DE10038019A1 - Substituted triazolopyride (az) ine - Google Patents

Abstract

The invention relates to novel substituted triazolopyrid(az)ines of general formula (I) in which R<1>, R<2>, R<3>, A<1>, A<2>, Q and Ar have the meanings given in the description, the use as selective herbicide and a method for production thereof.

Description

The invention relates to new substituted triazolopyrid (az) ine, process for their Production and their use as plant treatment agents, in particular as Herbicides and insecticides, acaricides and nematicides.

It is known that certain substituted triazolopyridines and triazolopyridazines have herbicidal properties (cf. EP-A-430385, EP-A-441718, EP-A-483027). However, the effectiveness of these known compounds is not in all Satisfactory.

The new substituted triazolopyrid (az) ine of the general formula (I)

in which
A ^{1 stands} for N or the grouping CR ⁴ ,
A ² for a single bond, for O (oxygen), S (sulfur), SO, SO ₂ , NH, for alkanediyl (alkylene) having 1 to 6 carbon atoms, which may be an oxygen atom at the beginning or end or within the hydrocarbon chain Contains sulfur atom, an NH group or a hydroxy substituent, for alkenediyl (alkenylene) or alkynediyl (alkynylene) each having 2 to 6 carbon atoms, for phenylene or for the grouping -CHR-ON = CH- [Ar] -, where R represents hydrogen or C ₁ -C ₄ alkyl,
Ar represents phenyl or pyridyl, each of which is optionally by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, by in each case optionally by cyano, carboxy, carbamoyl, halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ - Alkoximino, C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkyl sulfinyl or C ₁ -C ₄ -alkylsulfonyl substituted and in each case optionally alkyl which is interrupted up to three times by oxygen atoms, alkoxy, C ₁ -C ₄ alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each having 1 to 12 carbon atoms in the alkyl groups, optionally by halogen, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ - Haloalkyl substituted alkylenedioxy with 1 to 3 carbon atoms, or by cycloalkyl, cycloalkyloxy, cycloalkylalkyl or cycloalkylalkoxy, each with 3 to _4, optionally substituted by cyano, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl 6 carbon omen in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, or by in each case optionally by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted,
Q represents a single bond or O (oxygen), S (sulfur) or NH,
R ¹ , R ² , R ³ and R ^{4 are the} same or different and independently of one another are hydrogen, hydroxy, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or for each optionally by cyano, carboxy, carbamoyl , Thiocarbamoyl, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyimino, C ₁ -C ₄ alkoxycarbonyl or di (C ₁ -C ₄ alkyl) amino substituted and in each case alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkyl sulfinyl, alkylsulfonyl, alkylamino, alkylaminocarbonyl, dialkylamino, di alkylaminocarbonyl or dialkylaminosulfonyl, each with 1 to 12 carbon atoms in the alkyl groups, optionally having up to three times interrupted by oxygen atoms,
with the proviso
that Ar = pyridyl has at least one substituent from the halogen series, in each case optionally substituted by halogen and in each case optionally alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylamino each having 1 to 12 carbon atoms, each optionally substituted by nitro, optionally interrupted by oxygen atoms, Cyano, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or Contains pyridylmethoxy,
or that at Ar = pyridyl at least one of the substituents or at tri azolopyride (az) in at least one of the radicals R ¹ , R ² , R ³ , R ⁴ for alkoxy, alkylthio which is in each case substituted by halogen and in each case optionally up to three times interrupted by oxygen atoms , Alkylsulfinyl or alkyl sulfonyl having 1 to 12 carbon atoms or containing such a substituent,
or that at Ar = phenyl or pyridyl at least one of the substituents is cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms each substituted by cyano, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl,
or that at Ar = phenyl at least one of the substituents for each by nitro, cyano, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ Haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy,
or that at Ar = phenyl in the sum of the substituents on Ar and on the tri azolopyride (az) in (R ¹ , R ² , R ³ , R ⁴ ) at least one stands for alkyl substituted by halogen with 1 to 12 carbon atoms and at least another for halogen substituted alkyl with 1 to 12 carbon atoms or for each nitro, cyano, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ - haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy,
or that two adjacent radicals on Ar together represent alkylenedioxy with 1 to 3 carbon atoms optionally substituted by halogen and / or C ₁ -C ₄ alkyl,
found.

In the definitions are the hydrocarbon chains, such as alkyl, alkenyl or Alkynyl - also in combination with heteroatoms, such as in alkoxy, alkylthio or Alkylamino - straight or branched.

Preferred substituents or preferred ranges of those in above and below Formulations listed residues and groupings are shown below Are defined.

A ¹ preferably represents N or the grouping CR ⁴ .

A ² preferably stands for a single bond, for oxygen, sulfur, SO, SO ₂ , NH, for alkanediyl (alkylene) having 1 to 5 carbon atoms, which optionally has an oxygen atom, a sulfur atom, an NH at the beginning or end or within the hydrocarbon chain Contains a group or a hydroxy substituent, for alkenediyl (alkenylene) or alkindiyl (alkynylene) each having 2 to 5 carbon atoms, for phenylene or for the grouping -CHR-ON = CH- [Ar] -, where R is hydrogen or C ₁ -C ₄ alkyl,
Ar preferably represents phenyl or pyridyl, each of which is optionally by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, by in each case optionally by cyano, carboxy, carbamoyl, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Alkoximino, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkyl sulfinyl or C ₁ -C ₄ alkylsulfonyl substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each with 1 to 6 carbon atoms in the alkyl groups, by alkylene dioxy with 1 or 2 carbon atoms optionally substituted by halogen, C ₁ -C ₃ alkyl and / or C ₁ -C ₃ haloalkyl, or by in each case optionally by cyano, carbamoyl, Thiocarbamoyl, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl-substituted cycloalkyl, cycloalkyloxy, cycloalkylalkyl or cycloalkylalkoxy, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 3 carbon atoms in the alkyl part, or by jewe ils optionally substituted by nitro, cyano, carboxy, carbamoyl, thio carbamoyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy, Phenoxy, phenylthio, phenyl methoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted.

Q preferably represents a single bond or O (oxygen), S (sulfur) or NH.

R ¹ , R ² , R ³ and R ⁴ are the same or different and are preferably independently of one another hydrogen, hydroxyl, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or, if appropriate, by cyano, Halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyimino, C ₁ -C ₄ alkoxycarbonyl or di (C ₁ -C ₄ alkyl) amino substituted alkyl, alkoxy, alkoxycarbonyl, Alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkyl aminocarbonyl, dialkylamino, dialkylaminocarbonyl or dialkylamino sulfonyl each having 1 to 5 carbon atoms in the alkyl groups.

A ¹ particularly preferably represents N or the grouping CR ⁴ .

A ² particularly preferably stands for a single bond, for oxygen, sulfur, SO, SO ₂ , NH, for methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl, (dimethylene), propane 1,1-diyl (propylidene), propane-1,2-diyl, propane-2,2-diyl, propane-1,3-diyl (trimethylene), butane-1,1-diyl, butane-1,2- diyl, butane-1,3-diyl, butane-1,4-diyl, 1-oxa-ethane-1,2-diyl, 1-thia-ethane-1,2-diyl, 1-aza ethane-1,2 -diyl, 1-oxa-propane-1,2-diyl, 1-oxa-propane-1,3-diyl, 1-thia propane-1,2-diyl, 1-aza-propane-1,2-diyl, 1-thia-propane-1,3-diyl, 1-aza-propane-1,3-diyl, 2-oxa-propane-1,3-diyl, 2-thia-propane-1,3-diyl, 2-aza propane-1,3-diyl, for ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3 -diyl, 1-butene-1,4-diyl, 2-butene-1,4-diyl, ethine-1,2-diyl, propyne-1,3-diyl, 1-butyne-1,3-diyl, 1 -Butin-1,4-diyl, 2-butyne-1,4-diyl, for 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or for the grouping -CHR-ON = CH- [Ar ] -, where R is hydrogen, methyl or ethyl,
Ar particularly preferably represents phenyl or pyridyl, which in each case optionally by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, by in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n - or i-propoxy, n-, i-, s- or t-butoxy, methoximino, ethoxyimino, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-Propylsulfinyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i- Propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethyl amino, n- or i-propylamino, n-, i-, s- or t-butylamino, if necessary by fluorine and / or chlorine, methyl or Trifluoromethyl substituted M ethylenedioxy or ethylenedioxy, or by cyclopropyl which is optionally substituted by cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or trifluoromethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyl oxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutyl methoxy, cyclopentylmethoxy or cyclohexylmethoxy, or by in each case optionally substituted by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine , Bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, di fluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i- Propoxy, n-, i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy or chlorodifluoromethoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted.

Q particularly preferably represents a single bond or O (oxygen), S (Sulfur) or NH.

