EP1181267A1

EP1181267A1 - Halogen compounds

Info

Publication number: EP1181267A1
Application number: EP00931134A
Authority: EP
Inventors: Dieter Arlt; Martin Hendrix; Hans-Ludwig Elbe; Gerd Hänssler; Karl-Heinz Kuck; Christoph Erdelen; Haruko Sawada
Original assignee: Bayer AG
Current assignee: Bayer CropScience AG
Priority date: 1999-05-19
Filing date: 2000-05-08
Publication date: 2002-02-27
Also published as: WO2000071500A8; DE19922934A1; WO2000071500A1; JP2003500377A; AU4917700A

Abstract

The invention relates to novel halogen compounds, to a method for producing them and to their use for treating plants for protecting them against attack from phytopathogenic microorganisms and insects. The invention also relates to novel intermediate products and to methods for producing the same.

Description

HALOGEN CONNECTIONS

The invention relates to new halogen compounds, a process for their preparation and their use for the treatment of plants against attack by phytopathogenic microorganisms and insects. The invention further relates to new intermediates and processes for their production.

It has already been known that chemical compounds which are remotely similar to those mentioned below have an insecticidal activity or as

Intermediates for the production of insecticides are used (cf. for example Bull. Chem. Soc. Jpn. (1986), 59 (4), 1021-6; Pestic. Sci. (1983), 14 (1), 1-8 or DE 28 10 031). A fungicidal or resistance-inducing effect has not yet been described.

The new halogen compounds of the general formula (I) have now been found

in which

R.1 represents substituted or unsubstituted aryl- or heteroaryl,

R.2 for hydrogen, substituted or unsubstituted alkyl, aryl or

Heteroaryl is, with halogen, alkoxy and aryloxy radicals as substituents on the alkyl radicals, and substituents on the aryl or hetaryl radical

Halogen, alkyl and alkoxy radicals, and the CF ₃ - and the CF ₃ O radical and

NO ₂ are possible X * and χ2 are the same or different and are independently fluorine, chlorine or bromine,

X ^ represents hydrogen, fluorine, chlorine or bromine, and

N represents optionally substituted nitrogen-bonded heterocyclyl or a group -E-A-R ^, in which

E for oxygen, sulfur, or

R ³ I ^w is where R ^{J is} alkyl,

A represents a single bond or alkanediyl, alkenediyl, alkynediyl, -N = CH- or -N = C (CH ₃ ) - optionally interrupted by oxygen, sulfur or nitrogen and optionally substituted by phenyl, tolyl or 4-chlorophenyl, and

R ^ stands for hydrogen, or for optionally substituted aryl, cycloalkyl or heterocyclyl.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, also in combination with heteroatoms, such as in alkoxy, alkyl thio or alkylamino, are each straight-chain or branched, in particular 1 to 6 carbon atoms. If an alkyl or alkanediyl chain is interrupted by more than one heteroatom, these can be the same or different. If an alkyl or alkanediyl chain is interrupted by more than one oxygen atom, two oxygen atoms are not directly adjacent. Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

Haloalkyl stands for partially or completely halogenated alkyl with in particular 1 to 6 carbon atoms and 1 to 13 identical or different

Halogen atoms. In the case of polyhalogenated haloalkyl, the halogen atoms can be the same or different. Preferred halogen atoms are fluorine and chlorine and especially fluorine. If the haloalkyl carries further substituents, the maximum possible number of halogen atoms is reduced to the remaining free valences.

Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthryl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.

Heteroaryl stands for mono- or polycyclic heteroaryl compounds, preferably with 5 to 6 ring members, such as e.g. Thienyl, pyridyl or thiazole.

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped compounds in which at least one ring member has a hetero atom, i.e. H. one of

Carbon is different atom. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur. If the ring contains several oxygen atoms, they are not adjacent. If appropriate, the ring-shaped compounds together with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. A polycyclic ring system can be linked via the heterocyclic ring or a fused-on carbocyclic ring. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems. It was further found that the new halogen compounds of the general formula (I) are obtained (process a) if carboxylic acid halides of the formula (II)

in which

R, R ^, X 1, χ2 and X- ^ have the meanings given above and

χ4 represents halogen,

with a nucleophile of the formula (III),

H-Y (III) in which

Y has the meaning given above,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.

Finally, it was found that the new halogen compounds of the general formula (I) show a very strong fungicidal activity.

The compounds according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as e.g.

E and Z, or optical isomers are present. Both the E and the Z isomers, the individual enantiomers, the racemates, as well as any mixtures of these isomers, are claimed.

The present application preferably relates to halogen compounds of the formula (I) in which

R represents optionally mono- to tetrasubstituted phenyl, naphthyl or heteroaryl with 5 to 6 ring members, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro;

Alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;

Haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

Alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroxyalkoxycarbonyl,

Hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts;

each optionally monosubstituted to tetrasubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case double-linked alkylene or Dioxyalkylene, each having 1 to 6 carbon atoms; or

Cycloalkyl with 3 to 6 carbon atoms, R ^ stands for hydrogen, or for optionally mono- to tetrasubstituted phenyl, naphthyl or heteroaryl with 5 to 6 ring members, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro;

Alkyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 6 carbon atoms;

Alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroxyalkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts;

each up to fourfold, if necessary, the same or different

Halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, substituted and in each case doubly linked alkyl or dioxyalkylene, each having 1 to 6 carbon atoms; or

Cycloalkyl with 3 to 6 carbon atoms,

χl and X ^ are the same or different and are independently fluorine, chlorine or bromine, and X ^ represents hydrogen, fluorine, chlorine or bromine, and

Y represents heterocyclyl with 3 to 6 ring members which is optionally monosubstituted to tetrasubstituted by alkyl having 1 to 4 carbon atoms or a group -E-A-R ^, in which

HR ³ H

N N ^ / ^ for oxygen, sulfur,,, or

R ³

I stands for R ³ for alkyl with 1-4 carbon atoms,

A for a single bond or for alkanediyl with 1 to 7 chain links optionally interrupted by one or two oxygen, sulfur or nitrogen atoms and optionally substituted by phenyl, tolyl or 4-chlorophenyl, alkenediyl or alkynediyl with 2 to 7 chain links, -N = CH - or -N = C (CH ₃ ) - stands and

R4 represents hydrogen, or optionally mono- to tetrasubstituted phenyl, isoquinolyl, naphthyl, heterocyclyl with 5 to 6 ring members or cycloalkyl with 3 to 7 carbon atoms, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro;

Alkyl, alkoxy, alkylthio, alkylsulfmyl or alkylsulfonyl each having 1 to 6 carbon atoms; Haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

each optionally monosubstituted to tetrasubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case double-linked alkylene or Dioxyalkylene with 1 to 6 carbon atoms each; or

Cycloalkyl of 3 to 6 carbon atoms; or

Phenyl, phenylthio or phenoxy.

