DE19608244A1 - Pyridyl thiazoles - Google Patents

Abstract

New pyridyl-thiazoles have the formula (I), in which R stands for alkyl or for the groups (a) or (b), in which R<1> stands for hydrogen or -CO-R<5>, R<2> stands for hydrogen or -CO-R<6>, R<3> stands for hydrogen or alkyl, R<4> stands for alkoxy or dialkylamino, R<5> and R<6> represent independently from each other alkyl, alkoxycarbonyl, alkylamino, optionally substituted aryl, optionally substituted arylamino or optionally substituted arylsulfonylamino, or R<1> and R<2> form together with the nitrogen atom to which they are bound a cyclic imide having the formula (c), in which A stands for optionally substituted alkandiyl or optionally substituted alkendiyl; X<1> stands for hydrogen or halogen and X<2> for halogen. Also disclosed are the salts and acid addition products of these new substances, a process for preparing them and their use for protecting plants against infections by undesirable micro-organisms, as well as new intermediate products having the formulas (IIa), (X) and (XI), in which X<2>, X<5>, X<6>, R<9> and R<10> have the meanings given in the description. The compounds having the formula (XI), as well as their salts and acid addition products, are suitable for protecting plants against infections by undesirable micro-organisms.

Description

The present invention relates to new pyridyl thiazoles, several methods their manufacture and their use to protect plants against attack through unwanted microorganisms.

It has already been known that certain halopyridine-4- carboxylic acid derivatives for generating resistance in plants to attack by let phytopathogenic microorganisms be used (cf. EP-OS 0 268 775 and DE-OS 41 38 026). So z. B. 2,6-dichloropyridine-4-carboxylic acid, 2,6-dichloro methyl pyridine-4-carboxylate and α-2,6-dichloropyridine-4-carboxylate (4-chlorophenyl) benzyl esters can be used for the stated purpose. The However, these substances are not effective, especially at low application rates always satisfactory. In addition, the direct fungicidal activity of this leaves Connections to be desired.

There have now been new pyridyl thiazoles of the formula

in which
R for alkyl,

stands, where
R¹ represents hydrogen or -CO-R⁵,
R² represents hydrogen or -CO-R⁶,
R³ represents hydrogen or alkyl,
R⁴ represents alkoxy or dialkylamino,
R⁵ and R⁶ independently represent alkyl, alkoxycarbonyl, alkyl amino, optionally substituted aryl, optionally substituted arylamino or optionally substituted aryl sulfonylamino, or
R¹ and R² together with the nitrogen atom to which they are attached represent a cyclic imide of the formula

stand where
A represents optionally substituted alkanediyl or, if appropriate, substituted alkenediyl,
X¹ represents hydrogen or halogen and
X² represents halogen,
as well as their salts and acid adducts found.

It was also found that pyridyl thiazoles of the formula (I) and their Salts and acid adducts are obtained when one

• a) Haloacetyl pyridines of the formula in which
  X¹ and X² have the meanings given above and
  X³ represents halogen,
  with thio compounds of the formula in which
  R has the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  or
• b) aminothiazoles of the formula in which
  X¹ and X² have the meanings given above,
  either
• α) with carboxylic anhydrides of the formulas in which
  R⁵ has the meaning given above,
  or in which
  A has the meaning given above,
  or
• β) with carboxylic acid halides of the formula in which
  R⁵ has the meaning given above and
  X⁴ represents halogen,
  or
• γ) with isocyanates of the formula R⁷-N = C = O (VII) in which
  R⁷ represents alkyl, optionally substituted aryl or optionally substituted arylsulfonyl,
  or
• δ) with acetals of the formula in which
  R³ and R⁴ have the meanings given above and
  R⁸ represents alkyl,
  if appropriate in the presence of a diluent, if appropriate in the presence of a catalyst and if appropriate in the presence of an acid binder,

and if appropriate subsequently the compounds of the formula (I) thus obtained reacted with an acid or base.

Finally, it was found that the pyridyl-thiazoles of the formula (I) and their Salts and acid adducts are very good for protecting plants against infection by unwanted microorganisms can be used. The substances according to the invention are both suitable for creating resistance in plants to infestation by unwanted microorganisms as well as microbicides for direct control of microorganisms.