R ¹ , R ² , R ³ and R ⁴ are the same or different and are particularly preferably, independently of one another, hydrogen, hydroxy, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine or methyl, ethyl, n- or i, each optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoximino, ethoximino, dimethylamino or diethylamino Propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl , Methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino , n- or i-Propylamino, n-, i-, s- or t-butylamino, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylamino, diethylamino, dimethylamino carbonyl, diethylam inocarbonyl, dimethylaminosulfonyl or diethylamino sulfonyl.

A ¹ very particularly preferably represents N or the grouping CR ⁴ .

A ² very particularly preferably represents a single bond, oxygen, sulfur, SO, SO ₂ , NH, methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl, (dimethylene), propane 1,1-diyl (propylidene), propane-1,2-diyl, propane-2,2-diyl, propane-1,3-diyl (trimethylene), 1-oxa-ethane-1,2-diyl, 1- Thia-ethane-1,2-diyl, 1-azaethane-1,2-diyl, 1-oxa-propane-1,2-diyl, 1-oxa-propane-1,3-diyl, 1-thia-propane 1,2-diyl, 1-aza-propane-1,2-diyl, 1-thia-propane-1,3-diyl, 1-aza-propane-1,3-diyl, 2-oxa-propane-1, 3-diyl, 2-thia-propane-1,3-diyl, 2-aza-propane-1,3-diyl, for ethene-1,2-diyl, propene-1,2-diyl, propene-1,3 -diyl, ethyne-1,2-diyl, propyne-1,3-diyl, or for the grouping -CHR-ON = CH- [Ar] -, where R is hydrogen, methyl or ethyl,
Ar very particularly preferably represents phenyl or pyridyl, which in each case optionally by nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, by in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methoximino, ethoxyimino, methyl thio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted 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, n- or i-propylsulfinyl, Methylsulfonyl, ethyl sulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, by methylenedioxy or ethylenedioxy optionally substituted by fluorine and / or chlorine, or by in each case optionally by cyano, fluorine, chlorine, bromine, methyl , Ethyl, n- or i-propyl, or trifluoro methyl substituted Cyc lopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy or cyclo, hexyl, methoxy, cyclo, hexyl, methoxy, cyclo, hexyl, methoxy, cyclo, hexyl, methoxy, cyclo, hexyl, methoxy, cyclo, by cyclohexyl, methoxy, cyclo, hexyl, methoxy, cyclo, optionally by cyclohexyl, methoxy, cyclo, hexyl, methoxy, cyclo, by cyclohexyl, methoxy, cyclo, by cyclohexyl, methoxy, cyclo, by cyclohexyl, methoxy, cyclo, optionally by cyclo, methoxy, cyclo, by cyclo, methoxy, cyclo, Chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, methoxy, ethoxy, n- or i-propoxy, Di fluoromethoxy, trifluoromethoxy or chlorodifluoromethoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted.

Q very particularly preferably represents a single bond or O (Oxygen), S (sulfur) or NH.

R ¹ , R ² , R ³ and R ⁴ are the same or different and very particularly preferably stand independently of one another for hydrogen, hydroxy, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or each methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoximino, ethoximino, dimethylamino or diethylamino , Methoxycarbonyl, ethoxycarbonyl, n- or i-propoxy carbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethyl sulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino , n- or i-Propylamino, methyl aminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylamino, diethylamino, dimethylaminocarbonyl or dimethylamino sulfonyl.

Those compounds of the formula (I) are preferred according to the invention which is a combination of the meanings listed above as preferred is present.  

According to the invention, particular preference is given to those compounds of the formula (I) in which a combination of those listed as particularly preferred above Meanings exist.

According to the invention, those compounds of the Formula (I), in which a combination of the above is particularly preferred added listed meanings is present.

The following two groups of compounds of the formula (I) with the abovementioned radical definitions for A ¹ , A ² , Q, R ¹ , R ² , R ³ , R ⁴ are particularly emphasized:
Compounds of the formula (I) in which Ar is pyridyl which is substituted by one or more of the following radicals from the series fluorine, chlorine, bromine, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, optionally halogen substituted C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylamino, C ₄ -C ₇ optionally substituted by trifluoromethyl -Cycloalkyloxy, phenylthio and optionally substituted by cyano-substituted phenyloxy.

Compounds of formula (I) in which Ar is phenyl, which is substituted is that two adjacent substituents together for optionally by fluorine or chlorine and / or methyl, ethyl, n- or i-propyl substituted alkylenedioxy 1 to 2 carbon atoms, or preferably for difluoromethylene dioxy or Tetrafluoroethylene dioxy.

The radicals listed above or listed in preferred areas definitions apply both to the end products of the formula (I) and correspondingly for the starting or intermediate products required for the production. This Residual definitions can be between themselves, that is, between the specified ones areas can be combined as required.  

The new substituted triazolopyride (az) have the general formula (I) interesting biological properties. They are particularly characterized by strong effectiveness against weeds and against animal pests.

The new substituted triazolopyride (az) ine of the general formula (I) is obtained if
(a) hydrazinopyride (az) ine of the general formula (II)

in which
A ¹ , R ¹ , R ² and R ^{3 have} the meaning given above,
with halocarbonyl compounds of the general formula (III)

in which
Ar, A ² and Q have the meaning given above and
X ^{1 represents} halogen,
optionally in the presence of one or more reaction auxiliaries and, if appropriate, in the presence of one or more diluents
and the hydrazides of the general formula (IV) formed here

in which
A ¹ , A ² , Ar, Q, R ¹ , R ² and R ^{3 have} the meaning given above,
- if necessary without intermediate insulation -
with one or more dehydrating agents (dehydrating substances), if appropriate in the presence of one or more diluents,
or if you
(b) hydrazinopyride (az) ine of the general formula (II)

in which
A ¹ , R ¹ , R ² and R ^{3 have} the meaning given above,
with carboxy compounds of the general formula (V)

in which
Ar, A ² and Q have the meaning given above,
if appropriate in the presence of one or more diluents,
or if you
(c) halopyride (az) ine of the general formula (VI)

in which
A ¹ , R ¹ , R ² and R ^{3 have} the meaning given above and
X ^{2 represents} halogen
with arenes of the general formula (VII)

in which
Ar, A ² and Q have the meaning given above and
M represents hydrogen or a metal equivalent
if appropriate in the presence of one or more reaction auxiliaries and, if appropriate, in the presence of one or more diluents,
or if you
(d) pyrid (az) ine of the general formula (VIII)

in which
A ¹ , A ² , R ¹ , R ² and R ^{3 have} the meaning given above and
X ^{3 represents} halogen
with arenes of the general formula (IX)

in which
Ar and Q have the meaning given above and
M represents hydrogen or a metal equivalent
optionally in the presence of one or more reaction auxiliaries and, if appropriate, in the presence of one or more diluents.

The substi obtainable by the processes according to the invention specified above Tuiert triazolopyrid (az) ine of the general formula (I) can also according to usual  Methods in other compounds of the general formula (I) within the sub definition of a substituent.

Thus, for example, with compounds of the formula (I) in which at least one of the groups R ¹ , R ² , R ³ or one of the substituents on Ar is halogen (in particular fluorine or chlorine) in the usual way by reaction with nucleophilic compounds , such as fetching with optionally substituted alcohols, mercaptans, amines, phenols, optionally in the presence of customary acid acceptors, nucleophilic substitution reactions are carried out (cf. the preparation examples).

Furthermore, for example, compounds of the general formula (I) which Contain alkylthio substituents or arylthio substituents in the usual way Oxidation reactions, for example with hydrogen peroxide, to the corresponding Alkylsulfinyl, alkylsulfonyl, arylsulfinyl or arylsulfonyl derivatives carried out be (see the manufacturing examples).

If, for example, 3-chloro-2-hydrazino-5-trifluoromethyl-pyridine and 2-methylthio-pyridine-3-carboxylic acid chloride are used as starting materials, the reaction sequence in process (a) according to the invention can be outlined using the following formula:

If, for example, 3-chloro-2-hydrazino-5-trifluoromethyl-pyridine and 4-trifluoromethyl-mandelic acid are used as starting materials, the course of the reaction in process (b) according to the invention can be outlined using the following formula:

If, for example, 3-chloro-1,2,4-triazolo [4,3-a] pyridine and 2- (4-trifluoromethoxyphenyl) ethanol are used as starting materials, the course of the reaction in process (c) according to the invention can be carried out by the following formula scheme is outlined:

If, for example, 3-bromomethyl-6-trifluoromethyl-1,2,4-triazolo- [4,3-a] pyridine and 4- (5-chloro-pyridin-2-yl-oxy) phenol are used as starting materials, then the course of the reaction in process (d) according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the hydrazino pyrid (az) ines to be used as starting materials in processes (a) and (b) for the preparation of compounds of the general formula (I). In the general formula (II) A ¹ , R ¹ , R ² and R ³ preferably or in particular have those meanings which are preferred or as particularly in connection with the description of the compounds of the general formula (I) according to the invention particularly preferred for A ¹ , R ¹ , R ² and R ^{3 have been} given.