The present application relates in particular to compounds of the formula (I) in which

Rl represents phenyl, naphthyl, thienyl, pyridyl or thiazolyl which is optionally monosubstituted to tetrasubstituted, the possible substituents preferably being selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, Difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfmyl or trifluoromethylsulfonyl;

Acetyl, propionyl, acetyloxy, methoxycarbonyl, hydroxyethoxycarbonyl,

Hydroximinomethyl, hydroximinoethyl, methoximinomethyl, ethoximino-methyl, methoximinoethyl or ethoximinoethyl;

each optionally mono- or polysubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl, in each case doubly linked trimethylene (propane-1,3-diyl), methylenedioxy or ethylenedioxy,

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

stands for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or for optionally mono- to tetrasubstituted phenyl, naphthyl, thienyl, pyridyl or thiazolyl, the possible substituents being preferred are selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthioifluoromethyl, trifluoromethylsulfonyl;

Acetyl, propionyl, acetyloxy, methoxycarbonyl, hydroxyethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, ethoximino-methyl, methoximinoethyl or ethoximinoethyl; each optionally mono- or polysubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl, in each case doubly linked trimethylene (propane-1,3-diyl), methylenedioxy or ethylenedioxy,

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

X * and X ^ are the same or different and are independently fluorine, chlorine or bromine, and

X- ^{> represents} hydrogen, fluorine, chlorine or bromine, and

Y for pyrrolidine, piperidine, morpholine or, optionally substituted up to four times by methyl or ethyl and bound via nitrogen

Piperazine or a group -E-A-R ^ stands in which

E for oxygen, sulfur, ,, or

R ³ I is where R is methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

A for a single bond or for methylene, 1,1-ethanediyl, 1,2-

Ethanediyl 1,1-, 1,2-, 1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-,

2,2-, 2,3-butanediyl or 1,1-, 1,2- or l, 3- (2-methyl-propanediyl), and for -CH ₂ -CH ₂ -O-, -C (CH ₃ ) ₂ ) -O-, pentanediyl, hexanediyl,

Heptanediyl, -N = CH-, -N = C (CH ₃ ) -, -C (CH ₃ ) ₂ -, -C≡C-, -CH (C ₆ H ₅ ) -,

-CH (4-C1-C ₆ H ₄ ) - or -CH (4-methyl-C ₆ H ₄ ) - stands and R ^ stands for hydrogen, cyclohexyl, benzothiazolyl, cyclohexanothienyl, dioxoanyl or for optionally mono- to tetrasubstituted phenyl, isoquinolyl, naphthyl, thienyl, pyridyl or thiazolyl, the possible substituents preferably being selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i-propylthio, methylsulfonyl, ethylsulfmyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, difluoromethylthio, difluorochloromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromifluoromethyl,

Acetyl, propionyl, acetyloxy, methoxycarbonyl, hydroxyethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl;

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

Phenyl, phenylthio, phenoxy.

Compounds in which

X ^{1 represents} chlorine. Compounds in which

X ^{2 represents} chlorine.

Compounds in which

X ^{3 represents} hydrogen.

Compounds in which

R ^{1 represents} 4-fluorophenyl, 4-bromophenyl, phenyl, 3-chlorophenyl, in particular 4-chlorophenyl.

Compounds in which

R ^{2 represents} hydrogen.

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

The radical definitions given in detail for these radicals in the respective combinations or preferred combinations of radicals are replaced as desired by radical definitions of others, irrespective of the respectively specified combination of the radicals.

The following connections are mentioned as examples, not limiting the scope of the invention: Esters such as ethyl 3- (4-chloro-phenyl) -5,5-dichloro-4-pentenoate, benzyl 3- (4-chlorophenyl) - 5,5-dichloro-4-pentenoate, 3- (2,6-dichloro-phenyl) - 3-methyl-5,5-dichloro-4-pentenoic acid and 3- (2,6-dichloro-pyridyl-4 -) - 5,5-dichloro-4-pentenoic acid methyl ester. Amides of the pentenoic acids prepared by the process according to the invention can also be used as biologically active substances. Examples include 3- (4-chloro-phenyl) -5,5-dichloro-4-pentenoic acid-N- (4-chlorophenyl) amide, 3- (4-chloro-phenyl) -5,5-dichloro-4-pentenoic acid-N- cyclohexyl amide, 3- (4-chloro-phenyl) -5,5-dichloro-4-pentenoic acid-N-α-phenethylamide, 3- (4-chloro-phenyl-5,5-dichloro-4-pentenoic acid-N-α-p -chloro-phenethylamide, 3- (4-chloro-phenyl) -5,5-dichloro-4-pentenoic acid-N- (3,5-dichloro-phenyl) -amide, 3- (2,6-dichloro-phenyl) -5.5 -dichloro-4-pentenoic acid-

N-α-p-methylphenethylamide, 3- (4-chlorophenyl) -5,5-dichloro-4-pentenoic acid-N- (6-chloropyridyl-2) -amide, 3- (2,6-dichloro -pyridyl-4) -5,5-dichloro-4-pentenoic acid-N- (4- chlθφhenyl) -amide, and 3- (2-chloro-6-fluorophenyl) -5,5-dichloro-4-pentenoic acid -N-methyl-N- (4-chlθφhenyl) amide.

Formula (II) provides a general definition of the carboxylic acid halides required as starting materials for carrying out process a) according to the invention for the preparation of the compounds of the formula (I). In this formula (II) R, R2, χ, X ^ and X ^ preferably or in particular have those meanings which have already been in connection with the description of the compounds of the invention

Formula (I) was given as preferred or as particularly preferred for R, R2, X ¹ , χ2 and X ^. X ^ stands for halogen, especially chlorine.

The nucleophiles of the formula (III) which are furthermore required as starting materials for carrying out the process a) according to the invention for the preparation of the compounds of the formula (I) are known synthetic chemicals.

The carboxylic acid halides of the formula (II) are not yet known; they are also the subject of the present application as new substances.

They are obtained (process b) if carboxylic acids of the formula (IV), in which

R, R ^, X 1, χ2 and X ^ have the meanings given above,

with a halogenating agent, by way of example and preferably phosgene, phosphorus trichloride, phosphorus tribromide, phosphopentachloride, phosphorus oxychloride, thionyl chloride or thionyl bromide, if appropriate in the presence of a diluent, for example and preferably dichloromethane, trichloroethane or chlorobenzene, and if appropriate in the presence of a catalyst, for example and preferably Pyridine or dimethylformamide.

Formula (IV) provides a general definition of the carboxylic acids required as starting materials for carrying out process b) according to the invention for the preparation of the compounds of the formula (II). In this formula (IV), Rl, R2, χl, χ2 and X ^ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R% R2 , χl, χ2 and X ^ were specified.