Surprisingly, the substances according to the invention are better suited for Generation of resistance in plants to attack by phytopathogenic micro organisms as the 2,6-dichloropyridine-4-carboxylic acid, the 2,6-dichloropyridine-4- carboxylic acid methyl ester and the 2,6-dichloropyridine-4-carboxylic acid α- (4-chloro phenyl) -benzyl ester, which is constitutionally similar, from the prior art are known compounds of the same direction of action. Also excel surprisingly, the substances according to the invention are also structurally similar most beautiful, previously described substances with regard to their fungicidal activity.  

The substances according to the invention can optionally be mixed the possible isomeric forms, such as. B. in the form of stereoisomers or Tautomers. The invention relates to both stereoisomers and Tautomers and also any mixtures of these isomers.

The pyridyl thiazoles according to the invention are general by the formula (I) Are defined.

R preferably represents straight-chain or branched alkyl having 1 to 6 Carbon atoms as well as for the groups

R¹ is also preferably hydrogen or -CO-R⁵.

R² is also preferably hydrogen or -CO-R⁶.

R³ preferably represents hydrogen or straight-chain or branched Alkyl with 1 to 4 carbon atoms.

R⁴ is preferably alkoxy having 1 to 4 carbon atoms or Dialkylamino with 1 to 4 carbon atoms in each alkyl group.

R⁵ and R⁶ independently of one another are preferably straight-chain or branched alkyl having 1 to 6 carbon atoms, alkoxycarbonyl having 1 up to 4 carbon atoms in the alkoxy group, alkylamino with 1 to 6 Carbon atoms, aryl with 6 to 10 carbon atoms, arylamino with 6 up to 10 carbon atoms or arylsulfonylamino with 6 to 10 Carbon atoms, each of the last three radicals mentioned in the Aryl part can be substituted one to three times, in the same way or differently can by halogen, cyano, nitro, formyl, carboxyl, carbamoyl, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, Alkylthio with 1 to 6 carbon atoms, alkylsulfinyl with 1 to 4 carbons atoms, alkylsulfonyl having 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine,  Chlorine and / or bromine atoms, haloalkylthio with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, halogen alkylsulfinyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or Bromine atoms, haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 Carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the Alkyl part and / or by double linked alkanediyl with 3 or 4 Carbon atoms in which one or two (not adjacent) carbon atoms can be replaced by oxygen and in which the alkanediyl part can be substituted up to four times, the same or different by halogen, alkyl having 1 to 4 carbon atoms and / or Haloalkyl with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or Bromine atoms.

R¹ and R² also stand together with the nitrogen atom to which they are attached are bound for a cyclic imide of the formula

wherein
A preferably represents alkanediyl having 2 or 3 carbon atoms or alkenediyl having 2 or 3 carbon atoms, it being possible for the radicals mentioned to be monosubstituted to tetrasubstituted, identical or different, by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, Haloalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms.

X¹ preferably represents hydrogen, fluorine, chlorine or bromine.  

X² preferably represents fluorine, chlorine or bromine.

R particularly preferably represents methyl, ethyl, n-propyl, isopropylene, n-butyl, sec-butyl, iso-butyl, tert-butyl and for the groups

R¹ also particularly preferably represents hydrogen or -CO-R⁵.

R² is also particularly preferably hydrogen or -CO-R⁶.

R³ particularly preferably represents hydrogen, methyl or ethyl.

R⁴ particularly preferably represents methoxy, ethoxy, dimethylamino or diethylamino.

R⁵ and R⁶ independently of one another are particularly preferably methyl, Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, methoxycarbonyl, ethoxycarbonyl, methylamino, Ethylamino, n-propylamino, isopropylamino, n-butylamino, sec-butylamino, isobutylamino, tert-butylamino, phenyl, Naphthyl, phenylamino, naphthylamino, phenylsulfonylamino or Naphthylsulfonylamino, each of the last six Residues in the aryl part from single to triple, identical or different can be substituted by fluorine, chlorine, bromine, cyano, nitro, Formyl, carboxy, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, Ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, Methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, Trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluor methylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, Methoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methox iminomethyl, ethoximinomethyl, methoximinoethyl or ethox iminoethyl and / or by in each case simply until fourfold, identical or different by fluorine, chlorine, methyl,  Trifluoromethyl, ethyl, n- or i-propyl substituted, each doubly linked trimethylene (propane-1,3-diyl), methylenedioxy or ethylenedioxy.