The starting materials of the general formula (II) are known and / or can be according to processes known per se (cf. Heterocycles 22 (1984), 117-124; J. Chem. Soc., Perkin Trans. I 12 (1972), 1483-1488; J. Heterocycl. Chem. 6 (1969) 223-228; J. Med. Chem. 40 (1997), J. Org. Chem. 35 (1970), 808-811; 4420-4425; Tetrahedron 24 (1968), 2687-2696; DE-A-34 43 308; EP-A-22578; EP-A-70376; EP-A-705 831; EP-A-759 429; GB-A-1161492; US-A-3799935; US-A-4127575; US-A-4260767; US-A-4578464; US-A-5167691; US-A-5321002; US-A-5371086; WO-A-97/10243; Preparation Examples).

Formula (III) provides a general definition of the halogen carbonyl compounds to be used as starting materials in process (a) according to the invention for the preparation of compounds of the general formula (I). In the general formula (III), Ar, A ² and Q preferably or in particular have those meanings which, in connection with the description of the compounds of the general formula (I) according to the invention, are preferred or as particularly preferred for Ar, A ² and Q have been given; X ¹ preferably represents fluorine, chlorine or bromine, especially chlorine.

The starting materials of the general formula (III) are known and / or can be according to known processes can be produced (cf. DE-A-19 27 919, DE-A-19 59 703, DE-A-21 17 650, DE-A-23 25 089, DE-A-31 29 274, DE-A-36 42 256, EP-A-198797, EP-A-293747, EP-A-333658, EP-A-636622, US-A-4832879, US-A-5047584, US-A-5346881, WO-A-94/21640, WO-A-95/25099, WO-A-95/25105, Preparation Examples).

Formula (V) provides a general definition of the carboxyver compounds to be used as starting materials in process (b) according to the invention for the preparation of compounds of the general formula (I). In the general formula (V), Ar, A ² and Q preferably or in particular have those meanings which, in connection with the description of the compounds of the general formula (I) according to the invention, are preferred or particularly preferred for Ar, A ² and Q have been given.

The starting materials of the general formula (V) are known and / or can be according to known processes can be prepared (cf. DE-A-28 19 788, DE-A-38 36 175, EP-A-636622, US-A-4895871, US-A-5346881, WO-A-93/22287, J. Chem. Soc., Perkin Trans. I, 1995, 1265-1271, production examples).

Formula (VI) provides a general definition of the halopyride (az) ines to be used as starting materials in process (c) according to the invention for the preparation of compounds of the general formula (I). In the general formula (VI), A ¹ , R ¹ , R ² and R ³ preferably or in particular have those meanings which are preferred or particularly preferred in connection with the description of the compounds of the general formula (I) according to the invention for A ¹ , R ¹ , R ² and R ^{3 have been} given; X ² preferably represents fluorine, chlorine or bromine, especially chlorine.

The starting materials of the general formula (VI) are known and / or can be according to known processes can be prepared (cf. J. Heterocycl. Chem. 8 (1971), 415-419; loc. cit. 15: 439-444 (1978); J. Org. Chem. 31 (1966), 3522-3527; loc. cit. 35: 708-811 (1970); Monatsh. Chem. 103 (1972), 1624-1631; EP-A-71434).

Formula (VII) provides a general definition of the arenes to be used further as starting materials in process (c) according to the invention for the preparation of compounds of the general formula (I). In the general formula (VII), Ar, A ² and Q preferably or in particular have those meanings which are preferred or as particularly preferred for Ar, A ² already in connection with the description of the compounds of the general formula (I) according to the invention and Q have been given; M preferably represents hydrogen, lithium, sodium or potassium, in particular hydrogen, sodium or potassium.

The starting materials of the general formula (VII) are known organic Chemicals for synthesis.

Formula (VIII) provides a general definition of the pyrid (az) ines to be used as starting materials in process (d) according to the invention for the preparation of compounds of the general formula (I). In the general formula (VIII), A ¹ , A ² , R ¹ , R ² and R ³ preferably or in particular have those meanings which, in connection with the description of the compounds of the general formula (I) according to the invention, preferably or as particularly preferred for A ¹ , A ² , R ¹ , R ² and R ³ ; X ³ preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine or bromine.

The starting materials of the general formula (VIII) are known and / or can can be prepared by processes known per se (cf. J. Heterocycl. Chem. 15 (1978), 439-444; DE-A-43 26 758; EP-A-210648).

The process (d) according to the invention for the preparation of compounds of General formula (I) arenes to be used as starting materials are by the formula (IX) is generally defined. In the general formula (IX), Ar and Q preferably or in particular those meanings which have already been mentioned above in Zu connection with the description of the compounds of the invention my formula (I) preferably or as particularly preferred for Ar and Q have been given; M preferably represents hydrogen, lithium, sodium or Potassium, especially for hydrogen, sodium or potassium.

The starting materials of the general formula (IX) are known organic synthesis chemicals.

The processes (a), (c) and (d) according to the invention are preferably carried out under Ver using one or more reaction aids. As reaction aids agents for processes (a), (c) and (d) according to the invention generally come the usual inorganic or organic bases or acid acceptors in Consideration. These preferably include alkali metal or alkaline earth metal acetate, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as for example sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, Lithium, sodium, potassium or calcium hydroxide, sodium or potassium methanolate, ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; Farther also basic organic nitrogen compounds, such as trimethylamine, Triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl-2,4-di  methyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2.2.2] - octane (DABCO), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), or 1,8-diazabicyclo- [5.4.0] -undec-7-en (DBU).

The method according to the invention is carried out using one or more De hydrating agent performed. It can be used for chemical withdrawal of water usual substances are used. Examples include phosphorus (V) oxide and phosphoryl chloride called.

The processes according to the invention for the preparation of the compounds of general My formula (I) are preferably made using diluents carried out. As a diluent for carrying out the ver drive (a), (b), (c) and (d) come in addition to water, especially inert organic Solvent. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as as petrol, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, Hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ether like Diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol di methyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-Di methylformamide, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrroli don or hexamethylphosphoric triamide; Esters such as methyl acetate or Ethyl acetate, sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, Ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol mono ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the Mix with water or pure water.

The reaction temperatures can be carried out when carrying out the inventive Processes (a), (b), (c) and (d) can be varied over a wide range. Generally  I think one works at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The processes (a), (b), (c) and (d) according to the invention are generally described under Normal pressure carried out. However, it is also possible to use the ver drive under increased or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible Lich to use one of the components in a larger excess. The order settlement is generally in a suitable diluent in the presence carried out a reaction auxiliary and the reaction mixture is in all agitated several hours at the required temperature. The on work is carried out according to customary methods (cf. games).

The active compounds according to the invention can be used as defoliants, desiccants, kraut tabs killers and especially used as a weed killer. Weeds in the broadest sense are understood to mean all plants that are found in places grow where they are undesirable. Whether the substances according to the invention as total or Selective herbicides act essentially depends on the amount used.

The active compounds according to the invention can, for. B. used in the following plants:
Dicotyledon weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Gupopsisia, Euphorbia , Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsesb, Senania, Senecio , Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Fistula, Eriochaimis, Antherocho, Eriocha, Antherocho , Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Monocot cultures of the genera: Allium, pineapple, asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.

However, the use of the active compounds according to the invention is by no means limited to these Limited genres, but extends in the same way to others Plants.

The active compounds according to the invention are suitable depending on the con center for total weed control, e.g. B. on industrial and track systems and on Because of and places with and without tree cover. Likewise, the fiction active agents for weed control in permanent crops, e.g. B. Forst, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, Cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture areas and for selective weed control in annual crops become.  

The compounds of formula (I) according to the invention show strong herbicidal activity solvency and a wide range of effects when used on and on the floor aerial parts of plants. To a certain extent, they are also suitable for selective use Control of monocot and dicot weeds in monocot and di cotyledon cultures, both pre-emergence and post-emergence.

The active ingredients are also suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and spiders, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. 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 z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. 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 z. B. Onychiurus armatus.
From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Pemphigodumonpp padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantü, Aspidiotus hederae, Pseudococcus spp. Psylla spp.
From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplocapsia n. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia po dana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnidana, Homona magnidanana.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Bruchidius obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.
From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Choroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The plant parasitic nematodes include z. B. Pratylenchus spp., Radopholus spp., Ditylenchus spp., Tylenchulus spp., Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Tylenchus spp., Helicotylenchus spp., Rotylenchus spp., Tylenchulus spp.

The active compounds according to the invention can be used in certain concentrations or Application rates also to control fungal or bacterial plants diseases are used. If necessary, they can also be used as intermediate or use precursors for the synthesis of other active ingredients.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including naturally occurring crops). Cultivated plants can be plants that through conventional breeding and optimization methods or through biotech biological and genetic engineering methods or combinations of these methods can be obtained, including the transgenic plants and inclusive plant varieties that can or cannot be protected by plant breeders' rights. Plant parts should include all above-ground and underground parts and organs the plants, such as sprout, leaf, flower and root are understood, with playful leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. To the plant parts also includes crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, cuttings and seeds.

