ## - CN 2.5 2 0 - 0 0 4 0 0 0 0 H (known) 5 5 5 5 5 5 5 5 1 2 2 70 2.5 5 5 5 5 4-5 5 4-5 0 1 1 5 5 5 5 5 5 5 5 4-5 4 4 3 2.5 5 5 5 5 5 5 5 4-5 4 3 Table B (continuation) Pre-emergence test In- Active ingredient- Echino- Cheno- Galin- Stella- Lolium Matri- Sina- Maize oat tree play effort chloa podium soga ria caria pis wool no. Kg / ha 90 5 5 5 - 5 5 5 5 3 4-5 3 2.5 5 5 - 5 5 5 5 3 4-5 2 89 5 5 5 - 5 5 5 5 3 4 1 2.5 5 5 - 5 5 5 5 2-3 3 0 41 5 5 5 - 5 5 4 5 4 4 2 2.5 5 5 5 - 5 5 4 5 3 4 2 142 5 4 5 5 5 4 5 5 3 4 3 2.5 4 5 5 5 4 5 5 2 4 2 237 5 5 5 5 5 4 5 4 4 4 3 2.5 5 5 5 5 4 5 4 3 4 2 238 5 3 5 5 4 3 5 5 2 3 2 2.5 3 5 5 4 3 5 4 2 3 2 239 5 3 5 5 5 3 5 5 3 3 2 2.5 2 5 5 5 3 5 5 3 3 2 144 5 4-5 5 5 5 4 5 5 2 5 4 2.5 4 5 5 5 4 5 5 1 4 3 145 5 5 5 5 5 4 5 5 3 5 4 2.5 5 5 5 5 4 5 5 2 4 4 147 5 5 5 5 5 4 5 5 5 2 5 4 2.5 5 5 5 5 4 5 5 0 4 3 Table B (continuation) Pre-emergence test In- Active substance- Echino- Cheno- Galin- Stella- Lolium Matri- Sina- Maize oat tree play effort chloa podium soga ria caria pis wool no. Kg / ha 148 5 4 5 5 5 4 5 5 3 5 4 2.5 4 5 5 5 3 4 5 2 4 2 149 5 5 5 5 5 4 5 5 3 5 4 2.5 5 5 5 5 3 4 5 1 5 3 150 5 5 5 5 5 4 5 5 2 5 4 2.5 4 5 4 5 2 5 5 1 4 3 Example C Sprout treatment test / grain rust / protective (leaf-destroying mycosis) .06 parts by weight of emulsifier W and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for protective effectiveness, single-leaved ones are inoculated Wheat young plants of the Michigan Amber variety with a uredospore suspension of Puccinia recondita in 0.1% water agar. After the spore suspension has dried on the wheat plants are sprayed with the preparation of active compound dew-damp and set them for incubation for 24 hours at about 20 ° C and 100% humidity in a greenhouse.

After 10 days of residence time of the plants at a temperature of 200C and a humidity of 80-90% one evaluates the population of the plants with rust pustules the end. The infestation on the inoculated leaves is evaluated using values from 1 to 9. 1 means 100 beige effect, 3 = very good effect, 5 = moderate effect and 9 = no effect.

Active ingredients, active ingredient concentrations in the spray mixture and degrees of infestation are shown in the table below.

Table C Sprout treatment test / grain rust protective Active ingredients Active ingredient concentration in% of Example tration in the untreated No spray liquid in control Wt% a N 0.025 9 H 21 0.025 1 23 0.025 1 32 0.025 2 35 0.025 3 39 0.025 1 Table C Sprout treatment test / grain rust protective active ingredients Active ingredient concentration in% of the example tration in the untreated no. Spray mixture in control% by weight 5 0.025 2 28 0.025 3 29 0.025 1 6 0.025 1 44 0.025 3 65 0.025 3 Table C Sprout treatment test / Grain rust protective active ingredients active ingredient concentration in% of the example tration in the untreated no - Infection in% of the example tration in the untreated no Spray mixture in control% by weight 128 0.025 3 139 0.025 1 136 0.025 1 129 0.025 3 132 0.025 1 Example of mycelium growth test Nutrient medium used: 20 parts by weight of agar-agar -200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 parts by weight of Na2HPO4 0.3 parts by weight of Ca (N03) 2 ratio of solvent mixture to nutrient medium: 2 parts by weight of solvent mixture 100 parts by weight of agar medium Composition of solvent mixture 0.19 parts by weight of DMF or acetone 0.01 parts by weight Emulsifier alkylaryl polyglycol ether 1.80 parts by weight water 2 parts by weight solvent mixture The amount of active substance required for the desired concentration of active substance in the nutrient medium is mixed with the stated amount of the solvent mixture. The concentrate is thoroughly mixed in the stated proportions with the liquid nutrient medium, cooled to 42 ° C., and poured into Petri dishes with a diameter of 9 cm. Furthermore, control plates are set up without adding any preparation.

If the culture medium is cold and solid, the plates are filled with the in The mushroom species indicated in the table are inoculated and incubated at about 210C.

The evaluation is carried out depending on the growth rate of the fungi after 4 - 10 days. When evaluating the radial mycelial growth on the treated Compare culture media with growth on control media.

The rating of the fungal growth is done with the following key figures: 1 no fungal growth up to 3 very strong growth inhibition up to 5 moderate growth inhibition up to 7 weak growth inhibition 9 growth of the same untreated control active ingredients, active ingredient concentrations and results are shown in the table below: T table DP ilze and 1 bacterium growth test Active ingredients Example- No. N # -CN 9 9 9 9 9 9 9 9 9 9 9 9 9 9 - - 9 N (known) 22 10 5 1 5 - 1 1 - - 5 1 - 1 - 1 - 1 - 23 - 1 1 1 1 1 - - 5 1 - 1 1 1 - 1 - 28 1 2 1 2 2 2 2 1 1 1 1 1 1 1 1 - 1 1 39 - - - - 1 1 - - 5 1 - 1 5 1 - 1 - 56 - 1 - - 1 3 5 5 - 5 - 1 5 3 - - - 61 5 3 5 - 5 3 5 3 5 3 - 1 - 3 - - - 69 - 5 - - - 5 5 - 5 1 - 1 5 3 - 5 - Table DP ilze and 1 bacterium growth test Active ingredients Example- No. 84 10 - 1 - 5 5 5 - 5 5 1 - 1 - - - - - 132 - - - - - - 5 5 - 1 - 1 - 1 - 1 - 40 - - - - 1 2 5 - - 1 - 1 - 1 - 1 - 73 - 3 - 5 5 5 5 - 5 1 - 1 - 5 - - - 48 3 1 3 3 - 3 3 5 1 1 5 1 - 5 - 1 1 47 3 1 3 1 5 3 3 - 1 1 5 1 - 3 - 1 1 92 5 3 5 1 5 3 3 - 1 1 5 1 3 5 - 3 - 97 3 2 3 1 1 5 2 5 1 1 5 1 1 5 - 1 1 95 3 3 3 5 3 - 3 - 5 1 - 1 - 5 - 1 5 119 - - - - - - - - - 1 - 1 - 1 - - 1 Example A Phaedon larvae test Solvent: 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound dripping wet and populated with mustard beetle larvae (Phaedon cochleariae).

After the specified times, the destruction is determined in%. Included 100% means that all beetle larvae have been killed; 0% means that none Beetle larvae were killed.

Active ingredients, active ingredient concentrations, times of evaluation and results are shown in the table below: Table (plant-damaging insects) Phaedon larvae test Active ingredients active ingredient killing degree centering in 96 in, after 3d O oC-NH-CH3 0.1 100 -CH (CH3) 2 0.01 (known) / Cl o 0.1 100 Cl LNl NH0CF3 H 0.01 100 Cl Cl Q C-NH SCF3 0.1 100 C 0.01 " c Cl Cl 1, '0.1 100 Cl HN "4 0.01 100 ,, NCF3 0.1 100 Cl NC "N 0.01 100 H -CF H 3 Table (plant-damaging insects) (Phaedon larvae test) Active ingredients active ingredient killing centering degree in% in 46 after 3 d Cl Cl 0.1 CON 4 0.1 100 s HN-0.01 100 H CF3 C1 Cl C $ CF 0.1 100 0.01 100 Cl 7 / NN N CF3 H Cl Cl CF, 100 Cl 4 C 0.01 100 Cl C C1 CF tNX aN t CF3 0.1 100 Cl N1 0.01 100 H Example B Plutella test Solvent: 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed dew-damp with the preparation of the active compound and populated them with caterpillars of the cabbage peel (Plutella maculipennis).

After the specified times, the destruction is determined in%.

100% means that all caterpillars have been killed, 0 * means that no caterpillars were killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in the table below: Table (plant-damaging insects) Plutella test Active ingredients active ingredient killing degree concentration in% in% after 3 d H3 O CH3 0-CN (CH3) 2 0.1 0 -CN (CH,) 2 0.1 0 N (CH3) 2 (hek8nDt) C1. ClC11 - NH- C1 01 100 H 0 C1 C) 3 \ ol 100 Cl NHCl HO Cl C1 | 0 b ° 1 100 C11 & 11NH CF3 H Cl Cl C1 trN) CF3 0.1 100 I II H 0 Table (plant-damaging insects) Plutella test Active ingredients active ingredient killing degree concentration in% in% after 3 d C1 1 CF3 Cl 0 [C-NH b Cl Cl 0.1 100 A. Cl 0 ClC1 - Nd OCF3 0.1 100 0 Cl 1 ClEN3 C ~ NHb 0w1 100 O Cl Cl C1LN C- NHg3 Cl 0 # 1 100 Cl Cl Cl C1 H 0.1 100 0 0 Cl Cl Cl ClV no Cl Qt1 100 H Table (plant damaging insects) Plutella test Active ingredients active ingredient killing degree concentration in% in% after 3 d Cl II ¼SlFC: Cl Cl NH 0.1 100 Cl N CF3 F Cl LNt C NH o 1 100 0.1 100 0 Cl II C1 NC - NH O CF3 0.1 100 0 C CF3 Cl N a NH e CF3 0.1 100 O Cl C16 "'0.1 loo c1N C-NH 0.1 100 O CF3 Table (plant damaging insects) Plutella test Active ingredients active ingredient killing degree concentration in% in% after 3 d Cl N 0.1 100 CN1C 1 Cl H NH - Cl Cl Cl Cl Cl c 0.1 100 Cl H> Cl Cl 1 Cl CF3 0.1 100 N C \ / CF3 HH Table (plant damaging insects) Plutella test Active ingredients Active ingredient concentration degree of destruction stepped ion in% in% 3 days C Cl C gg CO ~ NH q 0.1 100 H 3 3 Cl C1 a: CO-NH-C1 01 100 H F3 F3 Cl Cl O-NH OCF2-CHC1F 0.1 100 Cl H 0.1 100 Cl H FFF F. C1 Cl 0.1 100 Cl XND Cl H NN ») Table (plant damaging insects) Plutella test Active ingredients active ingredient killing degree centering in% in% 3 days C1 CF, 0.1 100 C INH CCl Cl Cl Cl II / NH 0.1 100 Cl C ClF3 H Cl Cl C1 H 100 CF3 Cl C / NH-CF3 0.1 100 H wN-43 1 Table (plant damaging insects) Plutella test Active ingredients active ingredient killing degree centering in% in% 3 days Cl C1 4 1 / cl o 3 0.1 100 H C1 Cl C 1N CF3 U NH Cl 0.1 100 HN Cl Example C Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is premixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phasoolus vulgaris), which strongly differ from all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are infected, sprayed dripping wet.