The carboxylic acids of the formula (IV) are not yet known, they are new substances and, as a subgroup of the compounds of the formula (I), are also the subject of the present application.

The carboxylic acids of the formula (IV) also have a strong fungicidal and resistance-inducing action and can be used for the treatment of plant diseases. Examples of compounds of the formula (IV) which do not limit the scope of the invention are:

3-phenyl-5,5-dichloro-4-pentenoic acid, 3- (4-chloro-phenyl) -5,5-dichloro-4-pentenoic acid, 3-

(3-chlorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (2-chlorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (4-fluorophenyl) -5, 5-dichloro-4-pentenoic acid, 3- (3-fluorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (2-fluorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (4-bromophenyl) - 5,5-dichloro-pentenoic acid, 3- (4-methylphenyl) -5,5-dichloro-4-pentenoic acid, 3- (2-methylphenyl) -5,5- dichloro-4-pentenoic acid, 3- (2-trifluoromethyl-phenyl) -5,5-dichloro-

4-pentenoic acid, 3- (3-trifluoromethylphenyl) -5,5-dichloro-4-pentenoic acid, 3- (4-trifluoromethylphenyl) -5,5-dichloro-4-pentenoic acid, 3- (4-dodecyl -phenyl) -5,5-dichloro-4-pentenoic acid, 3- (4-tert-butylphenyl) -5,5-dichloro-4-pentenoic acid, 3- (2-isopropylphenyl) -5, 5 - dichloro-4-pentenoic acid, 3 - (4-methoxyphenyl) -5, 5 -dichloro-4-pentenoic acid, 3- (2-isopropoxyphenyl) -5,5-dichloro-4-pentenoic acid, 3- (4th -

Trifluoromethoxy-phenyl) -5,5-dichloro-4-pentenoic acid, 3- (3-trifluoromethoxy-phenyl) -5,5-dichloro-4-pentenoic acid, 3- (2,4-dichloro-phenyl) -5.5 -dichlor-4-pentenoic acid, 3- (2,6-dichlorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (2,5-dichlorophenyl) -5,5-dichloro-4-pentenoic acid , 3- (2,3-dichlorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (3,4-dichlorophenyl) -5,5-dichloro-4-pentenoic acid, 3- (2- Chloro-6-fluoro-phenyl) -5,5-dichloro-4-pentenoic acid, 3- (2-chloro-5-trifluoromethyl-phenyl) -5,5-dichloro-4-pentenoic acid, 3- (2,6- Dichloro-4-trifluoromethylphenyl) -5,5-dichloro-4-pentenoic acid, 3- (2,6-dichloro-4-trifluoromethoxyphenyl) -5,5-dichloro-4-pentenoic acid, 3- ( 4-chlorophenyl) -3-methyl-5,5-dichloro-4-pentenoic acid, 3- (3-chlorophenyl) -3-methyl-5,5-dichloro-4-pentenoic acid, 3- (2, 6-dichlorophenyl) -3-methyl-5,5-dichloro-4-pentenoic acid, 3- (2-chloro-6-fluorophenyl) -3-methyl-5,5-dichloro-4-pentenoic acid, 3 - (3,4-dichlorophenyl) -3-isopropyl-5,5-dichloro-4-pentenoic acid, 3- (2-chlorophenyl) -5,5-difluoro-4-pentenoic acid, 3- (4- Methylphenyl) -5, 5-difluoro-4-pentenoic acid, 3- (3-trifluoromethyl-phenyl) -5,5-difluoro-4-pentenoic acid, 3- (4-trifluoromethoxy-phenyl) -5,5-difluoro-4-pentenoic acid, 3- (2-chloro-6-fluorophenyl) -5,5-difluoro-4-pentenoic acid, 3- (2-chloro-6-fluorophenyl) -3-methyl-5,5-difluoro-

4-pentenoic acid, 3- (2-chloro-6-fluorophenyl) -5,5-dibromo-4-pentenoic acid, 3- (pyridyl-2 -) - 5,5-dichloro-4-pentenoic acid, 3- (pyridyl-3 -) - 5,5-dichloro-4-pentenoic acid, 3- (pyridyl-4 -) - 5,5-dichloro-4-pentenoic acid, 3- (2-chloro-pyridyl-3 -) - 5,5-dichloro-4-pentenoic acid, 3- (2,6-dichloro-pyridyl-4 -) - 5,5-dichloro-4-pentenoic acid, 3- (2nd , 6-dichloropyridyl-4) -5,5-difluoro-4-pentenoic acid, 3- (2,6-dichloropyridyl-4 -) - 5,5-dibromo-4-pentenoic acid, 3- (2, 3-dibromothiophenyl-5 -) - 5,5-dichloro-4-pentenoic acid, 3- (3,4-dichloro-l, 2-thiazolyl-5 -) - 5,5-di-chloro-4-pentenoic acid .

Carboxylic acids of the formula (IV) with χ3 in their meaning as hydrogen are obtained (process c) if dihalogenethene derivatives of the formula (V),

in which

R, R2, χl and χ2 have the meanings given above and

Z stands for a grouping which forms an acidic condition

Carbonium ions is split off,

with 1,1-dichloroethene in the presence of water-containing acids.

Formula (V) provides a general definition of the dihaloethene derivatives required as starting materials for carrying out process c) according to the invention for the preparation of the carboxylic acids of the formula (IV). In this formula (V), R, R2, χ and χ preferably or in particular have those meanings which already in connection with the description of the compounds of the invention

Formula (I) were given as preferred or as particularly preferred for Rl, R, χl and χ. Z stands for a group which is split off under the reaction conditions, a cationic reactive intermediate being formed, which reacts electrophilically with the olefinic component (1,1-dichloroethane) to form a further reactive intermediate which is finally solvolysed. As Grouping Z are, for example, chlorine, bromine, hydroxy, alkoxy, preferably methoxy or ethoxy, or aryloxy, preferably phenoxy.

Process c) according to the invention for the preparation of the new carboxylic acids of the formula (IV) with X ^ in its meaning as hydrogen is carried out according to the schematic formula equation (A):

(V) (IV)

The reaction takes place more strongly when the reactants are mixed in the presence

Acids, where 1,1-dichloroethene is advantageously used in excess.

The reaction is carried out at temperatures from 0 ° to 30 ° C., preferably at 0 ° to 10 ° C. It is surprising that the products of formula (IV) are obtained smoothly and in high yield, although the -CH = Cχlχ2 groupings of the starting compounds can also be electrophilically solvolysed.

Strong acids which can be used as mediators of the synthesis reaction are, for example and preferably, sulfuric acid, methanesulfonic acid, trifluoroacetic acid or phosphoric acid. Sulfuric acid is particularly preferred, especially in the concentration range of 60-95%.