The treatment according to the invention of the plants and parts of plants with the active ingredients substances takes place directly or by influencing their surroundings, living space or Storage room according to the usual treatment methods, e.g. B. by diving, spraying, Evaporation, misting, scattering, spreading and in the case of propagation material, in particular especially in the case of seeds, still by wrapping them in one or more layers.  

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient im impregnated natural and synthetic materials as well as very fine encapsulation in polymers Substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, optionally using surface-active agents, thus emulsifiers and / or dispersants and / or foam-producing Means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, 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, and water.

As solid carriers come into question: B. ammonium salts and natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silicic acid, aluminum oxide and silicates, as solid carriers for granules come into question: z. B. 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; as emulsifying and / or foam  Generating funds are possible: z. B. non-ionic and anionic emuls gators, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants come into question: z. B. lignin sulfite and Methylcellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho lipids such as cephalins and lecithins and synthetic phospholipids. Further Additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan 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 Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known herbicides and / or with substances which Improve crop tolerance ("safeners") for weed control ver can be used, whereby ready formulations or tank mixes are possible. It So mixtures with weed control agents are also possible, which a or contain several known herbicides and a safener.

Known herbicides are suitable for the mixtures, for example Acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine,  Azafenidin, Azimsulfuron, Beflubutamid, Benazolin (-ethyl), Benfuresate, Bensulf uron (-methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxime, Bromoxynil, Butachlor, Butafenacil (-allyl), Butroxydim, Butylate, Cafenstrole, Caloxydim, carbetamides, carfentrazone (-ethyl), chloromethoxyfen, chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cini don (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Clor ansulam (methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichloroprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimetha metryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop (-P ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Flufenacet, Flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, fluometuron, Fluorochloridones, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Foramsulfuron, glufosinate (-ammonium), glyphosate (-isopropylammonium), Halosafen, Haloxyfop (-ethoxyethyl, -P-methyl), Hexazinone, Imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, Imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Lin uron, MCPA, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, metha benzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, Metoxuron, Metribuzin, Metsulfuron (-methyl), Molinate, Monolinuron, Napro anilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, Oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfinorfen, paraquat,  Pelargonic acid, Pendimethalin, Pendralin, Pentoxazone, Phenmedipham, Picolinafen, Piperophos, Pretilachlor, Primisulfuron (-methyl), Profluazol, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalid, Pyriminobac (methyl), pyrithiobac (sodium), quinchlorac, quinmerac, quin oclamine, quizalofop (-Pethyl, -P-tefuryl), rimsulfuron, sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulf uron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, Thiafluamides, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Thiobencarb, Tio carbazil, tralkoxydim, triallates, triasulfuron, tribenuron (-methyl), triclopyr, tri diphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used become. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after emergence of the plants are applied. They can also be planted in the soil before sowing be working.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 1 g and 10 kg of active ingredient per hectare of soil area, preferably between 5 g and 5 kg per ha.  

The manufacture and use of the active compounds according to the invention start out the following examples.  

Preparation Examples

example 1

(Method (a))

A mixture of 2.5 g (11.8 mmol) of 2-hydrazino-3-chloro-5-trifluoromethyl-pyridine and 2.1 g (11.2 mmol) of 2-methylthio-pyridine-3-carboxylic acid chloride is used for 60 minutes heated to 140 ° C. After cooling, the mixture is stirred with diethyl ether and the crystalline product isolated by suction.

3.3 g (77% of theory) of N '- (3-chloro-S-trifluoromethyl-2-pyridyl) -2-methylthio-pyridine-3-carboxylic acid hydrazide are obtained.
¹ H NMR (DMSO): 11.0 (NH); 10.17 (NH); 8.65 (1H); 8.61-8.21 (3H); 7.24 (1H); 2.43 (3H) ppm.

35 ml of phosphoryl chloride (POCl ₃ ) are added to 3.2 g of N '- (3-chloro-5-trifluoromethyl-2-pyridyl) -2-methylthio-pyridine-3-carboxylic acid hydrazide and the mixture is stirred under reflux for 18 hours. The mixture is concentrated under reduced pressure, water is added to the residue and the mixture is made basic with ammonia. The crystalline product is isolated by suction.

1.5 g (49% of theory) of 8-chloro-3- (2-methylthio-3-pyridyl) -6-trifluoromethyl- [1,2,4] -triazolo- [4,3-a] are obtained pyridine.
¹ H NMR (CDCl ₃ ): 8.73 (1H); 8.07 (1H); 7.82 (1H); 7.54 (1H); 7.25 (1H); 2.61 (3H) ppm.

Example 2

(Method (a))

1.5 g (5.23 mmol) (2-chloro-) are slowly added dropwise to a solution of 0.8 g (5.57 mmol) of 3-chloro-2-hydrazino-pyridine in 30 ml of dichloromethane and 3 ml of triethylamine. 2,3,3-trifluoro-2,3-dihydro) -1,4-benzodioxin-6-carbonyl chloride. After the weakly exothermic reaction has subsided, the mixture is stirred for a further 24 hours at room temperature (approx. 20 ° C.). The mixture is concentrated under reduced pressure, 25 ml of phosphoryl chloride (POCl ₃ ) are added to the residue and stirring is continued for 18 hours under reflux. It is concentrated again under reduced pressure, then the residue is diluted with water and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and filtered. The solvent is carefully distilled off from the filtrate under reduced pressure.

2.1 g (61% of theory) of 8-chloro-3- (2-chloro-2,3,3-trifluoro-2,3-dihydro- 1,4-benzodioxin-6-yl) - [1,2,4] -triazolo- [4,3-a] -pyridine, melting point 192 ° C.  

Example 3

(Method (b))

A mixture of 0.8 g (3.8 mmol) of 2-hydrazino-3-chloro-5-trifluoromethyl-pyridine and 1.0 g (4.5 mmol) of 4-trifluoromethyl-mandelic acid is stirred at 160 ° C. for 3 hours. After cooling, shake with 10% sodium hydroxide solution / methylene chloride. The solvent is removed from the organic phase under reduced pressure distilled off.

0.8 g (53% of theory) (8-chloro-6-trifluoromethyl- [1,2,4] -triazolo- [4,3- a] -pyridin-3-yl- (4-trifluoromethyl-phenyl) -methanol with a melting point of 160 ° C.

Example 4

(Method (b))

A mixture of 1.2 g (9.7 mmol) of 3-methyl-6-hydrazino-pyridazine and 2.3 g (13.4 mmol) 6-chloro-3-pyridyl-acetic acid is stirred at 160 ° C. for 3 hours. To cooling is shaken with 10% sodium hydroxide solution / methylene chloride. Of the organic phase, the solvent is carefully removed under reduced pressure distilled.  

1.6 g (64% of theory) of 3- (6-chloro-3-pyridyl-methyl) -6-methyl- [1,2,4] - triazolo- [4,3-b] -pyridazine are obtained.
¹ H NMR (CDCl ₃ ): 8.51 (1H); 7.98 (1H); 7.75 (1H); 7.27 (1H); 7.00 (1H); 4.54 (2H); 2.60 (3H) ppm.

Example 5

(Method (c))

A mixture of 0.6 g (3.9 mmol) of 3-chloro [1,2,4] triazolo [4,3-a] pyridine and 0.8 g (3.9 mmol) 2- (4-trifluoromethoxy-phenyl) -ethanol is dissolved in 80 ml of toluene with 2.2 g (15.9 mmol) potassium carbonate and 0.6 g (15 mmol) sodium hydroxide and 50 mg Tris- [2- (2-methoxy-ethoxy) ethyl] amine (TDA-1) as a phase transfer catalyst Stirred at 100 ° C for 18 hours. After cooling, dilute with water, separate the organic phase, dries it over magnesium sulfate and congeals under ver reduced pressure. The remaining residue is in the Kugelrohr under ver reduced pressure (230 ° C / 0.1 mm) distilled.

0.4 g (32% of theory) of 3- [2- (4-trifluoromethoxyphenyl) ethoxy] - [1,2,4] -triazolo- [4,3-a] pyridine as an oil.  

Example 6

(Subsequent reaction)

A mixture of 0.6 g (1.9 mmol) 6-chloro-3- (2,2-difluoro-1,3-benzodioxol-5-yl) - [1,2,4] -triazolo- [4,3-b] -pyridazine and 10 g (142 mmol) of n-butylamine are dissolved in 10 ml Ethanol stirred at 100 ° C for 18 hours. After cooling, concentrate under ver reduced pressure. The remaining residue is stirred with water and that unresolved product isolated by suction.

0.65 g (97% of theory) of 6-n-butylamino-3- (2,2-difluoro-1,3-benzo) is obtained dioxol-5-yl) - [1,2,4] -triazolo- [4,3-b] -pyridazine, melting point 153 ° C.