After the specified times, the destruction is determined in%.

100 X means that all spider mites have been killed; O% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are shown in the following table: Table (plant-damaging mites) Tetranychus test Active ingredients active ingredient killing degree concentration in% in% after 2 d CH3 O CH3 O-C11-N (CH3) 2 0.1 0 OCN (CH3) 2 N (CH3) 2 (known) Cl C1II N Cl NH C11 - NH OCF3 0.1 100 0 Cl Cl ß N1, C, - NH CF3 99 CF Cl = N Cl Õ H - NU - CF3 0.1 90 Table (plant-damaging mites) Tetranychus test Active ingredients active ingredient killing degree concentration in% in% after 2 d Cl) - N CH2 NH CF Cl PO NH Cl 0.1 98 C1 HC 0 Cl C N Cl 0.1 90 Cl H C6 NHÖ Cl N Cl t NA C1 N)% 3 CF3 0.1 99 Example D Phytophthora test (tomatoes) / Protective Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkyl aryl polyglycol ether Water: 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the specified amount of solvent and dilutes the concentrate with the specified amount of water, which contains the additives mentioned.

Young tomato plants are sprayed with the spray liquid 2 to 4 leaves to dripping wet. The plants remain on for 24 hours 20 ° C and a relative humidity of 70% in the greenhouse. Then be the tomato plants with an aqueous spore suspension of Phytophthora infestans inoculated. The plants are in a humid chamber with 100% humidity and brought to a temperature of 18 to 20 ° C.

The attack on the tomato plants is determined after 5 days. The received Rating values are converted to percent infestation.

0% means no infestation, 10.0% means that the plants are complete are infested.

Active ingredient, active ingredient concentrations and results are based on the following Table.

Table Phythphthora test (tomatoes) / Protective Active ingredient infestation in% with an active substance concentration of 0.0025% known: S CH2 - NH - C - 5 Zn 56 CH2 - NH - C - ll S. according to the invention: H C11 NH C2H5 7 0 Cl Cl Cl EN C11 - NH CF3 1 0 C "- CF3 CH "4 2 o CF3 CliPN C NH CF3 4 Cl H N 0 Example mycelium growth test Nutrient medium used: 20 parts by weight of agar agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 parts by weight of Na2HP04 0.3 parts by weight of Ca (NO3) 2 ratio of solvent mixture to culture medium: 2 parts by weight of solvent mixture 100 parts by weight of agar culture medium 0.19 part by weight of DMF 0.01 part by weight of emulsifier alkylaryl polyglycol ether 1.80 part by weight of water 2 parts by weight of solvent mixture The amount of active substance required for the desired concentration of active substance in the nutrient medium is mixed with the stated amount of the solvent mixture. The concentrate is thoroughly mixed with the liquid nutrient medium, cooled to 420 ° C., in the specified proportions and poured into Petri dishes with a diameter of 9 cm. Furthermore, control plates are set up without adding any preparation.

If the culture medium is cold and solid, the plates are filled with the in the mushroom species and a bacterium indicated in the table and inoculated at about 21 0C incubated.

The evaluation takes place after 4 - 10 days, depending on the growth rate of the organisms. During the evaluation, the radial growth on the treated culture media is compared with the growth on the control culture media. The growth is rated using the following key figures: 0 no growth 1 very strong growth inhibition 2 moderate growth inhibition 3 weak growth inhibition 4 growth equal to the untreated control active ingredients, active ingredient concentrations and results are shown in the table below: Fungi and 1 bacterium Tabel Mycelium Growth Test Active ingredients Cl # -CO-NH- # 10 - - - - 5 5 5 - - 1 1 - 1 - Cl H Cl CF3 # -C-NH- # - - - - - 3 5 5 - 1 1 - 1 - Cl H O Cl Cl N - # - Cl # -C 1 1 5 1 1 1 2 - 5 1 1 2 1 - Cl H N - # - Cl H Cl Cl Cl O Cl # -C-NH- # 1 1 5 1 1 1 1 - 5 1 1 3 1 5 Cl H Cl Cl O # -C-NH- # - - - - 5 5 - - 5 1 1 5 1 - Cl H Fungi and 1 bacterium Tabel Mycelium Growth Test Active ingredients Cl # -C-NH - # - Cl 10 1 1 5 5 5 5 5 5 - 1 1 1 - - Cl HO CF3 Cl N- # # -C - 1 5 - 3 3 5 5 5 3 5 5 - 5 Cl H NH- # CF3 Cl Cl # -C-NH - # - CF3 1 1 5 3 5 5 5 5 - 5 1 - - - Cl HO Table mushrooms and 1 bacterium Mycelium Growth Test Active ingredients Cl O CF3 # -C-NH - # - CF3 10 - - - 5 - 3 - 5 - 3 1 5 5 - Cl H Cl Cl N - # - CF3 # -C - - 5 - 3 3 - - 5 1 5 - 1 - Cl Cl H N - # - CF3 H CH3 Cl N - # - Cl # -C - 1 5 - 1 3 5 5 - 1 1 - - - Cl H N - # - Cl H CH3 Table Mycelium Growth Test Mushrooms and 1 Bacterium Active ingredients Cl Cl N - # - CF3 # -C 10 - 5 - 5 5 - 5 - - 1 1 - 5 5 Cl H N - # - CF3 H Cl Cl Cl O # -C-NH- # 10 - 3 - - 5 5 5 3 - 5 3 5 3 - Cl H Cl CF3 N - # - Cl Cl # -C CF3 10 3 1 3 1 1 5 1 2 3 1 1 - - - Cl H N - # - Cl H Table Mycelium Growth Test Mushrooms and 1 Bacterium Active ingredients Cl # CF3 Cl C-NH - # - Cl 10 - 1 - 2 3 2 5 5 - 1 2 5 1 - HO Cl # -C-NH - # - OCF3 10 5 1 3 1 2 1 3 5 - 1 1 5 1 - Cl HO Cl # -C-NH - # - S-CF3 10 - - - 5 5 5 5 5 5 1 3 - - - Cl H O Table Mycelium Growth Test Mushrooms and 1 Bacterium Active ingredients Cl N - # - OCF3 # Cl C 10 5 5 5 5 5 5 5 5 - 1 1 - - - H N - # - OCF3 H Cl # Cl C-NH - # - Cl 10 5 1 5 1 2 3 5 3 - 1 5 3 5 - H CF3 O Cl # -C-NH - # - OF 10 - 1 - 1 1 3 5 5 - 1 1 5 5 - Cl F HO OF F. Table Mycelium Growth Test Mushrooms and 1 Bacterium Active ingredients Cl Cl NH - # - CF3 # 10 - - 5 1 1 5 - - 5 1 1 - 2 - Cl C Cl H N- # Cl CF3 Cl NH - # - Cl # 10 5 1 3 1 1 3 3 5 5 1 3 1 5 - Cl C H Cl N- # Cl Example F Sprout treatment test / grain rust / protective (leaf-destroying mycosis) To produce an appropriate preparation of active ingredient, 0.25 parts by weight of active ingredient in 25 parts by weight of dimethylformamide and 0.66 parts by weight of emulsifier alkylaryl polyglycol ether are added, and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

To test for protective effectiveness, single-leaved ones are inoculated Wheat young plants of the Michigan Amber variety with a uredospore suspension of Puccinia recondita in 0.1% water agar. After the spore suspension has dried on the wheat plants are sprayed with the preparation of active compound dew-damp and set incubate them for 24 hours at about 20 ° C and 100% humidity in a greenhouse.

After 10 days of residence time of the plants at a temperature of 200C and a humidity of 80 - 90% one also evaluates the stocking of the plants Rust pustules from. The degree of infestation is expressed as a percentage of the infestation of the untreated Control plants expressed. 0% means no infestation and 100% the same Degree of infestation as in the untreated control. The active ingredient is all the more effective the lower the amount of rust.

Active ingredients, active ingredient concentrations in the spray mixture and degrees of infestation are shown in the table below.

T able sprout treatment test / grain rust / protective wilkstofre active ingredient concentration in% of the tration in the uflbuhandLcn Spray mixture in E weight control Cl Cil cl (N! C NH 0.025 25 II " cl Cl 1LN) C -NH ~ N ° 2 NO, O Q Cl CN '25 C1 itN - - H0 Cl C1 Cl (N) t C- NH- <CF3 or similar H Cll} Ü CH3 C1 H Cl CH3 Cl C11 C- NHgCl to H Cl C1 Hi) NH o F n 25 Cl o Cl AtNC 25 H H Br Cl CF3 1 25 Cl 'C 1. 25 Cl Table (sprout treatment test / grain rust protective Active ingredients Active ingredient concentration in% of tration in the untreated Spray mixture in control Wt% CF3 Clt-N Cl II CCF3 H \ NG Cl 0.025 o CN CF -NHi \ -Cl H " 0 Cl Cl 1 Cl 0.025 25 Cl N g <Cl C u ClN II- 0.025 0 Cl tH nC-NH-G -OCF3 0 Cl LN - / == r \ CF 0.025 0 H nt - SCF3 0 Table sprout treatment test / grain rust protective Active ingredients Active ingredient concentration in% tration in the untreated Spray mixture in control Wt% Cl Cl Cl N C1 EN ß C t 0.025 12.5 H HC 1 Cl l -S-CF3 0.025 25 Cl NH C -S-CF3 Cl N C: IN C1 0.025 12.5 Cl N C-NH- G 0 cm3 CX Cl 1N NC 0.025 12.5 ClNH CF H t Cl N CF3 0.025 25 H no CF3 Table sprout treatment test / grain rust protective Active ingredients active ingredient contamination in% of tration in the untreated Spray mixture in control Wt% Cl C1 AC-NH-C1 0.025 0 CHF2 C1 N 0x025 0 CN C-NHY0 0.025 0 FOXFF F. Cl NF Cl nu C11-NH- -F 0.025 0 H 0 C1 Cl NH -Cl Cl 51 0.025 25 Cl Cl t11 / NH-C) CF 3 0.025 12.5 H XC1 = W. Cl Table sprout treatment test / grain rust protective Active ingredients Active ingredient concentration in% of stepped ion in the untreated Spray mixture in control Wt% CF CF C1 'H Cl 0.025 0 Cl H ci example 1 Dry hydrogen chloride is passed into a solution of 218 g (1.0 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in about 2 liters of dry toluene until the formation of a precipitate (at least 1 mol) has ended. After cooling (the HCl addition is exothermic), suctioning off and drying, 235 g (89% of theory) of 4,5-dichloro-2-trichloromethyl-imidazole with a melting point of 210 ° C. (with decomposition) are obtained.