Some compounds of formula V are known and can be obtained by methods known per se (see, for example, Izv.Akad.Nauk SSSR Ser.Khim., 1956, 313, 317; English edition p. 303, 306). The reaction yields and the flexibility of the production method described leave something to be desired.

The compounds of the formula (V) are obtained particularly advantageously if (process d) trihalomethyl compounds of the formula (VI)

in which

R, R2, χl and χ2 have the meanings given above,

X-> stands for halogen, and

7X stands for halogen

with an aqueous base, such as sodium hydroxide solution.

Formula (VI) provides a general definition of the trihaloethane derivatives required as starting materials for carrying out process d) according to the invention for the preparation of the trihalomethyl compounds of the formula (V). In this

Formula (VI) has R, R, χl and χ preferably or in particular those meanings which have already been given in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for Rl, R2, Formell and χ were. χ5 represents halogen, preferably chlorine or bromine. Z * also stands for halogen, preferably for

Chlorine or bromine.

The compounds of formula VI are known and can be obtained by known methods (see e.g. Phosphorus Sulfur 19, 1984, 199-204).

Carboxylic acids of the formula (IV) with X ^ in their meaning as halogen are obtained if (process e) esters of the formula (VII), in which

R, R2, χ and χ2 have the meanings given above, and

χ6 represents halogen,

R ^{5 represents} alkyl,

with a base, preferably an alkaline earth metal or alkali metal hydroxide, such as, for example, lithium hydroxide, sodium hydroxide or potassium hydroxide, if appropriate in the presence of water and if appropriate in the presence of a further diluent, such as, for example, tetrahydrofuran, dimethoxyethane or dioxane.

Formula (VII) provides a general definition of the esters required to carry out process e) according to the invention for the preparation of the carboxylic acids of the formula (IV) with X ^ as halogen as starting materials. In this formula (VII), Rl, R2, χl and χ2 preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for Rl, R, χl and χ were specified. χ6 represents halogen, preferably fluorine, chlorine or bromine. R- is alkyl, preferably methyl or ethyl. The esters of formula (VII) are not yet known, they are new substances and, as a subgroup of the compounds of formula (I), are also the subject of the present application. They are obtained if halogen alkyl esters of the formula (VIII),

in which

R, R, R5, χl χ2 and ^~ ß have the meanings given above, and

X ^{7 represents} halogen,

with a base, preferably an alkaline earth metal or alkali metal hydride, or alcoholate, such as sodium hydride, sodium methylate, sodium ethylate or potassium tert-butoxide, optionally in the presence of a diluent, such as methanol, ethanol, tetrahydrofuran, dimethoxyethane, dioxane, dimethyl thylformamide or dimethyl sulfoxide.

The haloalkyl esters required as starting materials for carrying out the process f) according to the invention for the preparation of the esters of the formula (VII) are generally defined by the formula (VIII). In this formula (VIII), R ¹ , R ² , R5, χl χ2 and χ6 preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (VII) according to the invention, are preferred or particularly preferred for R. , R2, R5, χl χ2 and X "have been specified. X ⁷ represents halogen, preferably fluorine, chlorine or bromine. The haloalkyl esters of the formula (VIII) are not yet known; they are also the subject of the present application as new substances.

They are obtained (process g) if halogen compounds of the formula (I-a),

in which

R, R2, R5 χl and χ2 have the meanings given above, with a conventional chlorination, bromination and iodination agent, such as, for example

Chlorine, bromine, iodine or sulfuryl chloride, optionally in the presence of a diluent, such as carbon tetrachloride, is reacted.

The halogen compounds required as starting materials for carrying out the process g) according to the invention for the preparation of the haloalkyl esters of the formula (VIII) are generally defined by the formula (I-a). In this formula (Ia), Rl, R2, R5, χl and χ2 preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (VII) according to the invention, are preferred or particularly preferred for R, R, R5 χl and X were specified.

The halogen compounds of the formula (I-a) are a subgroup of the compounds of the formula (I) according to the invention and can be obtained by process a).

Suitable diluents for carrying out process a) according to the invention are all inert organic solvents. These include, for example and preferably, aliphatic, alicyclic or aromatic carbon hydrogen, for example and preferably petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example and preferably, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, for example and preferably diethyl ether, diisopropyl ether, methyl t-butyl ether,

Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; or amides, by way of example and with preference N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpynolidone or hexamethylphosphoric triamide.

Process a) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydroxides, acetates, carbonates or hydrogen carbonates, by way of example and with preference sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate,

Calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate and tertiary amines, for example and preferably trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmoφholin, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicyclonecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process a) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.

To carry out the process according to the invention for the preparation of the compounds of the formula (I), 1 to 15 mol, preferably 1 to 8 mol, of a nucleophile are generally employed per mol of the carboxylic acid halide of the formula (II)

Fonnel (III) a. All of the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar - u.

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used to control Plasmodiophoromycetes,

Use Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens of fungal and bacterial are exemplary but not limiting

Diseases that fall under the generic names listed above: Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or

Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea

(Conidial form: Drechslera, Syn: Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodomm;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae; Pseudocercosporella species, such as, for example, Pseudocercosporella heφotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or cultivated plants (including naturally occurring cultivated plants). Cultivated plants can be plants by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these Methods can be obtained, including transgenic plants and including plant varieties that can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as sprout, leaf, flower and root, examples being leaves, needles, stems, stems, flowers, fruiting bodies,

Fruits and seeds as well as roots, tubers and rhizomes are listed. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of plants and parts of plants according to the invention with the

Active substances take place directly or by influencing their surroundings, living space or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multilayer coating.

The active compounds according to the invention can be used particularly successfully to combat rice diseases, for example against Pyricularia species. The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols,

Fine encapsulation in polymeric materials and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using of surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic

Hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. 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, highly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates. The following are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifiers and / or foaming agents are: e.g. nonionic 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 hydrolyzates. Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments, for example iron oxide, titanium oxide, fenocyanine blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used .