R¹ and R² also stand together with the nitrogen atom to which they are attached are for a cyclic imide of the formula

wherein
A particularly preferably represents alkanediyl having 2 or 3 carbon atoms or alkenediyl having 2 or 3 carbon atoms, it being possible for the radicals mentioned to be monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy and / or trifluoroethoxy.

X¹ particularly preferably represents hydrogen, fluorine or chlorine.

X² particularly preferably represents fluorine or chlorine.

The radicals listed above in general or in the preferred ranges definitions apply to both the end products of formula (I) and correspondingly for the respective starting materials or Intermediates.

These residual definitions can be among each other, that is, between the specified given areas of preferred connections, can be combined as desired.

Preferred compounds according to the invention are also salts which pass through Implementation of pyridyl-thiazoles of the formula

in which
R⁶, X¹ and X² have the meanings given above,
with strong bases of the formula

HOMe (IX)

in which
Me stands for an alkali metal ion, an equivalent of an alkaline earth metal ion, an ammonium ion, an alkylammonium ion with 1 to 4 carbon atoms, a dialkylammonium ion with 1 to 4 carbon atoms in each alkyl group or a trialkylammonium ion with 1 to 4 carbon atoms in each alkyl group,
are available.

Such salts of pyridyl-thiazoles of the formula (Ib) are particularly preferred which R⁶, X¹ and X² have the meanings mentioned above as being particularly preferred have and Me for a lithium, sodium or potassium ion, for an equivalent a magnesium, calcium, strontium or barium ion, for an ammonium, Methylammonium, ethylammonium ion, dimethylammonium, diethyl ammonium, trimethylammonium or triethylammonium ion.

Preferred substances according to the invention are also addition products from acids and those pyridyl-thiazoles of formula (I) in which X¹, X² and R as have preferably indicated meanings.

The acids that can be added preferably include halogen water Substance acids, such as B. the hydrochloric acid and hydrobromic acid,  in particular hydrochloric acid, also phosphoric acid, nitric acid, Sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as B. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, Citric acid, salicylic acid, sorbic acid and lactic acid as well as sulfonic acids, such as e.g. B. p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid or camphorsulfonic acid, Saccharin and thiosaccharin.

If 4-bromoacetyl-2,6-dichloropyridine and thiourea are used as the Aus starting materials, the course of process (a) according to the invention can be determined by the following formula scheme can be illustrated:

If [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] amine and acetic acid are used anhydride as starting materials, the course of the invention Method (b) according to variant (α) using the following formula are illustrated:

Using [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] amine and 2-trifluoro methyl-phenyl-sulfonyl-isocyanate as starting materials, so the course of the Method (b) according to the invention according to variant (γ) by the following Formula scheme to be illustrated:

If one uses N- [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] -N '- (2-trifluoromethyl phenyl-sulfonyl) urea as the starting material and sodium hydroxide as the reaction component, so the production of salts according to the invention Procedures are illustrated by the following formula scheme:

The salt specified above can also be in the tautomeric form of the structure

available.

Those used to carry out process (a) according to the invention as starting materials required haloacetylpyridines are generally defined by the formula (II). In of this formula (II), X 1 and X 2 preferably have those meanings which already in connection with the description of the verb according to the invention of formula (I) as preferred for X¹ and X². X³ stands preferred for chlorine or bromine.

The haloacetyl pyridines of the formula (II) are known in some cases (cf. DE-A 18 11 833).

The haloacetyl pyridines of the formula

in which
X² represents halogen,
X⁵ represents halogen and
X⁶ represents chlorine, bromine or iodine,
are new.

The new haloacetyl-pyridines are generally defined by the formula (IIa).

X² preferably represents fluorine, chlorine or bromine.

X⁵ is preferably fluorine, chlorine or bromine.

X⁶ is preferably chlorine or bromine.