Example 2 25 g of 4,5-dichloro-2-dichloromethylene-imidazole are stirred in 100 ml of HF in an autoclave at 1000 ° C. for 4 hours. After cooling and letting down the pressure, the excess HF is removed by distillation. The residue is dissolved in ether, washed twice briefly with cold water, dried over Na2SO4 and then the solvent is removed. 21 g of 4,5-dichloro-2-dichlorofluoromethyl-imidazole are obtained after recrystallization once from toluene / petroleum ether. F: 1720C under decomp.

Example 3 380 g of 4,5-dichloro-2-trichloromethyl-imidazole are placed in a fluorination autoclave and 400 ml of HF are allowed to run in at OOC. The autoclave is then closed and a protective pressure of approx. 2 ätu Cl2 is applied. In the course of 1 hour, the mixture is heated to 100 ° C., in a further 2 hours to 1400 ° C. and this temperature is maintained for a further 3 1/2 hours. The pressure rising due to the resulting HCl is released via a cooler through a regulating valve at 20 bar.

After cooling and releasing the pressure, the remaining HF is distilled off, the residue was dissolved in tetrahydrofuran and shaken with NaF. After filtration and distilling off the solvent, 262 g (85.5% of theory) of 4,5-dichloro-2-trifluoromethyl-imidazole remain from F: 186-80C.

Example 4 To the mixture of 28.2 g (0.3 mol) of phenol, 27.3 g (0.3 mol) of conc. Sodium hydroxide solution and 200 ml of dioxane are added in portions at 10-150 ° C. with vigorous stirring 25.5 g (0.075 mol) of 4,5-dichloro-2-trichloromethyl-imidazole. The reaction mixture is stirred for a further 2 hours at room temperature and then 1 l of water is added. The deposited crystals are filtered off with suction and dried. Yield: 25 g (78 96 d. Th.) 4,5-dichloro-2-triphenoxymethyl-imidazole. F: 192-1940 (ethyl acetate).

Example 5 Using 4-chloro-benzene instead of phenol, 4,5-dichloro-2-tris- (4-chloro-phenoxy) -methyl-imidazole of the formula is obtained in an analogous manner Example 6 Methyl mercaptan is introduced into a solution of 9.2 g (0.4 mol) of sodium in 300 ml of ethanol until it is saturated. 25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethyl-imidazole are added in small portions at 0-5 ° C. The mixture is stirred for 2 hours at room temperature, the precipitated common salt is filtered off and the filtrate is evaporated in vacuo. The residue is taken up in 300 ml of water and acidified with hydrochloric acid.

The deposited crystals are filtered off with suction, washed with water and dried. 23 g (78.5 96 d. Th) 4,5-dichloro-2-tris- (methylmercapto) -methyl-imidazole of F: 175-1770C (from toluene) Example 7 are obtained 50 g (0.23 mol) of 4,5-dichloro-2-dichloromethyleneimidazole are boiled with approx. 250 ml of water for 5 to 10 minutes, a colorless solution being formed. After cooling, color divide.

Crystals of 4, 5-dichloro-imidazole-2-carboxylic acid monohydrate from the at 1800C with decomposition (decarboxylation to the well-known 4,5-dichloro-imidazole) melt. Yield: 35 g (80% of theory). One arrives at the same connection, when using 4,5-dichloro-2-trichloromethylimidazole.

Example 8 40 g (0.44 mol) of 50 percent aqueous ethylamine are mixed with concentrated hydrochloric acid until the acidic reaction occurs and then briefly boiled with 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethyleneimidazole until formation a clear solution. After cooling, it is made slightly alkaline with sodium bicarbonate. The resulting precipitate is filtered off with suction, washed with water and dried. 14 g (62% of theory) of the ethylamine salt of 4,5-dichloroimidazole-2-carboxylic acid with a melting point of 290 ° C. are thus obtained. Recrystallizable from water in long fine needles.

Example 9 In a similar manner to Example No. 8 described above, the isopropylamine salt of 4,5-dichloro-imidazole-2-carboxylic acid having a melting point of> 290 ° C. was obtained.

Example 1C In 1 kg (13.2 mol) of glycol monomethyl ether, 560 g (2.56 mol) of 4,5-dichloro-2-dichloromethylene-imidazole are gradually added with slight cooling and stirring to such an extent that the temperature of the exothermic reaction increases Holds 80 - 1000C. It is then evaporated to dryness in vacuo. This gives the 4,5-dichloro-imidazole-2-carboxylic acid methoxy ethyl ester in practically quantitative yield. Melting point 1300C.

The same compound is obtained if, instead of 4,5-dichloro-2-dichloromethyleneimidazole the 4,5-dichloro-2-trichloromethylimidazole is used, where appropriate on 90 -1000C post-heated.

Similarly, the following 4,5-dichloro-imidazole-2-carboxylic acid esters of the general formula can be obtained: Table 1 Example No. R FpOC 11 CH3 160 3 160 12 C2H5 111 13 CH2-CH2-CH3 85 14 CH (CH3) 2 168 15 CH2-CH2Cl 136 16 CH2-CC13 220 17 CH2-CH = CH2 105 18 CH2-C = CH185 19 C4H9 (n) 94 20 94H9 (i) 156 21 C4H9 (sec.) 157 22 C5H11 (n) 40 23 C6H13 (n) 58 24 CH2-C (CH3) 3 195 25 C8H17 (n) ~ 50 26 C10H21 (n) zur40 27 C12H25 (n) y40 FH2C1 28 CH / 2 131 CH3 CH2C1 29 CH ~ 150 2 OCH 30 CH2-CH2-CHCH3 89 UV 0 Example No. R Fp C 31 CH2-CH2-CN 168 32 CH2-CH2-0-C2H5 70 33 CH2-CH2-O-CH (CH3) 2 01 34 CH2-CH2-O-C4H9 (n) oil 35 CH2-CH2-0-CH2-CH2-OCH3 oil 36 CH2-CH2-O-CH2-CH2-OC2H5 oil 37 -CH2- Ü \ / 139 38 -CH2 <Cl 137 39 ~ CH2 ~ CH2 ~ O 119 40 1 163 Example 41 65 ml of concentrated sulfuric acid were added dropwise. A slow stream of gaseous isobutylene is then passed through the reaction mixture at room temperature for about 12 hours.

After standing overnight, excess dissolved isobutylene and some of the dioxane are stripped off in vacuo at room temperature and the residue is added to about 5 l of ice water. The resulting precipitate is filtered off with suction, washed with water and dried. 43 g (28% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid tert-butyl ester are obtained in this way. Colorless acetonitrile needles with a melting point of 180 ° C (with decomposition). Example 42 9.4 g (0.1 mol) of phenol and 25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethyl-imidazole are dissolved in 150 ml of tetrahydrofuran. To this, 27 g (approx. 0.3 mol) of conc. Caustic soda. The mixture is stirred for 1 hour while cooling and for a further 1 hour at room temperature. Then 1 liter of water is added, acidified with hydrochloric acid and the separated crystals are filtered off with suction. These are washed with water and dried. Yield: 11.2 g (43.5, d. Th.), 4,5-dichloro-imidazole-2-carboxylic acid phenyl ester of F: 102-1030C (from toluene) Example 43 In a similar manner, 4-nitro- phenol instead of phenol 4,5-dichloro-imidazole-2-carboxylic acid (4-nitro-phenyl ester) of the formula vom F: 216-2180C (from ethanol) Example 44 19.6 (0.1 mol) 4,5-dichloro-imidazole-2-thiocarboxamide are refluxed with 17 g (0.12 mol) methyl iodide in 150 ml dioxane for 3 hours. Small amounts of insoluble constituents are filtered off and the solution is evaporated in vacuo. a. The residue is stirred with about 5% aqueous hydrochloric acid, filtered off with suction, washed with water and dried. 13.5 g (63% of theory) of 4,5-dichloro-imidazole-2-thiocarboxylic acid S-methyl ester of F: 162-1640C (from petroleum ether) are obtained.

Example 4 A solution of 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in 100 ml of dioxane is mixed with 24 g (0.2 mol) of 3-methylaminopropionitrile hydrochloride and heated to reflux temperature for two hours with stirring . After cooling, it is precipitated in water, filtered off with suction, washed with water and dried. This gives 16.5 g (67% of theory) of 4,5-dichloroimidazole-2-carboxylic acid N- (2-cyanoethyl) -N-methyl amide. Melting point 1840C (from acetonitrile).

Similarly, the following 4,5-dichloro-imidazole-2-carboxamides of the general formula can be obtained: Table 2: / R Example No. -N \ Fp C R. 46 -NtCH3) 2 245 (chlorobenzene) 47 -N (C2H5) 2 119 (acetonitrile) 48 -ND 213 (acetonitrile) 49 - e 215 (acetonitrile) Example 50 25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethyl-imidazole are introduced into the mixture of 30.3 g (0.3 mol) of diisopropylamine and 150 ml of methanol at 0 ° -50 ° C. in small portions .

The mixture is stirred for 1 hour at room temperature, then 150 ml of water are added and the mixture is stirred for a further hour at room temperature. The mixture is then acidified with hydrochloric acid and cooled in ice. The deposited crystals are filtered off with suction, washed with water and dried. Yield: 16.5 g (62.5% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid diisopropylamide. F: 133-1350C (mineral spirits) Example 51 a) 654 g (3 mol) of 4,5-dichloro-2-dichloromethylene are added to a mixture of 783 g (9 mol) of isopropylformamide, 162 g (9 mol) of water and 3 l of acetonitrile with stirring and with cooling at about OOC -imidazole in finely powdered form added in parts over the course of about an hour. The clear solution is then poured into approx. 15 kg of ice water. The resulting white precipitate is filtered off with suction, washed with water and dried. 630 g (84% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N-formyl-isopropylamide with a melting point of 1420 ° C. are obtained in this way. The same result can be obtained without adding water.

b) To 87 g (1 mol) of isopropylformamide are added partially with stirring 21.8 g (0.1 mol) 4,5-dichloro-2-dichloromethyleneimidazole given in finely powdered form, the reaction mixture warms up to approx. 40-50 ° C.

After the exothermic reaction has subsided, it will be in excess Poured ice water. At first a viscous precipitate arises, which after about standing for one hour. After vacuuming, washing with water and drying 23 g of a substance are obtained, the majority of which with that described under a) Product is identical. Melting range about 132-137 ° C. Through fractional crystallization from acetonitrile can be after separation of a sparingly soluble secondary component isolate the product described under a) in pure form with a melting point of 1420C.

c) If approach b) is carried out at a reaction temperature of about 1000C, no significant change in the product composition is observed opposite b).

Similarly, the following 4,5-dichloro-imidazole-2-carboxylic acid-N-formyl-amides of the general formula can be obtained: Table 4 f 88 Example No. R FpOC 52 H 250 53 CH3 216 3 54 C2H5 169 55 CH2-CH20H 135 56 CH2-CH2-CH3 140 57 CH2-CH2-CN 150 58 CH2-CH = CH2 147 59 CH2 CH2 CH2 CH3 130 60 -o 172 (Z) 61 -CH2-Q 142 Example 62 a) from 4,5-dichloro-imidazole-2-carboxylic acid-N-formyl-isopropylamide (see Example 61) 25 g (0.1 mol) 4,5-dichloro-imidazole-2-carboxylic acid-N-formyl- isopropylamide are stirred with 200 ml of concentrated sulfuric acid for about 15 minutes at 50-700C.