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

Fungicides:

Aldimoφh, Ampropylfos, Ampropylfos Potassium, Andoprim, Anilazine, Azaconazole, Azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyphodaminazol, cypodaminazol, cypodinconol Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomoφh, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianonodolone, dithianonodol, dithianonodol, dithianonodol, dithianonodol,

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimoφh, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, fliusrimidol, fliusrimidol,

Flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

Guazatin,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan,

Isovaledione,

Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol, Ofürace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazole, pefürazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb,

Propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

Quinconazole, quintozen (PCNB), quinoxyfen,

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutichl, triazoxid, triazoxid, triazoxid, triazoxide

Tridemoφh, triflumizole, triforin, triticonazole,

Uniconazole,

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G,

OK-8705,

OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichloro phhenyl) -ß-fluorine -b-propyl-1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichloφhenyl) -ß-methoxy-a-methyl-1 H-1, 2,4-triazole-1 -ethanol, α- (5-methyl-1, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] - 1 H- 1, 2,4-triazol-1 - ethanol, (5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1 H-1, 2,4-triazol-1-yl) -3-octanone,

(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide, {2-Methyl- 1 - [[[1 - (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester

1 - (2,4-dichloφhenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) -oxime,

1 - (2-methyl-1-naphthalenyl) - 1 H-pynol-2,5-dione, 1 - (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pynolidinedione, l- [ (Diiodomethyl) sulfonyl] -4-methyl-benzene,

1 - [[2- (2,4-dichlorothenyl) -1,3-dioxolan-2-yl] methyl] -1 H-imidazole,

1 - [[2- (4-chloro-phenyl) -3-phenyloxiranyl] methyl] - 1 H- 1, 2,4-triazole, l- [l- [2 - [(2,4-dichloro-phenyl) methoxy]] -phenyl] -ethenyl] -IH-imidazole, 1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide,

2,2-dichloro-N- [1 - (4-chloro-phenyl) ethyl] - 1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate, 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,

2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(l-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole,

2 - [[6-Deoxy-4-O- (4-O-methyl-ß-D-glycopyranosyl) -aD-glucopyranosyl] -amino] -4- methoxy-lH-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile,

2-aminobutane,

2-bromo-2- (bromomethyl) pentandinitrile,

2-chloro-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide,

2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide, 2-phenylphenol (OPP),

3,4-dichloro-l- [4- (difluoromethoxy) phenyl] -IH-pyrrole-2,5-dione,

3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,

3- (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile,

3- [2- (4-Chlθφhenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -lH-imidazole-l- sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one, 8- (1, 1-dimethylethyl) -N-ethyl-N-propyl-1, 4-dioxaspiro [4.5] decane-2-methanamine,

8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2- [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-Chlθφhenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -cycloheptanol, cis-4- [3- [4- (l, 1-dimethylpropyl) -phenyl -2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,

Ethyl - [(4-chloro-phenyl) -azo] cyanoacetate,

Potassium hydrogen carbonate, methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1 H-imidazole-5-carboxylate,

Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,

Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,

N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexane carboxamide. N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,

N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,

N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,

N- (4-cyclohexylphenyl) - 1, 4,5,6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) - acetamide,

N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,

N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,

N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,

N-formyl-N-hydroxy-DL-alanine sodium salt, O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,

O-methyl-S-phenyl-phenylpropylphosphoramidothioat €,

S-methyl-l, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, r (3'H) -isobenzofuran] -3'-one, Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, popilliae azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin, Bacillus, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis ,

Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomethrin, Biopermethrin, BPMC, Bromophos A, Bufencarb, Buprofezin, Butocarboxidobox, Carbocarboxofan, Carboxafaben, Carbathofoxyl, Carboboxyl Cartap

Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloφyrifos, Chloφyrifos M, Chlovaporthrin, Cis-Resmethrin, Cispermethrin, Clocythrin, Cloethocarb, Clofentezine, Cyanophoputhrin, Cycloprin, Cycloprin, Cycloprin M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,

Dichlorvos, diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, doenapyn,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrine

Fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethxate, granulosfonarbiazolate, fosti firhiazolate, fosti firhiazolate, fosti firhiazole

Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

Nuclear polyhedron viruses

Lambda cyhalothrin, lufenuron

Malathion, mecarbam, metaldehyde, methamidophos, metharhilic anisopliae, metharhilic flavoviride, methidathione, methiocarb, methomyl, methoxyfenozide,

Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,

Naled, Nitenpyram, Nithiazine, Novaluron

Omethoate, Oxamyl, Oxydemethon M

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A,

Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pymetrozine,

Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridathion, Pyrimidifen,

Pyriproxyfen,

Quinalphos, Ribavirin

Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos,

Tau fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,

Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Thetacypermethrin, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thuringiensin, Tralocythrin, Tralomethrin

Triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon,

Triflumuron, trimethacarb,

Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302 Zeta-cypermethrin, Zolaprofos

(IR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate

(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine -2 (lH) - imine

2- (2-chloro-6-fluoro-phenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazole 2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione

2-Chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide

2-Chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy) phenyl] amino] carbonyl] benzamide

3-methylphenyl propyl carbamate 4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene

4-chloro-2- (l, l-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] -

3 (2H) pyridazinone

4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone 4-chloro-5 - [(6-chloro-3 -pyridinyl) methoxy] -2- (3,4-dichloφhenyl) -3 (2H) -pyridazinone

Bacillus thuringiensis strain EG-2348

Benzoic acid [2-benzoyl-1 - (1, 1-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloro-phenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester [3 - [(6-chloro-3-pyridinyl ) methyl] -2-thiazolidinylidene] cyanamide

Dihydro-2- (nitromethylene) -2H- 1,3-thiazine-3 (4H) -carboxaldehyde

Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate

N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine

N- (4-Chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide

N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine

N-methyl-N '- (1-methyl-2-propenyl) - 1, 2-hydrazinedicarbothioamide

N-methyl-N '-2-propenyl-1, 2-hydrazinedicarbothioamide

O, O-Diethyl- [2- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate

A mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators are possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The Application takes place in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to apply the active ingredient preparation or the active ingredient itself to the soil to inject. The seeds of the plants can also be treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.

In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which are found in agriculture, in forests, in the protection of Vonats and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chilopoda, for example Geophilus caφophagus, Scutigera spp .. From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus.

From the order of the Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera e.g. Reticulitermes spp ..

From the order of the Phthiraptera e.g. Pediculus humanus coφoris, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp ..

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

Thrips palmi, Frankliniella accidentalis.

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, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigususpp. Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysonhoea, Lymantria spp., Bucculatrix thurberiisisppppi, Fitrella, Phyllocnist spp., Mamestra brassicae, Panolis flammea, Spodoptera Spp., Trichoplusia ni, Caφocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionellaosellaanaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaellaella pellaella pellaella , Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp ..

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica,

Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephispp., Oryzaephispp assimilis, Hypera postica, Dermestes spp., Trogoderma spp.,

Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Costimallontra solitudes.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera e.g. 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 spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomy

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

From the class of the Arachnida e.g. Scoφio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I. Chorioptes spp., Sarcoptes spp.,

Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp ..

Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.

When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.

The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, impregnated with active ingredients

Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents. thus emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as

Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Possible solid carriers are: e.g. Ammonium salts and natural rock flours, such as kaolins, clays,

Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. 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 hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho- lipids such as cephalins and lecithins and synthetic phosphophides. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, fenocyanine blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

When used as insecticides, the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight. The application takes place in a customary manner adapted to the application forms.

When used against hygiene and Vonat pests, the active substance is characterized by an excellent residual effect on wood and clay as well as a good stability to alkali on limed substrates.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

The following examples serve to explain the invention. However, the invention is not limited to the examples.