Example 7

(Subsequent reaction)

A mixture of 0.5 g (2.2 mmol) of 3- (6-chloro-3-pyridyl) - [1,2,4] -triazolo- [4,3-a] - pyridine and 2.5 g (25 mmol) of 2,2,2-trifluoroethanol in 50 ml of toluene with 2.5 g  (18 mmol) potassium carbonate and 0.8 g (20 mmol) sodium hydroxide for 18 hours 100 ° C stirred. After cooling, dilute with water, separate the organic Phase and dries this over magnesium sulfate and filtered. The filtrate will The solvent is carefully distilled off under reduced pressure.

0.4 g (63% of theory) of 3- [6- (2,2,2-trifluoro-ethoxy) -3-pyridyl] - [1,2,4] - triazolo- [4,3-a] pyridine, melting point 156 ° C.

Example 8

(Subsequent reaction)

A mixture of 0.4 g (1.5 mmol) of 3- (2,5-dichloro-3-pyridyl) - [1,2,4] -triazolo- [4,3-a] - pyridine and 0.3 g (1.5 mmol) of 3-trifluoromethyl-phenol is dissolved in 5 ml of dimethyl sulfoxide with 2.6 g (19 mmol) of potassium carbonate and 0.2 g (5 mmol) of sodium hydroxide Stirred at 100 ° C for 18 hours. After cooling, dilute with water, separate the organic phase, dries over magnesium sulfate and filtered. from Filtrate, the solvent is carefully distilled off under reduced pressure.

0.15 g of 3- [5-chloro-2- (3-trifluoromethylphenoxy) -3-pyridyl] - [1,2,4] - is obtained triazolo- [4,3-a] pyridine, melting point 143 ° C.  

Example 9

(Subsequent reaction)

0.6 g (1.97 mmol) 6-chloro-3- (2-propylthio-3-pyridyl) - [1,2,4] triazolo- [4,3-a] pyridine are in 5 ml of acetic acid in the presence of a spatula tip with sodium tungstate 2.5 g (22 mmol) of hydrogen peroxide (30% aqueous solution) at 18 hours Room temperature (about 20 ° C) stirred. It is diluted with water and extracted with Dichloromethane. The organic phase is dried over magnesium sulfate and filtered. The solvent is carefully removed from the filtrate under reduced pressure distilled.

0.4 g (61% of theory) of 6-chloro-3- (2-propylsulfonyl-3-pyridyl) - [1,2,4] - triazolo- [4,3-a] pyridine, melting point 142 ° C.

Analogously to Examples 1 to 9 and in accordance with the general description of the production processes according to the invention, it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 1 below.

Table 1

Examples of the compounds of the formula (I)

The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.
(a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a) .
(b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b) .

The calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the Retention times through linear interpolation between two consecutive Alkanones).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm the maxima of the chromatographic signals determined.  

Starting materials of formula (II)

Example (II-1)

step 1

A solution of 27 g (16.3 mmol) of 2-ethyl-3,4-dichloropyridine, 30 ml of n-pentanol, 10 g of pyridine and 90 g of hydrazine hydrate are stirred at 140 ° C. for 18 hours. After this Cooling down is concentrated in a vacuum. The residue is diluted with water and extracted with dichloromethane. The organic phase is over magnesium sulfate dried and concentrated in vacuo.

There remain 24.5 g (93% of theory) of 2-ethyl-3-chloro-4-hydrazino-pyridine with a melting point of 79 ° C.
¹³ C NMR (DMSO): 157.9; 152.4; 146.9; 111.7; 105.0; 28.2; 12.5 ppm.

Level 2

2.6 g (15.2 mmol) of 2-ethyl-3-chloro-4-hydrazino-pyridine and 2 g are stirred (15.2 mmol) trimethylsilyl isothiocyanate in 100 ml of tert-butyl methyl ether for 24 hours at room temperature (approx. 20 ° C). The insoluble solid is removed from Ab suck isolated.

2.4 g (92% of theory) of 2-ethyl-3-chloro-6-hydrazino-pyridine of melting point 94 ° C. are obtained.
¹³ C NMR (DMSO): 155.2; 152.2; 139.1; 110.7; 104.6; 24.9; 12.1 ppm.

The compounds obtainable according to Example (II-1) - stages 1 and 2 - are still not known from the literature. The compounds 2-ethyl-3-chloro-4-hydrazino pyridine and 2-ethyl-3-chloro-6-hydrazino-pyridine are also new substances Subject of the present application.  

Starting materials of formula (III)

Example (III-1)

step 1

800 g urotropin and 800 g 2,2-difluoro-benzo [1.3] dioxole become 2 liters at 0 ° C Hydrogen fluoride (hydrogen fluoride) is added and the reaction mixture is Heated to 80 ° C for 7 hours. The hydrogen fluoride is then removed distilled, the residue poured into 3 liters of water and ex. with dichloromethane tracted. The organic extraction solution is concentrated and the residue under distilled under reduced pressure.

686 g (70% of theory) of 2,2-difluoro-benzo [1.3] dioxole-5-carboxaldehyde are obtained from the boiling point at 88 ° C (at 14 hPa) as a colorless product.

Level 2

50 g of 2,2-difluoro-benzo [1.3] dioxole-5-carboxaldehyde are dissolved in 200 ml of 2-chlorine dissolved benzotrifluoride. In this solution are under UV radiation at 120 ° C to 130 ° C introduced 50 g of chlorine. When the reaction is complete, the reaction mixture distilled under reduced pressure.  

38 g (62% of theory) of 2,2-difluoro-benzo [1.3] dioxole-5-carboxylic acid are obtained chloride (boiling temperature: 85 ° C to 88 ° C at 20 hPa).

The compound to be produced according to example (III-1) is already from the (patent) - Literature known (see US-A-4895871).

Example (III-2)

step 1

200 g urotropin and 200 g 2,2,3,4-tetrafluoro-benzo [1.4] dioxin are added at 0 ° C 500 ml of hydrogen fluoride (hydrogen fluoride) and the reaction mixture is heated to 80 ° C for 7 hours. The hydrogen fluoride is then removed distilled, the residue poured into 750 ml of water and ex. with dichloromethane tracted. The organic extraction solution is concentrated and the residue under distilled under reduced pressure.

164 g (71% of theory) of 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-6-carbox are obtained aldehyde (boiling point: 104 ° C at 14 hPa) as a colorless product.  

Level 2

50 g of 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-6-carboxaldehyde are dissolved in 200 ml of 2- Chlorobenzotrifluoride dissolved. In this solution are under UV radiation 120 ° C to 130 ° C initiated 50 g of chlorine. After the implementation is finished Distilled reaction mixture under reduced pressure.

35 g (60% of theory) of 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-6-carbon are obtained acid chloride (boiling temperature: 97 ° C to 100 ° C at 20 hPa).

The compound to be produced according to example (III-2) is already from the (patent) - Literature known (see. DE-A-195 01 365, DE-A-195 01 367).

Example (III-3)

95.2 g of thionyl chloride are added dropwise to 101 g of 2,2,3,3-tetra with ice cooling added fluoro-benzo [1.4] dioxin-5-carboxylic acid and the mixture is poured to the end the gas evolution stirred. Then excess thionyl chloride is added atmospheric pressure distilled off and the residue under reduced pressure distilled.

91.5 g (84% of theory) of 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-5-carbon are obtained acid chloride (boiling temperature: 99 ° C to 101 ° C at 18 hPa).  

The compound to be prepared according to Example (III-3) is not yet from the literature known. The compound 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-5-carboxylic acid chloride is therefore also a subject of the present application as a new substance.

Example (III-4)

step 1

A mixture of 580 g 4-bromo-4 '- (trifluoromethoxy) biphenyl, 600 ml cyclo hexane, 193 ml triethylamine, 58 g triphenylphosphine and 6 g bis (triphenylphos phino) palladium (II) chloride is 8 hours at 175 ° C and 100 bar hydrogen / carbon monoxide pressure stirred. The reaction mixture is then filtered, the filtrate was added to water and extracted with dichloromethane. The organic Extraction solution is dried over sodium sulfate and concentrated. The residue is distilled under reduced pressure.

334 g (69% of theory) of 4'-trifluoromethoxy-biphenyl-4-carboxaldehyde are obtained (Boiling point: 125 ° C at 0.3 hPa, melting point: 31 ° C).  

Level 2

In a solution of 30 g of 4'-trifluoromethoxy-biphenyl-4-carboxaldehyde in 4-chlorine Benzotrifluoride are 8 g of chlorine under UV radiation at 100 ° C to 130 ° C. directed. When the reaction has ended, the solvent is distilled off and the Washed residue with petroleum ether. The crude product is reduced under Distilled pressure.

26 g (74% of theory) of 4'-trifluoromethoxy-biphenyl-4-carboxylic acid are obtained chloride (melting point 82 ° C).

The compound to be prepared according to Example (III-4) is not yet from the literature known. The compound is 4'-trifluoromethoxy-biphenyl-4-carboxylic acid chloride as a new substance also subject of the present application.  