After cooling, it is poured onto ice, filtered off with suction, neutral with water washed and dried. 16 g (72% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid are thus obtained isopropylamide of melting point 1500C.

b) from 4,5-dichloro-2-dichloromethylene-imidazole ("one-pot process").

In a mixture of 783 g (9 mol) isopropylformamide and 162 g (9 mol) of water are stirred and with gentle cooling 654 g (3 mol) 4,5-dichloro-2-dichloromethyleneimidazole in finely powdered form partly in the course of about one hour was added, the internal temperature rising to about 75 ° C. Then it is heated to around 90 - 1100 for another half an hour. After this Cooling is precipitated in water, filtered off with suction, washed with water and dried. This gives 566 g (85% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid isopropylamide of melting point 1500C.

Similarly, the following 4,5-dichloro-imidazole-2-carboxamides of the general formula can be obtained: Table 5 Example No. R FP ° C 63 H 260 64 CH3 240 65 C2H5 146 66 CH2-CH2OH 236 67 CH2-CH2-CH3 140 Example no. R 68 CH2-CH-CONH2 194 69 CH2-CH2-CH2-CH3 105 C, H3 70 -C-CH3 218 CH3 C, H3 71-9-C2H5 153 CH3 72 C12H25 86 73 H 186 74 -CH2-Q 172 -CH2-CH2- 149 Example 76 10 g (0.043 mol) of the cyclic reaction product of the formula with 100 ml of concentrated sulfuric acid for about 5 min.

kept between 60 and 800C. After cooling, it is poured onto ice, Sucked off, washed neutral with water and dried. This gives 6 g (67, of theory) 4,5-dichloroimidazole-2-carboxylic acid ethylamide with a melting point of 146 ° C.

The starting product used in Example 75 can be prepared as follows: 87 g (1 mol) of N-ethyl-acetamide are mixed with 21.8 g (0.1 mol) of finely powdered 4,5-dichloro-2-dichloromethyleneimidazole with stirring, the temperature of the exothermic reaction rising to about 50.degree. After cooling, it is precipitated in water, filtered off with suction, washed with water and dried. 14 g (60% of theory) of the bicyclic compound of the above formula with a melting point of 1550 ° C. are thus obtained. Colorless hexane needles.

Similarly, starting from N-methyl-acetamide, the bicyclic compound of the formula with a melting point of 1940C. Their saponification with concentrated sulfuric acid leads, in accordance with the above example, to 4,5-dichloro-imidazole-2-carboxylic acid methylamide with a melting point of 2400 ° C. (see example no. 64).

Example 77 A mixture of 20 g (0.087 mol) of the tricyclic compound of the formula and 100 ml of anhydrous formic acid is refluxed for 2 hours. After cooling, suctioning off, washing with water and drying, 19 g (82% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid (3-carboxy-n-propylamide) with a melting point of 2850 ° C. are obtained. A further 3 g of the carboxylic acid are obtained if the formic acid filtrate is refluxed for a further 6 hours.

The same compound is obtained if you use the tricyclic starting product with about the amount of concentrated sulfuric acid for 15 minutes at about 1000C heated, cooled, poured onto ice and isolated in the usual way.

Similarly, the following 4,5-dichloro-imidazole-2-carboxylic acid (aS-carboxy-n-alkylamides) of the general formula can be obtained: Table 6 Example only. 78 n FpOC starting product 4 233 ci N 78 a C1: N 78 a Example No. 79 n FpOC starting product 5,215 Cl H. 79 a V The tricyclic starting materials used in Examples 77 to 79 can be prepared as follows: 21.8 g (0.1 mol) of finely powdered 4,5-dichloro-2-dichloromethyleneimidazole are added in portions to a mixture of 25 g (0.3 mol) of pyrrolidone and 125 ml of dioxane, the reaction temperature rising to about 50.degree . it is briefly reheated to about 90 ° C, then cooled and poured into water.

After suctioning off, washing with water and drying, 17 is obtained g (74% of theory) of the tricyclic compound of the above formula from the melting point 2300C.

The same compound is obtained if 4,5-dichloro-2-trichloromethylimidazole used as a starting product.

In a similar way, starting from s-valerolactam or ε-caprolactam, the tricyclic compounds of the formulas can be obtained.

Example 80 A solution of 15 g (0.11 mol) of N-methylbenzamide in 100 ml of dioxane is mixed with a solution of 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethylene-imidazole. Then it is briefly heated to the boil and poured onto ice water. The initially precipitated oil solidifies after a few hours. After filtering off with suction, washing with water and drying, 6.0 g (20% of theory) of N-benzoyl-N-methyl-4,5-dichloroimidazole-2-carboxamide with a melting point of 1680 ° C. (acetonitrile) are obtained.

Example 81 A suspension of 15 g (0.25 mol) of urea in 100 ml of dioxane is mixed with 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethyleneimidazole and heated briefly to the boil while stirring. After cooling, it is poured into water, filtered off with suction, washed with water and dried. This gives 18 g (67% theoretical) of 4,5-dichloro-imidazol-2-oylurea, which crystallizes with half a mole of dioxane. Melting point 12900C. The crystal dioxane can be removed at approx. 1400C in vacuo, as well as by briefly boiling in ethanol.

Similarly, the following substituted imidazoloylureas of the general formula can be obtained: Table 7 Example No. R FpOC 82 -CH3> 290 -cH ^ CH3 214 (from 83 sCH3 acetonitrile) 84 4 280 (from Acetonitrile) Example 85 A solution of 26 g (0.22 mol) of N, N'-diethylurea in 150 ml of water is mixed with 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethylene-imidazole and heated to 1000 ° C. with stirring heated. After cooling, it is filtered off with suction, washed with water and dried. 18.5 g (66% of theory) of 4,5-dichloro-imidazol-2-oyl-N, N'-diethylurea with a melting point of 159 ° C. are thus obtained.

If one part by weight of the reaction product is boiled for about 1 hour.

with about 10 times the amount of anhydrous formic acid, then pulls then the formic acid is removed in vacuo and the residue crystallizes out Acetonitrile in order to obtain 4,5-dichloroimidazole-2-carboxylic acid-N-ethylamide in good yield of melting point 1460C (see example no. 75).

Example 86 is obtained in a manner analogous to the compound described in Example No. 77 above. Melting point 2050C.

Already in the attempt, the reaction product from boiling acetonitrile recrystallize, cleavage to 4,5-dichloroimidazole-2-carboxylic acid-N-methylamide of melting point 2400C instead (see example no. 60).

Example 87 21.1 g (0.1 mol) of 4,5-dichloro-imidazole-2-thiocarboxylic acid S-methyl ester are refluxed for 3 hours with the solution of 11 g (0.25 mol) of dimethylamine in 100 ml of water. The solution is filtered, cooled and acidified. The deposited crystals are filtered off with suction, washed with water and dried. Yield: 9 g (43 46 d. Th) 4,5-dichloro-imidazole-2-carboxylic acid dimethylamide. F: 244-2460C (toluene) (see example 45).

Example 88 In a suspension of 10.0 g (0.0306 mol) of the dimeric ketene of the formula IV gaseous dimethylamine is introduced into 100 ml of dimethylformamide until a clear, practically colorless solution is formed. It is then evaporated to dryness in vacuo and recrystallized from chlorobenzene. 11.5 g (90% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N, N-dimethylamide with a melting point of 245 ° C. are thus obtained.

In a similar manner, the following 4,5-dichloro-imidazole-2-carbonamides of the general formula can be obtained: Table 8 Example No. for FpOC R. CH3 89 NH-CH 127 (petroleum ether) C2H CH3 90 NH-C <- cx 159 (cyclohexane) CH3 91 NH-CH2-CH2-O 182 (acetonitrile) 92 -N (CH2-CH2-CH3) 2 93 (petroleum ether) 93 -N (n-C4H9) 2 90 (PetrolEther) 94 -N (i-C4H9) 2 127 (petroleum ether) 95 -N 242 (dioxane) 96 -Dj> 290 (DMF) 97 -D 186 (acetonitrile) 98 NH-C12H25 (n) 86 (petroleum ether) 99 N (CH2-CH = CH2) 2 95 (petroleum ether) C, 2H5 100 NH-C-CsCH 173 (acetonitrile) C2H5 101 NH-C H 180 (acetonitrile) C-CH 102 NH-CH2 '184 (acetonitrile) 0 Table 8 (continued) Example No. -NX FpOC R. 103 NH-CH2c 133 (acetonitrile) 104 NH-CH2 <197 (dioxane) 105 NH-CH2- to 169 (acetonitrile) Example 106 could be obtained in a similar manner from ethylenediamine.

Mp 2900C (from ethanol).

Example 107 A suspension of 10.0 g (0.0306 mol) of the dimeric ketene of formula IV in 100 ml of glycol is heated to about 1500C until a clear solution is formed. The excess glycol is then spun off in vacuo. 13 g (14% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid (2-hydroxyethyl) ester with a melting point of 1700 ° C. are thus obtained. Colorless crystals from acetonitrile.

The dimeric ketene used in Examples 87 to 98 can be prepared as follows: a. In a boiling solution of 100 g (0.46 mol) of 4,5-dichloro-2-dichloromethylene-imidazole in 1 liter of petroleum ether (boiling range approx. 600 ° C.), 40 g (0.55 mol) of dimethylformamide are added in about 10 minutes added dropwise, a precipitate separating out.

After cooling, the petroleum ether is decanted and the precipitate stirred with acetone. Then it is suctioned off and washed with acetone for so long until this expires in light yellow. 41 g (55 d. Th.) Of the dimeric ketene are obtained in this way above formula in the form of a light yellow powder with a melting point of> 2900C.

b. A mixture of 500 g (2.51 mol) 4,5-dichloro-imidazole-2-carboxylic acid monohydrate (For preparation see Example No. 7) and 7.8 1 thionyl chloride is about 24 hours stirred under reflux (about 750C). After cooling, it is suctioned off, with a little thionyl chloride, then washed with petroleum ether and dried. This gives 362 g (89, d. Th.) of the dimeric ketene of the above formula in the form of a light yellow powder with a melting point of> 290 ° C, identical to that under a. manufactured product.

Example 108 A solution of 20 g (0.225 mol) of ethyl carbamate and 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethylene imidazole in 50 ml of dioxane is briefly heated to the boil (approx. 1150 ° C.). After cooling, it is precipitated with water, filtered off with suction, washed with water and dried. 15 g (60% of theory) of N- (4,5-dichloroimidazol-2-oyl) -carbamic acid ethyl ester with a melting point of 2080 ° C. (from acetonitrile) are obtained.

Example 109 In a manner similar to Example 89 described above, N- (4,5-dichloro-imidazol-2-oyl) -carbamic acid methyl ester of melting point 2470 ° C. (from ethanol) was obtained.