Manufacturing examples:

example 1

5, 5-dichloro-N- (3,5-dichloro-phenyl) -3- (4-fluoro-phenyl) -4-pentanamide (process a)

A solution of 1.5 g of 5,5-dichloro-N- (3,5-dichloφhenyι) -3- (4-fluoφhenyι) -4- pentenoic acid chloride in 10 mL dichloromethane is stirred at 0 ° C to a mixture of 0.94 g 3 , 5-dichloroaniline in 10 mL dichloromethane and 5.3 mL 10% sodium hydroxide solution. When the reaction has ended (TLC control), the phases are separated and the organic phase is concentrated in vacuo (2.3 g). The crude product is chromatographed on silica gel using toluene / ethyl acetate (10: 2 to 1: 1). 2.1 g (97% of theory) of 5,5-dichloro-N- (3,5-dichloφhenyl) -3- (4-fluoφhenyl) -4-pentenamide are obtained.

1H-NMR (CDC1 ₃ , TMS): δ = 7.35 (3, 2H) ppm

Example 2

5, 5-dichloro-3- (4-chloro-phenyl) -4-pentenoate (process a)

A solution of 3.0 g of 5,5-dichloro-3- (4-chloro-phenyl) -4-pentenoic acid chloride in 50 ml

Methanol is heated to reflux. After cooling, the reaction solution is concentrated in vacuo, taken up in dichloromethane and washed with water. The organic phase is dried over sodium sulfate and concentrated in vacuo. 2.7 g (91% of theory) of 5,5-dichloro-3- (4-chlorophenyl) -4-pentenoic acid methyl ester are obtained.

Η NMR (CDC1 ₃ , TMS): δ = 3.63 (s, 3H) ppm

Analogously to Examples (1) and (2), and in accordance with the general description of the production process a) according to the invention, the in Compounds of the formula (I) according to the invention listed in Table 1 below, in which R ^{2 represents} hydrogen:

Table 1:

Table:

Table 1:

Table:

Production of preliminary products:

Precursors of formula (II)

Example II-1

5,5-dichloro-3- (4-chloro-phenyl) -4-pentenoic acid chloride (process b)

A mixture of 28.1g 5,5-dichloro-3- (4-chloro-phenyl) -4-pentenoic acid, 150ml

Dichloromethane and 75 g of thionyl chloride were heated to boiling under reflux until gas evolution ceased. The mixture was concentrated in vacuo and fractionally distilled in a high vacuum. 24 g (80% of theory) of 5,5-dichloro-3- (4-chloro-phenyl) -4-pentenoic acid chloride with a boiling point of 135-150 ° C. at 0.4 mbar are obtained.

Analogously to Example (II-1) and in accordance with the general description of the production process b) according to the invention, the compounds of the formula (II) according to the invention listed in Table 2 below are also obtained:

Table 2:

Preproducts of the formula (IN)

Example IN-1

5,5-dichloro-3- (4-chlθφhenyl) -4-pentenoic acid (method c)

A mixture of 109.7g l-chloro-4- (l, 3,3-trichlor-2-propenyι) bertzole and 3,3-

Dichloro-l- (4-chlθφhenyl) -2-propen-l-ol and 166.3 g of vinylidene chloride are added dropwise to 450 ml of 88% sulfuric acid at about 5 ° C. with stirring. After the addition has ended, the mixture is stirred for 1.5 hours, the mixture is poured onto 1500 g of ice and extracted several times with dichloromethane. The combined organic phases are extracted with sodium hydroxide solution, the extract is acidified with concentrated hydrochloric acid and extracted back with dichloromethane. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. 63.7 g of 5,5-dichloro-3- (4-chloro-phenyl) -4-pentenoic acid are obtained.

Η NMR (CDC1 ₃ , TMS): δ = 2.81 (m, 2H) ppm Example IV-2

4,5,5-trichloro-3- (4-chloro-phenyl) -4-pentenoic acid (method e)

6.9 g of 4,5,5-trichloro-3- (4-chloro-phenyl) -4-pentenoate are dissolved in 60 ml of tetrahydrofuran and a solution of 2.6 g of lithium hydroxide in 30 ml of water is added. The mixture is stirred at 20 ° C. until the reaction has ended. Then the solution is slightly acidified with 1N hydrochloric acid, the tetrahydrofuran is distilled off in vacuo and the remaining aqueous mixture is extracted with ethyl acetate. The organic phase is washed with 1N hydrochloric acid, dried over sodium sulfate and concentrated under reduced pressure. 5.7 g (87% of theory) of 4,5,5-trichloro-3- (4-chlorophenyl) -4-pentenoic acid are obtained.

1H-NMR (CDC1 ₃ , TMS): δ = 4.82 (t, 3H, J = 7.0 Hz) ppm

Analogously to Examples (IV-1) and (IV-2), and in accordance with the general description of the production processes c) and e) according to the invention, the compounds of the formula (IV) according to the invention listed in Table 3 below are also obtained:

Table 3

Precursors of formula (V)

Example V-l

l-chloro-4- (l, 3,3-trichlor-2-propenyl) benzene and 3,3-dichloro-l- (4-chlθφhenyl) -2-propen-1-ol (method d)

175.4g l-chloro-4- (l, 3,3,3-tetrachloφropyl) benzene are dissolved in 500 ml dichloromethane and mixed with a solution of 26.4 g sodium hydroxide in 500 ml water. 2.5 g of tetrabutylammonium bromide are added and the mixture is heated under reflux and stirred for 16 hours. The phases are separated and the aqueous phase is subsequently extracted with dichloromethane. The combined organic phases are dried over sodium sulfate, concentrated in vacuo and the residue is fractionally distilled in a high vacuum. A mixture of 1-chloro-4- (1,3,3-trichloro-2-propenyl) benzene and 3,3-dichloro-l- (4-chlθφhenyl) -2-propen-l-ol, which as

Mixture can be used for further syntheses. Kp .: 121 ° C (0.74-0.81 mb)

The following are obtained analogously:

Table 4:

The compounds V-2 to V-5 were further implemented without purification.

Precursors of formula (VI)

Example VI-1

1 -Chlor-4- (1, 3, 3, 3 -tetrachloφropyl) benzene

(Phosphorus Sulfur 19, 1984, 199-204) 200 g of 4-chlorostyrene, 2000 ml of carbon tetrachloride and 3.5 g of ruthenium-tris-triphenylphosphine dichloride are stirred under reflux until the conversion is complete. This is checked by regular GC measurements of the reaction mixture. The solvent is removed in vacuo and the residue is fractionally distilled in a high vacuum. This gives 338 g (80% of theory) of l-chloro-4- (1,3,3,3-tetrachloφropyl) benzene with a boiling point of 130 ° C. at l mbar.