Halogenacetylpyridines of the formula (IIa) in which X 2 is fluorine or chlorine are particularly preferred,
X⁵ represents fluorine or chlorine and
X⁶ represents chlorine or bromine.

The new haloacetyl pyridines of the formula (IIa) can be prepared by one

• c) acetylpyridines of the formula in which
  X² and X⁵ have the meanings given above,
  with halogenating agents, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst.

In an analogous manner, the known haloacetyl pyridines of the formula (II) getting produced.

If 4-acetyl-2,6-dichloropyridine is used as the starting material and bromine Halogenating agent, the course of process (c) by the following Formula scheme can be illustrated.

Those required as starting materials when carrying out process (c) Acetylpyridines are generally defined by the formula (X). In this formula X² and X⁵ preferably have those meanings that are already in  Connection with the description of the compounds of formula (IIa) for this Residues were mentioned as preferred.

The acetylpyridines of the formula (X) are not yet known. You let yourself manufacture by

• d) malonic ester derivatives of the formula in which
  X² and X⁵ have the meanings given above,
  R⁹ represents alkyl and
  R¹⁰ represents alkyl,
  with water optionally in the presence of a diluent.

If 2,6-dichloro-iso-nicotinoyl-malonic acid dimethyl ester is used as the starting material substance and water as a reaction component, so the course of the process (d) are illustrated by the following formula scheme.

In a special variant, method (d) can also be carried out that only partial saponification and decarboxylation takes place. The one there resulting esters of the formula

in which
X², X⁵ and R⁹ have the meanings given above,
can be isolated and then reacted in a further step under the reaction conditions of process (d) to acetylpyridines of the formula (X).

Those required as starting materials when carrying out process (d) Malonic ester derivatives are generally defined by the formula (XI). In this Formula X² and X⁵ preferably have those meanings that are already in Connection with the description of the compounds of formula (IIa) for this Residues were mentioned as preferred. R⁹ is preferably alkyl having 1 to 6 Carbon atoms, particularly preferably for methyl, ethyl, n-propyl, isopropyl, n- Butyl, iso-butyl, sec-butyl or tert-butyl. R¹⁰ is also preferably Alkyl with 1 to 6 carbon atoms, particularly preferably for methyl, ethyl, n- Propyl, isopropyl, n-butyl, iso-butyl, sec-butyl or tert-butyl.

The malonic ester derivatives of the formula (XI) have hitherto not been known. she can be made by

• e) isonicotinic acid halides of the formula in which
  X² and X⁵ have the meanings given above and
  X⁷ represents halogen,
  with malon esters of the formula in which
  R⁹ and R¹⁰ have the meanings given above,
  if appropriate in the presence of a diluent, and if appropriate in the presence of an acid binder, and if appropriate in the presence of a catalyst.

The malonic ester derivatives of the formula (M) and their salts and acid adducts are very good for protecting plants against attack by unwanted Suitable for microorganisms.

If 2,6-dichloro-isonicotinic acid chloride is used as the starting material and Malonic acid dimethyl ester as a reaction component, the course of Ver driving (s) are illustrated by the following formula scheme.

The malonic ester derivatives of the formula (XI) are generally in the form of Mixtures of tautomers characterized by the following formulas can be:

Those required as starting materials when carrying out process (e) Formula (XIII) generally defines isonicotinic acid halides. In this formula X² and X⁵ preferably have those meanings that already in connection with the description of the compounds of formula (IIa) for these residues were mentioned as preferred. X⁷ is preferably chlorine.

The isonicotinic acid halides of the formula (XIII) are known or can be produce according to processes known in principle (cf. J. Chem. Soc. 71 (1897), 1076).

Those in the implementation of process (e) as reaction components required malonic esters are generally defined by the formula (XIII). In this Formula R⁹ and R¹⁰ preferably have those meanings that are already in Connection with the description of the malonic ester derivatives of the formula (XI) for these residues were mentioned as preferred.

The malonic esters of the formula (XIV) are known or can be prepared according to known ones Create methods.

All can be used as diluents when carrying out process (e) usual inert organic solvents can be used. Preferably polar, aprotic solvents such as ethers such as dioxane can be used Tetrahydrofuran or 1,2-dimethoxyethane, also amides, such as N, N- Dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone, furthermore  Nitriles, such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile, as well Sulfoxides, such as dimethyl sulfoxide, and also sulfones, such as sulfolane.