Example 110 A suspension of 22 g (0.114 mol) of the sodium salt of p-toluene-sulfonamide in 200 ml of water is stirred with a solution of 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethylene-imidazole in 25 ml of dioxane are added. It is then briefly heated to the boil and suctioned off while still boiling.

The precipitate is dried and recrystallized from acetonitrile or toluene. 14 g (42% of theory) of N- (4-methylphenylsulfonyl) -4,5-dichloroimidazole-2-carboxamide are thus obtained of melting point 2380C.

Example 111 20.9 g (0.1 mol) of ethyl 4,5-dichloro-imidazole-2-carboxylate are added in portions to the mixture of 15 g (0.3 mol) of hydrazine hydrate and 100 ml of ethanol while stirring at room temperature. The mixture is boiled for 2 hours and cooled. The hydrazine salt of 4,5-dichloro-imidazole-2-carboxylic acid hydrazide precipitates. This is filtered off with suction, suspended in 100 ml of water and brought into solution by adding dilute sodium hydroxide solution. The solution is acidified with acetic acid. The deposited crystals are filtered off with suction, washed with water and dried. Yield: 11 g (56.5 96 d. Th.) 4,5-dichloro-imidazole-2-carboxylic acid hydrazide of F: 210-211 ° C. (from ethanol).

Example 112 21.1 g (0.1 mol) of 4,5-dichloro-imidazole-2-thiocarboxylic acid S-methyl ester are refluxed with 10.8 g (0.1 mol) of phenylhydrazine in 150 ml of ethanol for 4 hours. The cooled reaction mixture is mixed with 500 ml of water, and the precipitated crystals are filtered off with suction and dried. 13.5 g (50-46 of theory) of 4,5-dichloro-imidazole-2-carboxylic acid N'-phenylhydrazide of F: 229-2300C (from ethyl acetate) are obtained.

Example 113 19.5 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid hydrazide and 7.2 g (0.1 mol) of isobutyraldehyde are concentrated in 150 ml of ethanol with the addition of 1 ml. Hydrochloric acid refluxed for 3 hours. After the solvent has been distilled off, the 4,5-dichloro-imidazoloyl- (2) -isobutyrhydrazone remains in quantitative yield. F: 172-1740C (from toluene) Example 114 If the equimolar amount of salicylaldehyde is used instead of isobuiyraldehyde, the corresponding hydrazone of the formula is obtained F: 3000C (from glycol monomethyl ether) Example 115 19.5 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid hydrazide and 10.1 g (0.1 mol) of triethylamine are placed in 150 ml of dioxane. 18.2 g (0.1 mol) of trichloroacetyl chloride are added dropwise to this at 10-15 ° C. while stirring. The mixture is stirred for 2 hours at room temperature, 500 ml of water are added and the crystals which have separated out are filtered off with suction. Yield: 26.2 g (77% of theory) of N- (4,5-dichloroimidazolyl- (2)) -N 'trichloroacetylhydrazine.

F: 192-1940C (ethyl acetate) Example 116 With the equimolar amount of ethyl chloroformate instead of trichloroacetyl chloride, the N '- (4,5-dichloroimidazoloyl (2)) - carbazic acid ethyl ester of the formula is obtained in an analogous procedure: F: 235-2370C (butanol) Example 117 Process variant a): 19.5 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid hydrazide are dissolved in 150 ml of 5-point aqueous hydrochloric acid. At 0-50C, the solution of 7 g (approx. 0.1 mol) of sodium nitrite in a little water is added dropwise with vigorous stirring. The mixture is stirred for 1 hour.

at the same temperature, filtered off with suction, washed the crystals with water and dry them at room temperature. Yield of 4,5-dichloro-imidazole-2-carboxylic acid azide practically quantitative. IR spectrum and mass spectrum confirm the structure.

The connection fizzles out at approx. 1750C without melting.

Process variant b): To a solution of 80 g (1.23 Mol) sodium azide in 1 liter of water is stirred and ice-cooled between about 10-30 ° C a solution of 21/8 g (1.0 mol) 4,5-dichloro-2-dichloromethylene-imidazole added dropwise in 250 ml of dioxane in the course of about 20 minutes. Then it is suctioned off, washed with water and dried. 196 g (95% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid azide are obtained in this way, identical to the product manufactured under a).

Example 11 8 25.45 g (0.1 mol) of 4,5-dichloro-2-trichloromethyl-imidazole are introduced in portions at room temperature with vigorous stirring into a solution of 24 g (0.5 mol) of sodium hydroxide in 150 ml of methanol, which is saturated with hydrogen sulfide . The mixture is stirred for 2 hours at room temperature and 2 hours at 50 ° C., the precipitated common salt is filtered off with suction and 14.2 g (0.1 mol) of methyl iodide are then added dropwise to the filtrate. The mixture is stirred for 1 hour at room temperature and 1 hour at 40-450C and then i. Vac. evaporated. The residue is dissolved in water, the solution is acidified, the precipitated crystals are filtered off with suction, washed with water and dried.

Yield: 19.7 g (80% of theory) 4,5-dichloro-imidazole-2-dithiocarboxylic acid methyl ester. F: 122-1240C (petroleum ether).

Example 119 16.2 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid nitrile are dissolved in 125 ml of pyridine. 10.1 g (0.1 mol) of triethylamine are added and, starting at room temperature, the temperature is gradually increased to 500 ° C. for 5 hours with dry hydrogen sulfide. The reaction mixture is i. Vac. evaporated, the residue dissolved in water, the solution acidified with hydrochloric acid, the precipitated crystals filtered off with suction. The crude product contains some elemental sulfur and is freed from this by dissolving it with dilute sodium hydroxide solution, filtration and renewed acidification. Yield: 16.2 g (82.5% of theory) 4,5-dichloro-imidazole-2-thiocarboxamide.

F: 171-1730C (toluene).

Example 120 16.2 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid nitrile are suspended in 150 ml of methanol. Dry hydrogen chloride is passed in at 10-15 ° C. until it is saturated. The undissolved material is filtered off, the filtrate i. Vac. evaporated, the residue pressed onto clay and dried in a desiccator over KOH. Yield: 13 g (56.5% of theory) 4,5-dichloro-imidazole-2-iminocarboxylic acid methyl ester hydrochloride. F:> 250 ° C.

Example 121 In 73 g (0.5 mol) of 50% strength aqueous tert-butylamine, 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethyleneimiadzole are stored with stirring, the reaction mixture increasing to about 80.degree warmed up. After cooling, it is precipitated in water, filtered off with suction, washed with water and dried. This gives 24 g (80% of theory) of 4,5-dichloro-imiadzol-2-carboxylic acid-N, N'-di-tert.-butylamidine. From ethanol / water, pale yellow crystals with a melting point of 1690C.

Similarly, the following 4,5-dichloro-imidazole-2-carboxamidines of the general formula can be obtained: Table 9 Example No. R FpOC 122 CH3 280 123 C2H 223 (from 2 5 methanol) FH, 124 -CH 3 3 Example 125 To a solution of 25.4 g (0.1 mol) 4,5-dichloro-2-trichloromethylimidazole in 200 ml dioxane is added dropwise with cooling at 10-15 ° C a mixture of 18.8 (0.2 mol) α- Amino-pyridine and 30.3 g (0.3 mol) of triethylamine. The mixture is stirred for 2 hours at room temperature, 1 l of water is added and the mixture is made weakly acidic with acetic acid. The deposited crystals are filtered off with suction, washed with water and dried. 25.4 g (77% of theory) of 4,5-dichloro-imidazole-carboxylic acid-N, N'-di-pyridyl- (2) -amidine are obtained. F: 199-2000C (from ethyl acetate / ligroin).

C14H10C12N6 (333.2) Calc .: 21.3% Cl, 25.23, N Found: 20.8 25.0 Example 126 16.2 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid nitrile are suspended in 120 ml of ethanol. To this are added 8 g (0.115 mol) of hydroxylammonium chloride and then in small portions 14; Potassium carbonate. The mixture is heated to the boil and boiled until there is no further evolution of CO2.

The salt-like components are suctioned off and washed with ethanol, the combined filtrates i. Vac. evaporated. The residue is made from ethyl acetate recrystallized. 12.2 g (63% of theory) of 4,5-dichloro-imidazole-2-carbamide-oxime are obtained. F: 270-275 ° C.

C4H4Cl2N4O (195.0) calc .: 36.36 [Cl, 28.74% N found: 36.9 28] Example 127 19.5 g (0.1 mol) of 4,5-dichloro-imidazole-2-carbamidoxime are dissolved in 150 ml of dioxane with 10.1 g (0.1 mol) of triethylamine. 14.05 g (0.1 mol) of benzoyl chloride are added dropwise to this at 15-20 °. The mixture is stirred for 1 hour at room temperature and 2 hours at 50 ° C. and then added to 500 ml of water. The deposited crystals are filtered off with suction, washed with water and dried. 18 g (60.2% of theory) of 4,5-dichloroimidazole-2-carbamid-0-benzoyl oxime are obtained. F: 177-1780C (from toluene) 4,5-dichloro-imidazole-2-carbamide-0-benzoyl-oxime. F: 177-178 ° C (from toluene).

Example 128 25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethyl-imidazole are introduced in small portions into 200 ml of ethanol saturated with ammonia, while cooling with ice and stirring vigorously. The mixture is stirred at 50 ° C. for a further 1/2 hour. The insoluble constituents are filtered off with suction, the filtrate i. Vac. evaporated. The combined residues are dissolved in hot water. The reaction product is precipitated by acidification with dilute hydrochloric acid.

This is filtered off with suction, washed with water and dried.

Yield: 14.6 g (90% of theory). F: 187-189 ° C (from toluene).

Example 129 10.9 g (0.1 mol) of 2-aminophenol and 40.4 g (0.4 mol) of triethylamine are dissolved in 200 ml of dioxane. 25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethyl-imidazole are introduced in portions with cooling at 15 ° -200 ° C. The mixture is stirred for 1/2 hour at room temperature and 2 hours at 60-700C. The reaction mixture is then added to 1 l of water and acidified with dil.

Hydrochloric acid and sucks off the precipitate. This is done with water washed and dried. Yield 12 g (47.2% of theory) 2- (4,5-dichloro-imidazolyl- (2)) benzoxazole, F: 196-1980C (from ethanol).

Using an analogous procedure with 10.8 g (0.1 mol) of phenylenediamine instead of 2-aminophenol, 2- (4,5-dichloroimidazolyl- (2)) benzimidazole of the formula Example 130 is obtained F: 3000C (from butanol) and with 6 g (0.1 mol) ethylenediamine 2- (4,5-dichloro-imidazolyl- (2)) -imidazoline of the formula Example 131 F> 2600C (ethyl acetate / ligroin) Example 132 To 23.5 g (0.11 mol) of 3,4-dichloro-isothiazole-5-carboxylic acid hydrazide (melting point 1560 ° C.; prepared in the usual way from the 3,4-dichloro-isothiazole-5 described in US Pat. No. 3,341,547 carboxylic acid) in 300 ml of dioxane are added with stirring 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethylene imidazole, the reaction mixture warms to about 50 ° C. and a voluminous precipitate separates out at the same time. After brief reheating to 1000C; cooled, filtered off with suction, washed with L) ioxane and dried.