Starting materials of formula (V)

Example (V-1)

186 g 2,2-difluoro-benzo [1.3] dioxol-5-carboxaldehyde (see example (III-1), step 1) are at 60 ° C to 70 ° C to a solution of 78.5 g of potassium permanganate in 850 ml Water added dropwise. The reaction mixture is at this for 5 hours Stirred temperature, then cooled to room temperature and filtered. The filtrate is acidified with 2N hydrochloric acid to pH = 1, which crystallizes fallen crude product separated by suction and recrystallized from n-hexane.

157 g (74% of theory) of 2,2-difluoro-benzo [1.3] dioxole-5-carboxylic acid are obtained.

The connection to be established according to example (V-1) is already from the (patent) - Literature known (see. DE-A-28 19 788, US-A-4895871).

Example (V-2)

A mixture of 200 g of 2,2-difluoro-benzo [1.3] dioxole-5-carboxaldehyde, 234 g Acetic anhydride, 94 g sodium acetate and 1.5 g triethylamine is under for 8 hours Reflux heated (140 ° C to 145 ° C), then allowed to cool to about 80 ° C and then poured onto 111 g of ice. The organic phase settles as an oil and solidifies when left standing overnight. The supernatant water is decanted off and the residue is stirred with water. The solid product is isolated by suction.  

242 g (98% of theory) of 3- (2,2-difluoro-1,3-benzodioxol-5-yl) propene are obtained acid.

The compound to be produced according to example (V-2) is in Chem. Abstracts registered (CAS-Reg.-No. 721-13-1) without known literature for their production is. In this respect, this connection is also to be regarded as new and also an object this registration.

Example (V-3)

Level 18441 00070 552 001000280000000200012000285911833000040 0002010038019 00004 18322e 1

235 ml of N, N-dimethylformamide and 35 g of sodium methoxide are presented, and 101 g of malonic acid dimethyl ester are added dropwise at 60 ° C. To when the addition is complete, the mixture is stirred for 15 minutes. Then a Mixture of 15.3 g of copper (I) bromide and 15.0 g of copper (I) iodide entered and the Mixture is heated to reflux. Then 118 g of 5-bromo-2,2-difluoro benzo [1.3] dioxole was added dropwise and the mixture was refluxed for 20 hours heated. After adding a further 5 g of copper (I) bromide and 5 g of copper (I) iodide the solution is refluxed for a further 18 hours. Then 171 g Sodium hydroxide is added and the mixture is refluxed for 4 hours touched. After cooling, the reaction mixture is added to 430 ml of water given, the precipitate separated by suction and the filtrate on a rotation evaporator evaporated. The residue is extracted with toluene and the organic Phase separated and discarded. The aqueous phase is made with 25% sulfur  acidified and extracted with tert-butyl methyl ether. The organic Extraction solution is dried over sodium sulfate and filtered. The filtrate is concentrated under reduced pressure and the residue (100 g) um n-hexane crystallized.

38 g of a crystalline solid with a melting point of 59-64 ° C. are obtained (according to GC <99% pure). The mother liquor is concentrated and the residue (29 g) with stirred n-hexane. Yield: another 22 g of product with a melting point of 60-63 ° C. (according to GC 98.5% pure).

The overall yield is 60 g (42% of theory) of 2- (2,2-difluoro benzo [1.3] dioxol-5-yl) malonic acid dimethyl ester.

Level 2

To a solution of 51 g of 2- (2,2-difluoro-benzo [1.3] dioxol-5-yl) -malonic acid di methyl ester in 200 ml of methanol are 200 g of a 20% potassium hydroxide solution dripped. The temperature rises from 20 ° C to 56 ° C. The mixture will Stirred overnight at 60 ° C, then concentrated and the residue diluted with Hydrochloric acid acidified. The crystalline product is suctioned off isolated.

22 g (58% of theory) of (2,2-difluoro-1,3-benzodioxol-5-yl) acetic acid are obtained (Melting point 67 ° C).

The compound to be produced according to example (V-3) is not yet from the literature known. The compound (2,2-difluoro-1,3-benzodioxol-5-yl) acetic acid is therefore as new substance also subject of the present application.  

Example (V-4)

Under a nitrogen atmosphere, 45 ml of 2.5 mol / l n-butyllithium Submitted solution in n-hexane and dropwise with stirring with 13.4 g of N, N, N ', N'- Tetramethyl-ethylenediamine (TMEDA) in 40 ml of n-hexane. After 30 minutes 20.5 g of 2,2,3,3-tetrafluoro-benzo [1.4] dioxin in 50 ml of n-hexane are added dropwise. After one hour the mixture is warmed to room temperature (approx. 20 ° C) and 50 g of carbon dioxide are introduced. After another hour, the temperature drops to 0 ° C cooled and hydrolyzed with 65 ml of 10% hydrochloric acid. The organic phase will separated and the aqueous phase extracted twice with tert-butyl methyl ether. The combined organic extraction solutions are mixed with 10% hydrochloric acid and Washed water, dried over sodium sulfate and filtered. The filtrate will The solvent is carefully distilled off under reduced pressure. Then will the residue dried.

14.9 g (58% of theory) of 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-5-carbon are obtained acid.

The compound to be produced according to example (V-4) is not yet from the literature known. The compound 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-5-carboxylic acid is therefore as a new substance also subject of the present application.

Example (V-5)

Under a nitrogen atmosphere, 44 ml of 2.5 mol / l n-butyllithium Submitted solution in n-hexane and with stirring dropwise with 13 g of N, N, N ', N'- Tetramethyl-ethylenediamine (TMEDA) in 40 ml of n-hexane. After 30 minutes 20 g of 3,3-difluoro-2,2-dimethyl-benzo [1.4] dioxin in 50 ml of n-hexane are added dropwise. After one hour the mixture is warmed to room temperature (approx. 20 ° C) and 50 g of carbon dioxide are introduced. After another hour, the temperature drops to 0 ° C cooled and hydrolyzed with 65 ml of 10% hydrochloric acid. The organic phase will separated and the aqueous phase extracted twice with tert-butyl methyl ether. The combined organic extraction solutions are mixed with 10% hydrochloric acid and Washed water, dried over sodium sulfate and filtered. The filtrate will The solvent is carefully distilled off under reduced pressure. Then will the residue dried.

12 g (49% of theory) of 2,2-dimethyl-3,3-difluoro-benzo [1.4] dioxin-5- are obtained. carboxylic acid (melting point: 128 ° C).

The compound to be produced according to example (V-5) is not yet from the literature known. The compound 2,2-dimethyl-3,3-difluoro-benzo [1.4] dioxin-5-carboxylic acid is therefore also a subject of the present application as a new substance.

Example (V-6)

42.6 g of potassium tert-butoxide in 150 ml of tetrahydrofuran are added under nitrogen -70 ° C 152 ml of 2.5 mol / l n-butyllithium solution added dropwise in n-hexane. Subsequently a solution of 38.8 g of diisopropylamine in 150 ml of tetrahydrofuran is added dropwise.  

After 30 minutes, a solution of 84 g of 2,2,3,3-tetrafluoro-5-methyl Benzo [1.4] dioxin in 200 ml of tetrahydrofuran was added dropwise. To 80 g of carbon dioxide are introduced for 2 hours. The mixture becomes another Hour stirred. The mixture is then heated to 0 ° C. and 400 ml of 2 mol / l salt acid hydrolyzed. The reaction mixture is extracted with ethyl acetate and the organic phase was concentrated. The residue is dissolved in 100 ml of 10% sodium hydroxide lye dissolved. The solution is extracted with tert-butyl methyl ether and the discarded organic phase. The product is acidified by the aqueous phase precipitated with dilute hydrochloric acid.

38.8 g (37% of theory) (2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzo) are obtained dioxin-5-yl) acetic acid.

The compound to be produced according to example (V-6) is not yet from the literature known. The compound (2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-5-yl) - Acetic acid is therefore also a subject of the present application as a new substance.  

applications Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Seeds of the test plants are sown in normal soil. After 24 hours the soil is sprayed with the active ingredient preparation so that the desired one Amount of active ingredient is applied per unit area. The drug concentration in the spray liquor is chosen so that in 1000 liters of water per hectare each desired amount of active ingredient is applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0% = no effect (like untreated control)
100% = total annihilation

In this test, for example, the compounds according to the preparation example show 29, 47, 63, 70, 75, 112, 113, 117, 122, 123, 133, 143, 144, 147, 155, 161, 162, 169, 172, 174, 181, 204, 206, 217, 240, 243, 263, 279, 283, 284 and 287 at partly good tolerance to crops, such as. B. corn, rapeseed, soybeans and Wheat, effective against weeds.  

Example B Post-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Test plants with a height of 5-15 cm are sprayed with the active substance preparation have so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 1000 l water / ha the desired amounts of active ingredient are applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation

In this test, for example, the compounds according to the preparation example show 75, 82, 112, 113, 117, 122, 123, 124, 133, 144, 149, 154, 155, 161, 162, 169, 172, 174, 181, 185, 187, 200, 204, 217, 219, 220, 223, 225, 240, 242, 243, 252, 263, 283, 284 and 287, some with good tolerance to crops, such as. B. Corn and wheat, strong weed control.  