The following were obtained analogously:

Table 5:

Precursors of formula (VII)

Example VII-1

4,5,5-Trichlor-3- (4-chloro-phenyl) -4-pentenoic acid methyl ester (process f)

14.1 g of methyl tetrachloro-3- (4-chlorophenyl) pentanoate in 50 ml of methanol are added dropwise to a solution of 1.7 g of sodium hydride (60% in mineral oil) in 200 ml of methanol. After stirring for 1 hour at room temperature, the reaction mixture is introduced into four times the amount of saturated ammonium chloride solution and extracted three times with methylene chloride. The combined organic phases are dried over magnesium sulfate and the solvent is removed under reduced pressure. The residue is chromatographed on silica gel using petroleum ether / toluene (3: 1 to 0: 1). 7.1 g (68% of theory) of 4,5,5-trichloro-3- (4-chloro-phenyl) -4-pentenoate are obtained.

1H-NMR (CDC1 ₃ , TMS): δ = 3.68 (s, 3H) ppm

Precursors of formula (VIII)

Example VIII-1

4,5,5,5-tetrachloro-3- (4-chloro-phenyl) pentanoic acid methyl ester (process g)

Chlorine is passed into a solution of 12.3 g of 5,5-dichloro-3- (4-chloro-phenyl) -4-pentenoate in 100 ml of carbon tetrachloride until complete conversion is reached after about an hour (monitored by regular GC analyzes ). Dissolved chlorine is blown out with argon and then the solvent is removed under reduced pressure. 15.2 g (99% of theory) of 4,5,5,5-tetrachloro-3- (4-chloro-phenyl) -pentanoic acid methyl ester are obtained as a mixture of two diastereoisomers.

Isomer A

1H-NMR (CDC1 ₃ , TMS): δ = 4.95 (d, IH, J = 2.9 Hz) ppm

Isomer B

H-NMR (CDCI ₃ , TMS): δ = 4.59 (d, IH, J = 1.9 Hz) ppm

Examples of use:

Example A

Pyricularia test (rice) / resistance induction

Solvent: 48.8 parts by weight of N, N-dimethylformamide emulsifier: 1.2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the mixture is diluted

Concentrate with water and the specified amount of emulsifier to the desired concentration.

To test for resistance-inducing activity, young rice plants are sprayed with the preparation of active compound in the stated application rate. 5 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and a temperature of 25 ° C.

Evaluation is carried out 4 days after the inoculation. 0% means a

Efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (18), (5), (4), (6), (15), (16) and (20) show one at an application rate of 375 g / ha

Efficiency of 90% or more. Example: B Plutella test

Solvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound 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 treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cabbage cockroach (Plutella maculipennis) while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test e.g. the compound of preparation example (13) at an exemplary active ingredient concentration of 0.1%, a kill of 100% after 3 days.

Claims

claims

1. Halogen compounds of the general formula (I)

in which

R represents substituted or unsubstituted aryl or heteroaryl,

R ^ is hydrogen, substituted or unsubstituted alkyl, aryl or

Heteroaryl is, where halogen, alkoxy and aryloxy radicals are substituents on the alkyl radicals, halogen, alkyl and alkoxy radicals as substituents on the aryl or hetaryl radical, and the CF3 and CF3O radicals and NO ₂ are suitable,

χ and X ^ are the same or different and independently of one another represent fluorine, chlorine or bromine,

χ3 represents hydrogen, fluorine, chlorine or bromine, and

Y represents optionally substituted nitrogen-bonded heterocyclyl or a group -E-A-R ^, in which

E for oxygen, sulfur,

R ³

or O, where R 3 is alkyl, A for a single bond or for alkane diyl, alkenediyl, alkynediyl, -N = CH- or -N = C (CH ₃ ) -, cycloalkyl or heterocyclyl optionally interrupted by oxygen, sulfur or nitrogen and optionally substituted by phenyl, tolyl or 4-chloro-phenyl stands, and

R4 represents hydrogen, or optionally substituted aryl, cycloalkyl or heteroalkyl.

2. Halogen compounds of formula (I) according to claim 1, characterized in that

R represents optionally mono- to tetrasubstituted phenyl, naphthyl or heteroaryl with 5 to 6 ring members, the possible ones

Substituents are preferably selected from the list below:

Halogen, cyano, nitro;

Haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

Alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroxyalkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts; in each case optionally up to four times, identical or different, halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or 5 different halogen atoms, in each case doubly linked alkylene or dioxyalkylene each having 1 to 6 carbon atoms; or

Cycloalkyl with 3 to 6 carbon atoms,

10

R2 represents hydrogen, or optionally mono- to tetrasubstituted phenyl, naphthyl or heteroaryl with 5 to 6 ring members, the possible substituents preferably being selected from the list below:

15

Halogen, cyano, nitro;

20th

25 alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroxyalkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts;

each optionally up to four times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched Haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted, in each case doubly linked alkylene or dioxyalkylene, each with 1 to 6 carbon atoms; or

Cycloalkyl with 3 to 6 carbon atoms,

χ and X ^ are the same or different and are independently fluorine, chlorine or bromine, and

X ^{~ represents} hydrogen, fluorine, chlorine or bromine, and

E for oxygen, sulfur, .

R ³

I or stands for, where R stands for alkyl with 1-4 carbon atoms,

A for a single bond or for alkane diyl with 1 to 7 chain links optionally interrupted by one or two oxygen, sulfur or nitrogen atoms and optionally substituted by phenyl, tolyl or 4-chloro-phenyl, alkenediyl, alkynediyl with 2 to 7 chain links,

-N = CH- or -N = C (CH ₃ ) - stands and R ^ represents hydrogen, or optionally mono- to tetrasubstituted phenyl, isoquinolyl, naphthyl or heteroaryl with 5 to 6 ring members or cycloalkyl with 3 to 7 carbon atoms, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro;

Alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 10 1 to 6 carbon atoms;

Haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different 15 halogen atoms;

Alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroxyalkoxycarbonyl, hydroximinoalkyl or alkoximmoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts;

each optionally optionally up to four times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each substituted twice linked alkylene or dioxyalkylene each having 1 to 6 carbon atoms;

30 cycloalkyl of 3 to 6 carbon atoms; or Phenyl, phenylthio or phenoxy.