This gives 33 g (84% of theory) of an intermediate product of the empirical formula C8H2Cl4N5OS, for one of the two tautomeric syrup formulas is likely. This intermediate product melts at 205 ° C. with evolution of Hcl, whereupon it solidifies again. A quantitative conversion into the oxdiazole derivative of the above formula, which melts at 2660C, has taken place.

The same oxdiazole derivative is obtained in the "one-pot process".

if the reaction is carried out in a high-boiling solvent instead of in dioxane, such as 1,2,4-trichlorobenzene, or 1-chloronaphthalene, at temperatures up to 200-250 ° C performs.

Similarly, the following imidazolyl-oxdiazoles of the general formula can be obtained: Table 10 Example No. R F'o0C ) 290 Example No. R FpOC 134Q -NO2> 290 135-262 136, N 290 example 1 To a solution of 25.4 g (0.1 mol) 4,5-dichloro-2-trichloromethylimidazole in 200 ml dioxane, 16.7 g (0.11 mol) phenyl carbazate are added in portions at room temperature. After the slightly exothermic reaction has subsided, the mixture is gradually heated to boiling and refluxed for a further 2 hours.

It is then cooled to room temperature and 20.2 g (0.2 mol) of triethylamine added dropwise. The mixture is stirred for a further 2 hours at 50 ° C. and the insoluble constituents are filtered off with suction and the filtrate evaporates i. Vac. a. The residue is treated with water, Sucked off, washed with water and dried. 21.5 g (72.5% of theory) are obtained 2- (4,5-dichloro-imidazolyl- (2)) -5-phenoxy-1,3,4-oxadiazole. F: 1090C (from toluene).

Example 138 9.1 g (0.1 mol) of thiosemicarbazide and 40.4 g (0.4 mol) of triethylamine are stirred in 200 ml of ethanol until a clear solution appears. At 0-5 ° with stirring, 25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethylimidazole are added in portions. The mixture is 1 hour with cooling, 1 hour.

Stirred at room temperature and at 50 ° C. for 1 hour. After cooling down the amine hydrochloride is suctioned off and the filtrate is evaporated i. Vac. a. The residue is treated with water, acidified with hydrochloric acid, filtered off with suction, washed with water and dried. 18 g (76.5% of theory) of 2- (4,5-dichloroimidazolyl- (2)) -5-amino-1,3,4-thiadiazole are obtained. F: 1470C (with decomposition) (from ethyl acetate / ligroin).

Example 139 If semicarbazide hydrochloride is used instead of thiosemicarbazide in the presence of 5 times the molar amount of triethylamine, with otherwise the same procedure, 3- (4,5-dichloroimidazolyl- (2)) -1,2,4-triazolone- (5 ) of the formula F: 176-1780C (from ethyl acetate / ligroin).

Example 140 9.6 g (0.1 mol) of 4,5-dichloro-imiazol-2-thiocarboxamide and 1> g (0.1 mol) of # -chloroacetophenone are dissolved in 200 ml of acetonitrile. 30 g of potassium carbonate are added and the mixture is gradually heated to the boil. After 5 hours of boiling, the insoluble constituents are filtered off with suction and the filtrate i. Vac. evaporated. The combined residues are introduced into water. Then hydrochloric acid is added until the reaction is weakly acidic and the insolubles are filtered off with suction, washed with water and dried.

Yield: 18 g (61% of theory); F: 159-160 ° (from mineral spirits) Example 141 With the same procedure as in Example 118 with bromopinacoline (17.9 g) instead of chloroacetophenone, 21 g (76% of theory) 2- (4,5-dichloro-imiadzolyl- (2)) -4-tert are obtained .-butyl-thiazole.

F: 157-158 ° (petroleum ether).

Example 142 16.2 g (0.1 mol) of 4,5-dichloro-imiadzol-2-carboxylic acid nitrile are dissolved in 150 ml of ethanol with heating. To this end, the solution of 2.3 g (0.1 mol) of sodium in a little ethanol is added. After a short rotation, the solution will i. Vac. evaporated. The water-soluble sodium salt remains in quantitative yield. F:> 250 °.

Example 143 22.3 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid isopropyl ester are dissolved in 150 ml of toluene with gentle heating. 10.1 g (0.1 mol) of triethylamine are added to this. The mixture is stirred for 1/2 hour at room temperature, cooled to OOC, the crystals are filtered off with suction and dried. The water-soluble triethylaminonium salt is obtained in quantitative yield. F:> 2500.

Example 144-150 16.2 g (0.1 mol) of 4,5-dichloro-2-carboxylic acid nitrile are dissolved in 150 ml of ethanol. 0.1 mol of an amine is added to this and the solvent is then evaporated off in vacuo. The amine salt remains as residue in quantitative yield.

Example 144: Triethylammonium salt F: 38-400C Example 145: Butylammonium salt F: 122-1240C Example 146: Pyridinium salt F: 74-760C Example 147: N, N-dimethylbenzylammonium salt F: 90-92 C Example 148: Dibutylammonium salt F. : 56-580C Example 149: Morpholinium salt F: 144-1460C Example 150: Tris (2-hydroxyethyl) ammonium salt F: 102 ° C Example 151 To a solution of 25.4 g (0.1 mol) 4,5-dichloro-2-trichloromethylimidazole in 200 ml dioxane, a mixture of 18.8 g (0.2 mol) as-amino is added dropwise with cooling at 10-150 ° C pyridine and 30.3 g (0.3 mol) of triethylamine. The mixture is stirred for 2 hours at room temperature, 1 liter of water is added and the mixture is made weakly acidic with acetic acid. The deposited crystals are filtered off with suction, washed with water and dried. 25.4 g (77% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N, N'-di-pyridyl- (2) -amidine are obtained. F; 199-2000C (from ethyl acetate / ligroin).

Example 152 16.2 g (0.1 mol) of 2,5-dichloroaniline and 10.1 g (0 , 1 mol) triethylamine at about 20 ° C. It is then briefly heated to about 1000C, cooled, precipitated in water, filtered off with suction, washed with water and dried.

22 g (94% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N, N'-di- (2,5-dichlorophenyl) -amidine are obtained.

Melting point 2120C (from toluene).

Similarly, the following 4,5-dichloro-imidazole-2-carboxylic acid-N, N'-diarylamidines of the general formula can be obtained.

Tabel Example No. R Fp OC 153 - Ç -Cl 204 (toluene) Cl C1 154-230 (benzene) Cl 155 CF3-210 (acetonitrile) 156 ~ W 220 (acetonitrile) Cl 157 9 -CF3 212 (toluene) Cl Example No. R Fp OC 158 ~ G Ccl 255 (chlorobenzene) CF3 159 ~ G 181 (cyclohexane) CF3 CH 160 t -CH3 290 (chlorobenzene) 161 o -CF3 285 (acetonitrile) 162 4 -F 285 (chlorobenzene) Cl 163 O -CF3 210 (acetonitrile) Br -164 ~ G 242 (chlorobenzene) Example No. R Fp OC CH 165 - 29O 240 (chlorobenzene) Cl 166 4-OCF3 190 (acetonitrile) Cl 167% 4 255 (chlorobenzene) Cl -Cl 127 (cyclohexane) 168 CF3 Cl Cl 169 229 (chlorobenzene) 170 co OCF3 242 (acetonitrile) 171 -SCF3 253 (acetonitrile) C1 172216 (acetonitrile) CF3 Example No. R FpOC 173 o O-CF> -CHClF 200 (acetonitrile) 174 QF 250 (acetonitrile) F. F. Example 175 A suspension of 16.3 g (0.05 mol) of the dimeric ketene of the formula (For preparation see example no.) In 100 ml of dimethylformanide is heated with 14 g (0.11 mol) of 2,4-difluoroaniline for about 5 minutes at 145-1550C, whereupon a solution is formed. After cooling, it is precipitated in water, filtered off with suction, washed with water and dried. This gives 24 g (83% of theory) of 4,5-dichloroimidazole-2-carboxylic acid N- (2,4-difluorophenyl) amide. / Melting point 2900C (from o-dichlorobenzene) Example 176 A mixture of 16 g (Q, 125 mol) of finely powdered 2-chloroaniline, 100 ml of water and 15 g (about 0.15 mol) of 37% strength aqueous hydrochloric acid is finely powdered at room temperature with 21.8 g (0.1 mol) 4,5-dichloro-2-dichloromethylene-imidazole was added with stirring and then heated to about 1000C for about 1 hour.

After cooling, vacuuming, washing with water and drying receives one 21.5 g (74% of theory) 4.5 + dichloroimidazole-2-carboxylic acid (2-chloroanilide) of melting point 2440C. The substance crystallizes from chlorobenzene or 1,2-dichlorobenzene in colorless needles. The same compound is also obtained starting from 4,5-dichloro-2-trichloromethyl-imidazole.

In a similar manner to the two examples described above, the following 4,5-dichloro-imidazole-2-carboxylic acid atilides of the general formula can be obtained.

Tabel Example No. R Fp OC s 177Q 243 (acetonitrile) CH, 178 ~ 4 195 (toluene) -C2H5 205 (toluene) 179 or Acetonitrile) CF3 180 i 2 200 (toluene) 0 Example No. R Fp C I. 181 CH '290 (o-dichlorobenzene) 182 o -C3 221 (o-dichlorobenzene) 182 -OCH3 Cl 183 - 4,258 (chlorobenzene) 184 G -NO2> 290 (o-dichlorobenzene) 185 o -C + CE3 290 (o-dichlorobenzene) ON 186-C1 290 (o-dichlorobenzene) Cl Cl 187 G 260 (o-dichlorobenzene) Example No. R Fp OC 188 t vCl 260 (o-dichlorobenzene) C1 189 iu / $ l> 290 (o-dichlorobenzene) 190 ~ n 290 t91 w -Cl 264 (chlorobenzene) 192 ç -CF3 265 (toluene) Cl 193 4 lCF3 257 (chlorobenzene) Cl 194 -Cl 280 (o-dichlorobenzene) CF3 195 ~ G 249 (acetonitrile) 3 Example No. R Fp 0C 196 - 9 -CH3 244 (chlorobenzene) CH3 197 9 -C 259 (chlorobenzene) 197 CH3 198 9 -CF3 228 (acetonitrile) 198 3 CF3 199 o -CF3 266 (acetonitrile) 200 o -F> 290 (dioxane) C1 201 - G 290 (chlorobenzene) Cl Br 202 - G 280 Cl - -OCF3 205 (acetonitrile) 203 Example No. R Fp OC Cl 204 4 -SCF2Cl 244 (acetonitrile) 205 -C1 215 (acetonitrile) CF3 Cl 206 ~ G to 290 (dioxane) Cl 207 4 -OCF3 202 (acetonitrile) Q SCF, 254 (acetonitrile) 208 F3 209 - Ç 211 (acetonitrile) Cl CF3 -Cl 236 (acetonitrile) 210 Example No. R 4 7 Fp C C. 1 CHFZ 211 -t6) -Cl 254 (acetonitrile) 212 -OCF -CHClF 202 (acetonitrile) 2 213 g O \ jF 218 (acetonitrile) 0 F. NC 214 nu 3 ~ CF3 280 (acetonitrile) Cit 215 ~ @ N 265 (toluene) Example 216 To a mixture of 81 g (0.5 mol) of finely powdered 2,6-dichloroaniline 500 ml of water and 75 g (approx. 0.75 mol) of 37% aqueous hydrochloric acid with a solution of 109 at 55-60 ° C. with stirring g (0.5 mol) of 4,5-dichloro-2-dichloromethylene-imidazole in 25 ml of dioxane were added dropwise in about 10-15 minutes. After stirring for about two hours, the mixture is filtered off with suction, washed with water and dried.