Example C Myzus Test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified the amount of emulsifier and dilute the concentrate with emulsifier Water to the desired concentration.

Seedlings of the broad bean (Vicia faba minor) by the green peach aphid (Myzus persicae) are infested in the drug preparation of the desired Concentration dipped and placed in a plastic can.

After the desired time, the kill is determined in percent. Here means 100% that all animals have been killed; 0% means that no animals are killed were.

In this test, e.g. B. the compounds of Preparation 99, 162 and 187 with an active ingredient concentration of 1000 ppm each a degree of killing from 100% after 6 days.  

Example D Nephotettix test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified given amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

Rice seedlings (Oryza sativa) are immersed in the active ingredient preparation desired concentration and treated with larvae of green rice leafhopper (Nephotettix cincticeps) occupied while the seedlings are still moist.

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

In this test, the compounds of Preparation Examples 30, 52 and 53 were shown with an active ingredient concentration of 1000 ppm, an efficiency of 100% after 6 days.  

Example E Phaedon larvae test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified given amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with horseradish leaf beetle larvae (Phaedon cochleariae) occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds of Preparation Examples 2, 127, 132, 218, 219, 225, 226, 231, 250, 276 and 279 at an active ingredient concentration of 1000 ppm each with an efficiency of 100% after 7 days.  

Example F Plutella Test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified given amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars (Plutella maculipennis) as long as 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 are killed were.

In this test, e.g. B. the compounds of Preparation Examples 2, 27, 35, 45 and 46 each with an active ingredient concentration of 1000 ppm degree of 100% after 7 days.  

Example G Spodoptera frugiperda test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified given amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the owl butterfly Spodoptera frugiperda occupied while the leaves are still moist.

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

In this test, e.g. B. the compounds of Preparation Examples 2, 35, 127, 160, 162 and 224 each with an active ingredient concentration of 1000 ppm Degree of killing of 100% after 7 days.  

Example H Tetranychus test (OP-resistant / immersion treatment)

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified the amount of emulsifier and dilute the concentrate with emulsifier Water to the desired concentrations.

Bean plants (Phaseolus vulgaris), strongly of all stages of the common Spider mite (Tetranychus urticae) are infested in an active ingredient preparation the desired concentration.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites were killed.

In this test, e.g. B. the compounds of Preparation Examples 2, 121, 127, 129, 140, 159, 185 and 188 at an active ingredient concentration of 1000 ppm Ab Degrees of killing from 95% to 100% after 7 days.  

Example I Meloidogyne Test

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Vessels are covered with sand, active ingredient solution, Meloidogyne incognita egg larvae suspension and lettuce seeds filled. The lettuce seeds germinate and the little plants develop. The galls develop at the roots.

After the desired time, the nematicidal effect is based on the formation of bile determined in%. 100% means that no galls were found; 0% means that the number of galls on the treated plants of the corresponds to untreated control.

In this test, e.g. B. the compounds of Preparation 95, 98 and 99 100% each at active substance concentrations between 20 ppm and 40 ppm Killing after 14 days.  

Example K Critical Concentration Test Test nematode: Meloidogyne incognita

Solvent: 4 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration. The active ingredient preparation is intimately mixed with the soil. The concentration of the active ingredient in the preparation is practically none Role, the only thing that matters is the amount of active substance per unit volume Soil, which is given in ppm (= mg / l). The treated soil is filled in Pots, seeds lettuce and keeps the pots at a greenhouse temperature of 25 ° C.

After three weeks, the lettuce roots are attacked by nematodes (root galls) examined and the efficiency of the active ingredient determined in%. The efficiency is 100% if the infestation is completely avoided, it is 0% if the infestation is exactly as high as in the control plants in untreated, but in the same Wise contaminated soil.

Active ingredients, application rates and results are shown in the table below out.

Claims (11)