3. Compounds of formula (I) according to claim 1, characterized in that

R ^{1 represents} phenyl, naphthyl, thienyl, pyridyl or thiazolyl which is optionally monosubstituted to tetrasubstituted, the possible substituents preferably being selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, difluoromethylthio, difluorochloromethylethylthio, trifluoromethyl or trifluoromethyl;

Acetyl, propionyl, acetyloxy, methoxycarbonyl, hydroxyethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoxyimino-methyl, ethoximonomethyl, methoximinoethyl or ethoximinoethyl;

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or phenyl which is optionally mono- to tetrasubstituted, Is naphthyl, thienyl, pyridyl or thiazolyl, the possible substituents preferably being selected from the list below:

Acetyl, propionyl, acetyloxy, methoxycarbonyl, hydroxyethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximino-methyl, ethoximinomethyl, methoxyiminoethyl or ethoximinoethyl;

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

X ¹ and X ^{2 are the} same or different and are independent of each other

Fluorine, chlorine or bromine are available, and

X ^{3 represents} hydrogen, fluorine, chlorine or bromine, and

Y for pynolidine, piperidine which is optionally up to four times substituted by methyl or ethyl and is bound via nitrogen, Moφholin or piperazine or a group -EAR ⁴ , wherein

for oxygen, sulfur, , or

ΓΛ ³

stands, wherein R ^{3 is} methyl, ethyl. is n- or i-propyl, n-, i-, s- or t-butyl,

A for a single bond or for methylene, 1,1-ethanediyl, 1,2-

Ethanediyl, 1,1-, 1,2-, 1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1,3-, 1,4-, 2,2-, 2, 3-butanediyl or 1,1-, 1,2- or l, 3- (2-methyl-propanediyl), and for -CH ₂ -CH ₂ -O- or -C (CH ₃ ) ₂ ) -O-, Pentanediyl, hexanediyl, heptanediyl, -N = CH-, -N = C (CH ₃ ) -, -C (CH ₃ ) ₂ -, -C≡C-, -CH (C ₆ H ₅ ) -, -CH ( 4-C ₆ H ₄ ) - or -CH (4-methyl-C ₆ H ₄ ) - is and

R ^{4 stands} for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or for optionally monosubstituted to tetrasubstituted phenyl, isoquinolyl, naphthyl, thienyl, pyridyl or thiazolyl, where the possible substituents are preferably selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl; Acetyl, propionyl, acetyloxy, methoxycarbonyl, hydroxyethoxycarbonyl, hydroximinomethyl, hydrximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl;

Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,

Phenyl, phenylthio, phenoxy.

4. Compounds of formula (II), characterized in that

R ¹ , R ² , X ¹ , X ² and X ^{3 are} as defined in claim 1, and

X ^{4 represents} halogen.

5. Compounds of formula (IV), characterized in that

R ¹ , R ² , X ¹ , X ² and X ^{3 are} as defined in claim 1.

Compounds of formula (VII), characterized in that

R ¹ , R ² , X ¹ and X ^{2 are} as defined in claim 1,

X ^{6 represents} halogen, and

R ^{5 represents} alkyl.

7. Compounds of formula (VIII), characterized in that

R ¹ , R ² , X ¹ , X ^{2 are} as defined in claim 1,

X ⁶ and R ^{5 are} as defined in claim 6, and

X ^{7 represents} halogen.

8. agents containing extenders and / or carriers and optionally surface-active substances, characterized by a content of at least one compound as defined in claims 1 to 3 and 5.

9. A method for controlling pests, characterized in that compounds as defined in claims 1 to 3 and 5 or agents as defined in claim 8 are allowed to act on pests and / or their habitat.

10. Use of compounds as in claims 1 to 3 and 5 or agents as defined in claim 8 for controlling pests.

11. A process for the preparation of compounds of formula (I), according to claim 1, characterized in that compounds of formula (II),

in which

R, R ^, χl, χ2 and X ^ have the meanings given in claim 1 and

X ^ represents halogen,

with a nucleophile of the formula (III),

HY (III) in which Y has the meaning given in claim 1,

12. A process for the preparation of compounds of the formula (II), according to claim 4, characterized in that carboxylic acids of the formula (IN),

in which

R, R ^, χl, χ2 and X- have the meaning given in claim 4,

with a halogenating agent, if appropriate in the presence of a diluent, and if appropriate in the presence of a catalyst.

13. A process for the preparation of compounds of the formula (IV) according to claim 5, characterized in that compounds of the formula (IV) in which X ^{3 represents} hydrogen are reacted by compounds of the formula (V),

in which R, R ^, χl and X ^ have the meanings given in claim 5 and

Z stands for a grouping under acidic conditions

Formation of a carbonium ion is split off,

with 1,1-dichloroethene in the presence of water-containing acids,

or for the preparation of compounds of the formula (IN), according to claim 5 with X ³ as halogen, by reacting esters of the formula (VII),

in which

R, R ^, χl and X ^ have the meanings given in claim 5, and

χ6 represents halogen,

R ^{5 represents} alkyl,

with a base, optionally in the presence of water and optionally in the presence of a further diluent.

14. Process for the preparation of compounds of formula (V),

^{H = α'χ!} (V) in which

R, R ^, χl, χ2 have the meanings given in claim 5 and

Z stands for a grouping under acidic conditions

Formation of a carbonium ion is split off,

characterized in that one

Trihalomethyl compounds of the formula (VI),

in which

R, R ^, χl and X ^ have the meanings given in claim 5,

χ5 represents halogen, and

Z stands for halogen

with an aqueous base.

15. A process for the preparation of compounds of the formula (VII), according to claim 6, characterized in that compounds of the formula (VIII), in which

R, R ^, R ^, χl χ2 _un j χ6 have the meanings given in claim 6, and

X ~ l represents halogen,

with a base, optionally in the presence of a diluent.

16. A process for the preparation of compounds of the formula (VIII) according to claim 7, characterized in that compounds of the formula (I-a)

in which

R, R ^, χl and X ^ have the meanings given in claim 1, and R ^{5 is} alkyl, with a customary chlorination, bromination and iodination agent, optionally in the presence of a diluent.

17. A process for the preparation of agents, characterized in that compounds as defined in claims 1 to 3 and 5 with stretch agents and / or carriers and / or surface-active agents mixed.

18. Fungicidal compounds of the general formula (I),

in which

R represents substituted or unsubstituted aryl or heteroaryl,

R2 for hydrogen, substituted or unsubstituted alkyl, aryl or

Heteroaryl, where halogen is the substituent on the alkyl radical,

Alkoxy and aryloxy radicals, halogen, alkyl and alkoxy radicals as substituents on the aryl or hetaryl radical, and the CF ₃ and CF ₃ O radicals and NO ₂ are possible,

X ^ represents hydrogen, fluorine, chlorine or bromine, and

Y represents optionally substituted nitrogen-bonded heterocyclyl or a group -EAR ^, in which for oxygen, sulfur,

or where R ^{3 is} alkyl,

A for a single bond or for alkanediyl, alkenediyl, alkynediyl, -N = CH- or -N = C (CH ₃ ) -, optionally interrupted by oxygen, sulfur or nitrogen and optionally substituted by phenyl, tolyl or 4-chloro-phenyl, Cycloalkyl or heterocyclyl and

10 R ^ represents hydrogen, or optionally substituted aryl or heteroaryl.