159 g (92% of theory) of 4,5-dichloroimidazole-2-carboxylic acid N- (2,6-dichlorophenyl) imide chloride are obtained. From acetonitrile or from chloroform, long skewers with a decomposition point of about 2000C.

Similarly, the following 4,5-dichloro-imidazole-2-carboxylic acid-N-arylimide chlorides of the general formula obtained: table Example No. R Fp OC 217 -Ç-CF3 170 (cyclohexane) CF3 Example 218 25 g (0.73 mol) of 4,5-dichloro-imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -imide chloride (preparation see Example No. 203 are stirred with 125 g of concentrated sulfuric acid for about 5 hours is poured onto ice, filtered off with suction, washed neutral with water and dried. This gives 18.5 g (78% of theory) 4,5-dichloroimidazole-2-carboxylic acid (2,6-dichloromide). Melting point 206 0C ( from acetonitrile).

Example 219 19 g (0.12 mol) of 3-trifluoromethyl aniline in 500 ml of water are mixed with 34.4 g (0.1 mol) of finely powdered 4,5-dichloroimidazole-2-carboxylic acid N- (2,6-dichlorophenyl ) imide chloride (see example no. 203) is added and the mixture is heated to about 1000C for 5 - 10 minutes while stirring. After cooling, it is filtered off with suction, washed with water and dried. 46 g (98% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -N '- (3-trifluoromethylphenyl) -amidine are obtained.

Melting point 2050C (from acetonitrile) Similarly, the following amidines of the general formula can be obtained.

Tabel Example No. R Fp OC C1 220 1 CM3 205 (acetonitrile) C1 221 4 S-CF2 C1 165 (acetonitrile) 222 w CF3 212 (acetonitrile) C1 223 t) C1 192 (acetonitrile) CF 224 4 ~ 1 195 (acetonitrile) CF3 Example no. R Fp OC C1 225 ~ G 190 CF3 Cl 226 - b CF3 170 CF3 227 - b -Cl 158 Cl 228 C1 250 (acetonitrile / Dioxane) 229 t 182 (acetonitrile) Cl Cl 230 3 \ / OCF2-CHClF 165 (acetonitrile) 231 232 t XF 187 (acetonitrile) -OF F. Example 233 20 g (0.06 mol) of finely powdered 4,5-dichloro-imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -imid chloride (see Example No. 203) are introduced into 200 ml of concentrated aqueous ammonia with stirring. After stirring for about one hour, the mixture is filtered off with suction, washed with water and dried. 15 g (77% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -amidine are obtained. Melting point 2700C (from acetonitrile).

Example 234 A solution of 17.2 g (0.05 mol) of 4,5-dichloro-imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -imidochloride (see example no. 203) in 200 ml of dioxane is at 20 -300C with 7.5 g of stirring for one hour is precipitated in water, neutralized with dilute hydrochloric acid, filtered off with suction, washed with water and dried. 18.5 g (97% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -N ', N'-diethylamidine are obtained. Melting point 1750 (from acetonitrile).

Example 235 34.4 g (0.1 mol of finely powdered 4,5-dichloro-imidazole-2-carboxylic acid-N- ( 2,6-dichlorophenyl) imide chloride (see example no. 203 entered. After stirring for about one hour at 200 ° C., the mixture is precipitated in water, neutralized with dilute hydrochloric acid, filtered off with suction, washed with water and dried. 26 g (77% of theory) are obtained 4,5-dichloro-imidazole-2-carboxylic acid (2,6-dichlorophenylimido) methyl ester, melting point 2030C (from benzene).

Example 236 To a solution of 4 g (0.071 mol) of potassium hydroxide and 9 g (0.062 mol) of 4-chloro-thiophenol in 200 ml of water are added at 20-250C with stirring, 17.2 g (0.05 mol) of 4,5-dichloro imidazole-2-carboxylic acid-N- (2,6-dichlorophenyl) -imide chloride (see example no. 203) in finely powdered from. After stirring for about five hours at 20-25 ° C., the mixture is filtered off with suction, washed with water and dried. 18 g (80% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid (2,6-dicholophenylimido) (4-chlorophenyl) thioester are obtained. Melting point 1900C (from a little isopropanol).

The following compounds can be produced analogously to the process described in Example No. 142: Table Example no. Cl -, - N 237 1, l Cl tN-CF3 e Nae C1 --N 0 238 CltNtl C-NH-C3H7i 0 CHO Cl r --- N ,, 239 Cl Ij CN-C3H7i

Claims (10)