1. Compounds of the general formula (I)
in which
A ^{1 stands} for N or the grouping CR ⁴ ,
A ² for a single bond, for O (oxygen), S (sulfur), SO, SO ₂ , NH, for alkanediyl (alkylene) having 1 to 6 carbon atoms, which optionally has an oxygen atom at the beginning or end or within the carbon hydrogen chain Contains sulfur atom, an NH group or a hydroxy substituent for alkenediyl (alkenylene) or alkynediyl (alkynylene), each with -CHR-ON = CH- [Ar] -, where R is hydrogen or C ₁ -C ₄ alkyl stands,
Ar represents phenyl or pyridyl, each of which is optionally by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, by in each case optionally by cyano, carboxy, carbamoyl, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoximino , C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl or C ₁ -C ₄ -alkylsulfonyl-substituted and in each case optionally up to three times interrupted by oxygen atoms, alkyl, alkoxy, C ₁ -C ₄ alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each having 1 to 12 carbon atoms in the alkyl groups, by optionally halogen, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ - Haloalkyl substituted alkylenedioxy with 1 to 3 carbon atoms, or by cycloalkyl, cycloalkyloxy, cycloalkylalkyl or cycloalkylalkoxy optionally substituted by cyano, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl 3 to 6 carbon atoms each Fatomen in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, or by in each case optionally by nitro, cyano, carboxy, carb amoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted,
Q represents a single bond or O (oxygen), S (sulfur) or NH,
R ¹ , R ² , R ³ and R ^{4 are the} same or different and independently of one another are hydrogen, hydroxy, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or for each optionally by cyano, carboxy, carbamoyl , Thiocarbamoyl, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy imino, C ₁ -C ₄ alkoxy carbonyl or di (C ₁ -C ₄ alkyl) amino substituted and in each case optionally alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylaminocarbonyl, dialkylamino, dialkylaminocarbonyl or di alkylaminosulfonyl each having 1 to 12 carbon atoms in the alkyl groups are mono- to triple-interrupted by oxygen atoms,
with the proviso
that Ar = pyridyl has at least one substituent from the halogen series, in each case optionally substituted by halogen and optionally optionally up to three times interrupted by oxygen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or alkylamino each having 1 to 12 carbon atoms, in each case optionally by nitro , Cyano, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridyl contains thio or pyridylmethoxy,
or that at Ar = pyridyl at least one of the substituents or at tri azolopyride (az) in at least one of the radicals R ¹ , R ² , R ³ , R ⁴ for alkoxy, alkylthio which is in each case substituted by halogen and in each case optionally up to three times interrupted by oxygen atoms , Alkylsulfinyl or alkylsulfonyl having 1 to 12 carbon atoms or containing such a substituent,
or that at Ar = phenyl or pyridyl at least one of the substituents is cycloalkyl or cycloalkyloxy, each having 3 to 6 carbon atoms, each substituted by cyano, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -haloalkyl .
or that at Ar = phenyl at least one of the substituents for each by nitro, cyano, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ Halogenoalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy,
or that at Ar = phenyl in the sum of the substituents on Ar and on the tri azolopyride (az) in (R ¹ , R ² , R ³ , R ⁴ ) at least one is halogen-substituted alkyl having 1 to 12 carbon atoms and at least one further for alkyl substituted by halogen with 1 to 12 carbon atoms or for each by nitro, cyano, carb amoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy,
or that two adjacent radicals on Ar together represent alkylenedioxy with 1 to 3 carbon atoms optionally substituted by halogen and / or C ₁ -C ₄ alkyl. 2. Compounds according to claim 1, characterized in that
A ^{1 stands} for N or the grouping CR ⁴ ,
A ² for a single bond, for oxygen, sulfur, SO, SO ₂ , NH, for alkanediyl (alkylene) having 1 to 5 carbon atoms, which optionally an oxygen atom, a sulfur atom, an NH-- at the beginning or end or within the hydrocarbon chain Grouping or a hydroxy substituent, represents alkenediyl (alkenylene) or alkynediyl (alkynylene) each having 2 to 5 carbon atoms, for phenylene or for the grouping -CHR-ON = CH- [Ar] -, where R is hydrogen or C ₁ -C ₄ alkyl,
Ar represents phenyl or pyridyl, each of which is optionally by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, by in each case optionally by cyano, carboxy, carbamoyl, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoximino , C ₁ -C ₄ alkoxy carbonyl, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkyl amino or dialkylamino each having 1 to 6 carbon atoms in the alkyl groups, by alkylenedioxy with 1 or 2 carbon atoms optionally substituted by halogen, C ₁ -C ₃ alkyl and / or C ₁ -C ₃ haloalkyl, or by in each case optionally by cyano, carbamoyl, thiocarbamoyl , Halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl-substituted cycloalkyl, cycloalkyloxy, cycloalkyl alkyl or cycloalkylalkoxy, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 3 carbon atoms in the alkyl part, or by respectively given phenyl, phenoxy substituted by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy, Phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted,
Q represents a single bond or O (oxygen), S (sulfur) or NH, and
R ¹ , R ² , R ³ and R ^{4 are} identical or different and independently of one another are hydrogen, hydroxy, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or for each optionally by cyano, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyimino, C ₁ -C ₄ alkoxycarbonyl or di (C ₁ -C ₄ alkyl) amino substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl , Alkylsulfonyl, alkylamino, alkylaminocarbonyl, dialkylamino, dialkylamino carbonyl or dialkylaminosulfonyl each having 1 to 5 carbon atoms in the alkyl groups. 3. Compounds according to claim 1, characterized in that
A ^{1 stands} for N or the grouping CR ⁴ ,
A ² for a single bond, for oxygen, sulfur, SO, SO ₂ , NH, for methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl, (dimethylene), propane-1,1- diyl (propylidene), propane-1,2-diyl, propane-2,2-diyl, propane-1,3-diyl (trimethylene), butane-1,1-diyl, butane-1,2-diyl, butane 1,3-diyl, butane-1,4-diyl, 1-oxa-ethane-1,2-diyl, 1-thia-ethane-1,2-diyl, 1-aza-ethane-1,2-diyl, 1-oxa-propane-1,2-diyl, 1-oxa-propane-1,3-diyl, 1-thia-propane-1,2-diyl, 1-aza-propane-1,2-diyl, 1- Thia-propane-1,3-diyl, 1-aza-propane-1,3-diyl, 2-oxa-propane-1,3-diyl, 2-thia-propane-1,3-diyl, 2-aza- propane-1,3-diyl, for ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3 -diyl, 1-butene-1,4-diyl, 2-butene-1,4-diyl, ethyne-1,2-diyl, propyne-1,3-diyl, 1-butyne-1,3-diyl, 1 - Butyne-1,4-diyl, 2-butyne-1,4-diyl, for 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or for the grouping -CHR-ON = CH- [Ar ] - where R is hydrogen, methyl or ethyl,
Ar represents phenyl or pyridyl, each of which is optionally substituted by nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, each optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i- Propoxy, n-, i-, s- or t-butoxy, methoximino, ethoxyimino, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i- Propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, Methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethyl amino, n- or i-propylamino, n-, i-, s- or t-butylamino, by ge optionally by fluorine and / or chlorine, methyl or trifluoromethyl substituted methylenedioxy or Ethylene dioxy, or by cyclopropyl, cyclobutyl, cyclo, each substituted by cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or trifluoromethyl pentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentyl methyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutyl methoxy, cyclopentylmethoxy or cyclohexylmethoxy, or by in each case, if appropriate, by nitro, carbamoyl, carbamoyl, carbamoyl, carbamoyl, carbamoyl, carbamoyl, carbamoyl, carbamoyl, carbamoyl, carboxy, bromoyl, carbamoyl, carboxy, bromoyl, carbamoyl, carboxy, bromoyl, carboxy, bromoyl, carbamoyl, carboxy, bromoyl, carboxy, bromoyl, carbamoyl, carboxy, bromobloyl, carboxy, bromobloyl, carbamoyl, carbamoyl, carboxy, bromobloyl, carbamoyl, carboxy, bromobloyl , Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, n- , i-, s- or t-butoxy, difluoromethoxy, trifluoromethoxy or chlorodifluoromethoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy are substituted,
Q represents a single bond or O (oxygen), S (sulfur) or NH, and
R ¹ , R ² , R ³ and R ^{4 are the} same or different and are preferably independently of one another for hydrogen, hydroxyl, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or for each optionally by Cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoximino, ethoximino, dimethylamino or diethylamino substituted methyl, ethyl, n- or i-propyl, n -, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxy carbonyl, n- or i-propoxycarbonyl, methylthio, Ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n - or i-Propylamino, n-, i-, s- or t-butylamino, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylamino, diethylamino, dimethylaminocarbonyl, diethylaminocarbonyl, dime are thylaminosulfonyl or diethylaminosulfonyl. 4. Compounds according to claim 1, characterized in that
A ^{1 stands} for N or the grouping CR ⁴ ,
A ² for a single bond, for oxygen, sulfur, SO, SO ₂ , NH, for methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl, (dimethylene), propane-1,1- diyl (propylidene), propane-1,2-diyl, propane-2,2-diyl, propane-1,3-diyl (trimethylene), 1-oxa-ethane-1,2-diyl, 1-thia-ethane 1,2-diyl, 1-aza-ethane-1,2-diyl, 1-oxa-propane-1,2-diyl, 1-oxa-propane-1,3-diyl, 1-thia-propane-1, 2-diyl, 1-aza-propane-1,2-diyl, 1-thia-propane-1,3-diyl, 1-aza-propane-1,3-diyl, 2-oxa-propane-1,3-diyl , 2-thia-propane-1,3-diyl, 2-aza-propane-1,3-diyl, for ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, Ethyne-1,2-diyl, propyne-1,3-diyl, or for the grouping -CHR-ON = CH- [Ar] -, where R is hydrogen, methyl or ethyl,
Ar represents phenyl or pyridyl, each of which is optionally through nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, through each optionally through cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, Methoximino, ethoxyimino, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethyl sulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted 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, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n - or i-Propyl sulfonyl, methylamino, ethylamino, n- or i-propylamino, by ge optionally substituted by fluorine and / or chlorine substituted methylenedioxy or ethylenedioxy, or by in each case optionally by cyano, fluorine, chlorine, bromine, methyl, ethyl, n - or i-propyl, or trifluoro methyl substituted cyclopropyl, cyclobutyl, cyclop entyl, cyclo hexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyl oxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclo pentylmethoxy or cyclohexylmethoxy, or by in each case, where appropriate, by nitro, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine , Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, chlorofluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy or chlorodifluoromethoxy substituted phenyl, phenoxy, phenylthio, phenylmethoxy, pyridyloxy, pyridylthio or pyridylmethoxy,
Q represents a single bond or O (oxygen), S (sulfur) or NH, and
R ¹ , R ² , R ³ and R ^{4 are the} same or different and independently of one another for hydrogen, hydroxy, amino, hydrazino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or for each if appropriate Cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoximino, ethoximino, dimethylamino or diethylamino substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, Ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethyl amino, n- or i-propylamino, methylaminocarbonyl, ethylamino carbonyl, n- or i-propylaminocarbonyl, dimethylamino, diethyl amino, dimethylaminocarbonyl or dimethylaminosulfonyl. 5. A method for producing connections according to claim 1, characterized in that
(a) hydrazinopyride (az) ine of the general formula (II)
in which
A ¹ , R ¹ , R ² and R ^{3 have} the meaning given in claim 1,
with halocarbonyl compounds of the general formula (III)
in which
Ar, A ² and Q have the meaning given in claim 1 and
X ^{1 represents} halogen,
optionally in the presence of one or more reaction auxiliaries and optionally in the presence of one or more diluents
and the hydrazides of the general formula (IV) formed here
in which
A ¹ , A ² , Ar, Q, R ¹ , R ² and R ^{3 have} the meaning given above,
- if necessary without intermediate insulation -
are reacted with one or more dehydrating agents (dehydrating substances), if appropriate in the presence of one or more diluents,
or that
(b) hydrazinopyride (az) ine of the general formula (II)
in which
A ¹ , R ¹ , R ² and R ^{3 have} the meaning given above,
with carboxy compounds of the general formula (V)
in which
Ar, A ² and Q have the meaning given above,
optionally reacted in the presence of one or more diluents,
or that
(c) halopyride (az) ine of the general formula (VI)
in which
A ¹ , R ¹ , R ² and R ^{3 have} the meaning given above and
X ^{2 represents} halogen
with arenes of the general formula (VII)
in which
Ar, A ² and Q have the meaning given above and
M represents hydrogen or a metal equivalent,
optionally in the presence of one or more reaction auxiliaries and optionally in the presence of one or more diluents,
or that
(d) pyrid (az) ine of the general formula (VIII)
in which
A ¹ , A ² , R ¹ , R ² and R ^{3 have} the meaning given above and
X ^{3 represents} halogen
with arenes of the general formula (IX)
in which
Ar and Q have the meaning given above and
M represents hydrogen or a metal equivalent,
optionally in the presence of one or more reaction auxiliaries and optionally in the presence of one or more diluents. 6. A method for controlling unwanted vegetation, thereby characterized in that at least one connection according to one of the Claims 1 to 4 on undesirable plants and / or their habitat can act. 7. Use of at least one compound according to one of the claims 1 to 4 for controlling unwanted plants. 8. Herbicidal agent, characterized by a content of a compound according to one of claims 1 to 4 and conventional extenders and / or surfactants. 9. The compounds 2-ethyl-3-chloro-4-hydrazino-pyridine and 2-ethyl-3-chloro 6-hydrazino-pyridine. 10. The compounds 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-5-carboxylic acid chloride, 2,2,3,3-tetrafluoro-benzo [1.4] dioxin-5-carboxylic acid, 2,2-dimethyl-3,3-difluoro benzo [1.4] dioxin-5-carboxylic acid, (2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzo dioxin-5-yl) acetic acid and (2,2-difluoro-1,3-benzodioxol-5-yl) acetic acid. 11. The compound 4'-trifluoromethoxy-biphenyl-4-carboxylic acid chloride.