Claims 1) 4,5-dichloro-imidazole-carboxylic acid derivatives of the formula I. in which the group stands for a three-fold hetero-oriented carbon atom, or its salts with bases. 2. 4,5-dichloroimidazole-2-carboxylic acid derivatives of the formula XVI in which W stands for O, S or the radical = N-aryl and Z when W stands for the radical P N-aryl, for halogen, alkoxy, alkyl mercapto, aryloxy, aryl mercapto, the radical -NH-aryl or the radical R11- N-R12, where R11 or R12 are identical or different and denote hydrogen, alkyl, alkenyl, which are optionally substituted by halogen, in particular chlorine, fluorine, bromine, OH, alkoxy, aryloxy, acyloxy, where acyl denotes the radical one aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid or the remainder of a heterocyclic carboxylic acid, in particular the remainder Alkyl mercapto, optionally substituted by aryl, aryl mercapto, CN, COOH, COOR, CONH2, CONH (C1 4 -alkyl) CON, (C1 4-alkyl) 2, CONH-aryl and aryl, cycloalkyl, an O, S or N eth-containing heterocycle or a group R11-N-acyl where R11 has the meaning given above and acyl denotes the radical of an aliphatic, cycloaliphatic, araliphatic, aromatic carboxylic acid or the radical of a heterocyclic carboxylic acid, in particular the radical Alkynyl, optionally substituted by optionally substituted aryl or cycloalkyl, cycloalkyl, optionally substituted by C14-alkyl, CF3, or optionally containing fused aromatic or cycloaliphatic rings; S, 0 or N-containing heterocycle, which can also contain cycloaliphatic, aromatic or further heterocyclic rings fused on, and can optionally be substituted. R11 and R12 can also together with the adjacent N-atom one 3-7 membered heterocyclic ring, which also has additional 0, S or N heteroatoms may contain, may optionally be substituted as well as optionally condensed, may contain aromatic or heterocyclic rings, R11 or R1 are also Aryl. R12 can also mean OH, alkoxy, optionally substituted by aryl, an acyl group where R denotes hydrogen, alkyl, alkenyl, each of which is optionally substituted by halogen, C1-4-alkoxy, aryloxy, alkyl mercapto, aryl mercapto, alkynyl, cycloalkyl, aryl O, S and N-containing heterocycles, the optionally condensed, cycloaliphatic, cycloaliphatic, contain cycloaromatic or heterocyclic radicals, a carboxylic acid ester group where R14 denotes alkyl, alkenyl, alkynyl, which are optionally substituted by halogen, C1-4 -alkoxy, aryl, cycloalkyl, a heterocycle containing 0, S or N; furthermore aryl, cycloalkyl, optionally substituted by C1-4-alkyl, a carboxamide group where R15 is identical or different and denotes hydrogen, alkyl, alkenyl, which are optionally substituted by halogen, NO2, C1 4 -alkyl, CF3, C14-alkoxy, also aryl, cycloalkyl, a sulfonyl group -SO2-R8, where R8 is the below has the meaning given, or the group R5-N-R6 where R5 and R6 are hydrogen, C1-4-alkyl, optionally substituted by aryl, or the group or the group -SO2-R8 where R7 denotes: hydrogen, C1-C12-alkyl, C2-8-alkenyl, each of which can be substituted by halogen, nitro, C1-4-alkyl mercapto, aryl mercapto, aryl, cycloalkyl with 5 or 6 Ring carbon atoms. C28 alkynyl, cycloalkyl with 3-6 ring C atoms, aryl, O, S or N-containing 5 or 6-membered heterocycle or a group -O-R26 or -S-R26 where R26 is C1-12-alkyl, C3-12-alkenyl, C3-12-alkynyl which may optionally be substituted by halogen, C14-alkoxy, optionally substituted by halogen, C1-4-alkyl, phenyl, cycloalkyl, O, S or N-containing 5 or 6-membered heterocycles, C3-6-cycloalkyl, aryl, a group R27-N-R27 where the radicals R27 can be identical or different and mean hydrogen, C1-12-alkyl, C3 ~ 8-alkenyl, which can be substituted by Halogen, C1 4-alkoxy, cycloalkyl with 5 or 6 ring carbon atoms, aryl. and where R8 is C1-2-alkyl, optionally substituted by halogen, aryl or a secondary amino group, both radicals R5 and R can also together be the group mean, where R9 is identical or different and means C1-12-alkyl, optionally substituted by OH, C1-4-alkoxy, COOH, COO (C1-4-alkyl) cycloalkyl with 5 or 6 ring carbon atoms, aralkyl with 1 -4-C-atoms in the alkyl part aryl, O-, S- or N-ethaltende 5 or 6-membered heterocycles, both radicals R9 can also form a carbocyclic or heterocyclic ring together with the adjacent carbon atom, one of the radicals R9 can also Both radicals R5 and R6 can form a (3 or 6-membered heterocycle, which can contain further heteroatoms, such as 0, N or S) with the adjacent N atom for the remainder -NH-aryl. 3) Process for the preparation of 4,5-dichloro-imidazolecarboxylic acid derivatives of the formula I according to claim 1, characterized in that 4,5-dichloro-2-dichloromethyl-imidazole of the formula (II) or 4,5-dichloro-2-trichloromethylimidazole of the formula (IIt) or the dimeric ketene of 4,5-dichloroimidazole-2-carboxylic acid of the formula (IV) reacted with suitable nucleophiles and the resulting reaction products optionally subjected to further subsequent reactions or converted into their salts. 4) Process for the preparation of 4,5-dichloro-imidazole-carboxylic acid derivatives of the formula I according to Claim 1, characterized in that a) 4,5-dichloro-2-dichloromethylene-imidazole of the formula II or 4,5-dichloro -2-trichloromethyl-imidazole of the formula III or the dimeric ketene of the formula IV according to claim 2 with nucleophiles of the formula HZ in which Z is fluorine, azide or a group -O-R10 or -S-R10 where R10 is hydrogen salt-forming cation, in particular a metal cation or ammonium cation -NR4 where R denotes hydrogen or an organic radical, alkyl and alkenyl, in particular C1-18-alkyl, C3-12-alkenyl optionally substituted by halogen, in particular chlorine, fluorine or bromine, OH, acyloxy acyl denotes the residue of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid or the residue of a heterocyclic carboxylic acid, in particular the residue Alkoxy, in particular with 1-4 C atoms, alkoxyalkyleneoxy, aryloxy, in particular phenoxy or naphthoxy, optionally substituted by halogen, C1 4 -alkyl, CF3, NO2 alkyl mercapto, in particular with 1-4 C atoms, optionally substituted by aryl, in particular phenyl which is optionally substituted by C1-4-alkyl or halogen, aryl mercapto, arylsulfinyl, arylsulfonyl, each of which is optionally substituted by C1-4-alkyl or halogen; Alkylsulfonyl, in particular with 1-4 carbon atoms, acylamino or diacylamino, where acyl denotes; the remainder of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic carboxylic acid or the remainder of a carbonic acid or thiocarbonic acid derivative CN, carboxylic acid ester, cycloalkyl, in particular with 5-6 ring carbon atoms. Aryl, in particular optionally by halogen, C14-alkyl, C1-4-alkoxy substituted phenyl, O, S or N-containing 5 or 6-membered heterocycle Alkynyl, in particular with 3-12 carbon atoms cycloalkyl, in particular with 3-6 ring carbon atoms, if appropriate substituted by halogen, C1-4-alkyl, C1-4-alkoxy or a fused ring containing, aryl, in particular phenyl or naphthyl, optionally substituted by C1 alkyl, polyhalogen (C1 4 alkyl), in particular CF3, halogen, C1 4 alkoxy, Aryloxy or aryl mercapto, in particular optionally by halogen, C1 4 -alkyl, CF3, C1 4-alkoxy, NO2-substituted phenoxy or phenyl mercaptoto, C1 4 alkyl mercapto, C1 4-alkylsulfonyl, alkoxycarbonal, aminocarbonyl, CN, NO21 mono- or dialkylamino, in particular with 1-4 carbon atoms per alkyl part, or the fused-on cycloaliphatic or contains heterocyclic radicals. 11 12 11 12 are a group identical or different and denote hydrogen, alkyl, in particular with 1-12 carbon atoms, alkenyl, in particular with 3-8 carbon atoms, which are optionally substituted by halogen, in particular chlorine, fluorine, bromine, OH, alkoxy, in particular C1 4, aryloxy, in particular phenoxy, optionally substituted by C1-4-alkyl, halogen, C1-4-alkoxy aryloxy, where aryl denotes the radical of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid or the radical of a heterocyclic acid Carboxylic acid, especially the rest Alkyl mercapto, in particular Cl -4, optionally substituted by aryl, in particular phenyl, aryl mercapto, in particular phenyl, optionally substituted by halogen or C 4 -alkyl CN, COOH, CONH2, CONH (C1-4-alkyl), CON (C1-4-alkyl ) 2, CONH-aryl and aryl, where aryl in particular denotes phenyl or naphthyl, cycloalkyl, in particular with 5 or 6 ring carbon atoms, which is optionally substituted by halogen, C1-4 alkyl, CF3, C1 4 alkoxy, NO2 , S or N containing in particular 5 or 6 membered heterocycle or a group R11-N-acyl where R11 has the meaning given above and acyl denotes the residue of an aliphatic, cycloaliphatic, araliphatic, aromatic carboxylic acid or the residue of a heterocyclic carboxylic acid, in particular the residue Alkenyl, in particular with 3-12 C atoms, optionally substituted by optionally substituted aryl, in particular phenyl or cycloalkyl, in particular with 5-6 ring C atoms. Cycloalkyl, in particular with 4-8 ring carbon atoms, optionally substituted by C1-4-alkyl, CF3, or optionally condensed, aromatic or cycloaliphatic Containing rings, ryi with 6-12 carbon atoms or an S, 0 or N containing, in particular 5 or 6 membered heterocycle, which is also cycloaliphatic, may contain aromatic or other heterocyclic rings fused, as well as may optionally be substituted. R11 and R12 can also be one together with the adjacent N atom 3-7 membered heterocyclic ring, which has additional 0, S or N heteroatoms may contain, may optionally be substituted as well as optionally condensed, may contain aromatic or heterocyclic rings. R12 can also denote OH, alkoxy, in particular C1 4, optionally substituted by aryl, in particular phenyl, which may optionally be substituted, O an acyl group -C-R13 where R13 denotes hydrogen, alkyl, in particular C1 12 alkenyl, in particular C28, the are each optionally substituted by halogen, C1 4 -alkoxy, aryloxy, in particular optionally halogen, methyl, NO2-substituted phenoxy, alkyl mercapto, in particular C1 4, aryl mercapto, in particular phenyl mercapto optionally substituted by halogen or methyl, aryl, in particular by halogen or C14 alkyl substituted phenyl alkynyl, in particular C2-8, cycloalkyl, in particular with 3-6 ring carbon atoms, aryl, in particular phenyl or naphthyl, optionally substituted by halogen, 1-4 alkoxy, C C1-4 alkyl, CF3, NO2 O, S or N-containing, in particular 5 or 6-membered heterocycles, which optionally contain fused, cycloaliphatic, cycloaromatic or heterocyclic radicals e hold, a carboxylic acid ester group where R14 denotes alkyl, in particular C112, alkenyl, in particular C3-12, alkynyl, in particular C3-12, which are optionally substituted by halogen, C1 4-alkoxy, aryl, in particular phenyl cycloalkyl optionally substituted by halogen or C1-4-alkyl, in particular with 5-6 ring carbon atoms, a 0, S or N-containing, in particular 5-6 membered heterocycle cycloalkyl, in particular with 5-6 ring carbon atoms, optionally substituted by C1-4-alkyl aryl, in particular phenyl or Naphthyl, optionally substituted by halogen, C1-4-alkyl, CF3, C1-4-alkoxy, C14-alkylmercapto, NO2, CN. a carboxamide group where R15 is identical or different and denotes hydrogen, alkyl, in particular C1-12, alkenyl, in particular C3-8, which are optionally substituted by halogen, NO2, C1-4-alkyl, CF3, C1 4 -alkoxy, aryl, in particular phenyl , optionally substituted by halogen, C1 4 -alkyl, CF3, C1 4-alkoxy, C1-4-alkyl mercapto, NO2 cycloalkyl, in particular with 5-6 ring carbon atoms; a sulfonyl group -SO-R8, where R8 has the meaning given above, The group R -N-R6 where R5 and R can be the same or different and are hydrogen, C1 4-alkyl, optionally substituted by aryl, in particular phenyl, which is optionally the group -C-R7 is substituted by halogen or C1 4 -alkyl, in particular methyl, aryl, in particular phenyl, optionally substituted by halogen, NO2, C1-4-alkyl, in particular methyl, C1 4-alkoxy, CF3, O (S) where R7 has the meaning given above or the group -SO2-R3 where R8 is C112-alkyl, optionally substituted by halogen, in particular chlorine or fluorine, aryl, in particular phenyl, optionally substituted by halogen, in particular chlorine, C 1-4 alkyl, C1 ~ 4-alkoxy, CF3, NO2 a secondary amino group R5 and R6 can together form the group mean, where R9 is the same or different and means C1-12-alkyl, optionally substituted by OH, C1-4-alkoxy, COOH, COO (C1-4-alkyl) cycloalkyl with 5 or 6 ring carbon atoms, aralkyl with 1 -4 C atoms in the alkyl part and in the aryl part, in particular phenyl or naphthyl which is optionally substituted by halogen, NO2, C1 4 -alkyl, C1 4-alkoxy, aryl, in particular phenyl or naphthyl, optionally substituted by OH, halogen, NO2, C14- Alkyl, C1-4-alkoxy, C1-4-alkylmerecapto, CF3 O, S or N-containing 5 or 6 membered heterocycles, both radicals R9 can also form a carbocyclic or heterocyclic ring together with the adjacent carbon atom, one of the radicals R9 can also mean hydrogen. R5 and R6 can form a 5 or 6-membered atom with the adjacent nitrogen atom Form a heterocycle which can contain further heteroatoms, such as 0, N or S. optionally in the presence of acid-binding agents and / or in the presence of water, or the reaction products of this reaction are subsequently treated with water and the hydrolysis products thus obtained are converted into their salts, optionally with the aid of bases, or b) characterized in that compounds of the formulas VI, VII and VIII in which R10 stands for lower alkyl with 1-4 C atoms, benzyl or phenyl optionally substituted by Cl, CH3 or NO2, and Alk stands for lower alkyl with 1-4 C atoms with nucleophins of the formula XV in which R11 and R are as defined above, or c) characterized in that 4,5-dichloroimidazole-2-carboxonitrile is reacted with nucleophiles of the general formula HZ, where Z is as defined above; or d) characterized in that 4,5-dichloro-imidazole-2-thiocarboxamide is reacted with alkylating agents and the reaction products are subsequently hydrolyzed or cyclized. -e) characterized in that the carboxylic acid of the formula XI with alcohols, if appropriate in the presence of organic diluents and if appropriate in the presence of catalysts. 5. Process for the preparation of esters of the carboxylic acid of the formula XI with tertiary alcohols, characterized in that the carboxylic acid of Formula XI with alkenes, optionally in the presence of acidic catalysts and optionally reacts in the presence of diluents. 6. A process for the preparation of the 4,5-dichloroimidazole-2-carboxylic acid derivatives according to Claim 2, characterized in that a) 4,5-dichloro-2-dichloromethylene-imidazole of the formula (11 or 4,5-dichloro-2-trichloromethylimidazole of the formula (III) or the dimeric ketene of 4,5-dichloroimidazole-2-carboxylic acid of the formula (IV) with amines of the formula (XVIII) H2N-aryl (XVIII), optionally in the presence of diluents and acid binders, or that b) an imide chloride of the formula (XIV) with compounds of the formula ZH where Z has the meaning given in claim 2, if appropriate reacted in the presence of diluents and acid binders, or that a) an imide chloride of the formula (XN) is hydrolyzed, if appropriate in the presence of diluents, or that b) 4.5 -Dichloro-2-dichloromethyleneimidazole of the formula (II) is reacted with equimolar amounts of an amine of the formula (XVIII), if appropriate in the presence of diluents at temperatures below about 90.degree. 7) Pesticides, characterized by a content of 4,5-duchloro-imidazole-carboxylic acid derivatives of the formula I according to Claim 1. 8) method for controlling pests, characterized in that that one 4,5-dichloro-imidazole-carboxylic acid derivatives of the formula I according to claim I. Plants and / or their habitat. 9) Use of 4,5-dichloro-imidazole-carboxylic acid derivatives of the formula I according to Claim 1 for combating pests. 10) Process for the manufacture of pesticides, thereby characterized in that one 4,5-dichloro-imidazole-carboxylic acid derivatives of the formula I according to Claim 1 mixed with extenders and / or surface-active agents.