All of the following can be used as acid binders when carrying out process (e) such reactions usual acid acceptors are used. Preferably tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N- Methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), Diazabicyclonones (DBN) or Diazabicycloundecen (DBU).

All catalysts are suitable for carrying out process (e) such reactions usual reaction accelerators in question. Preferably salts of polyvalent metals such as magnesium chloride, Zinc chloride, copper (II) sulfate or iron (III) chloride.

The reaction temperatures can be carried out when carrying out process (e) can be varied within a certain range. Generally works one at temperatures between -20 ° C and + 40 ° C, preferably between -10 ° C and + 30 ° C.

Both when carrying out process (e) and process (c) and (d) is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

When carrying out process (e), 1 mol is used Isonicotinic acid halide of the formula (XII) in general 0.5 to 2 mol, preferably 0.8 to 1.5 mol of malonic ester of the formula (XIV). The Refurbishment is carried out using customary methods. In general, one proceeds in the Way, that one acidifies, the resulting mixture with a water extracted little miscible organic solvent, the combined washes organic phases, if necessary dries and concentrates. The rest Product may possibly still be made by customary methods existing impurities are freed.

Diluents used in carrying out process (d) preferably water-miscible, organic solvents. As  Examples are tetrahydrofuran, acetonitrile, dimethyl sulfoxide and sulfolane called.

The reaction temperatures can be carried out when carrying out process (d) can be varied within a wide range. Generally you work at temperatures between 50 ° C and 200 ° C, preferably between 80 ° C and 180 ° C.

When carrying out process (d), 1 mol of malonic ester is used. Derivative of formula (XI) generally 2 to 5 moles, preferably 2 to 2.5 moles Water. The processing takes place according to usual methods. In general one proceeds in such a way that ice water is added, the resulting Mix several times with an organic that is not very miscible with water Solvent extracted, the combined organic phases with water in Washes the presence of a base, then dries, concentrates and the remaining Distilled residue.

Halogenating agents used in carrying out process (c) preferably bromine, chlorine, N-bromosuccinimide or N-iodosuccinimide in Consideration.

All can be used as diluents when carrying out process (c) usual inert, organic solvents are used. Preferably Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as hexane, cyclohexane, benzene, dichloromethane, Chloroform, carbon tetrachloride or trichloroethane.

Catalysts are preferred when carrying out process (c) Lewis acids, such as aluminum trichloride.

The reaction temperatures can also be carried out when carrying out process (c) can be varied within a wide range. Generally you work at temperatures between -20 ° C and + 120 ° C, preferably between 10 ° C and 50 ° C.

When carrying out process (c), 1 mol of acetylpyridine is used of the formula (X) generally 0.5 to 5 mol, preferably 0.8 to 1.2 mol  Halogenating agent. The processing takes place according to usual methods. in the generally one proceeds in such a way that the reaction mixture with Water added, the organic phase successively with water in the presence of Base and then washed with water, then dried and concentrated. The accruing product can possibly still be contained by usual methods Impurities are freed.

The to carry out the method (a) according to the invention as Formula (III) generalizes thio compounds required as starting materials Are defined. In this formula (III), R preferably has those meanings that already in connection with the description of the invention Compounds of formula (I) have been given as preferred for R.

The thio compounds of formula (III) are known synthetic chemicals.

Those used to carry out process (b) according to the invention as starting materials required aminothiazoles of the formula (Ia) are substances according to the invention which are: can be produced by process (a) according to the invention.

The when carrying out the method (b, variant α) as Reaction components required carboxylic anhydrides are given by the formulas (IV) and (V) generally defined.

In these formulas, R⁵ and A preferably have those meanings that already in connection with the description of the pyridyl according to the invention thiazoles of the formula (I) were mentioned as preferred for these radicals.

The carboxylic anhydrides of the formulas (IV) and (V) are known or can be produce by known methods.

When performing the method (b, variant β) as Reaction components required carboxylic acid halides are given by the formula (VI) generally defined. In this formula, R⁵ preferably has those Meanings already related to the description of the Pyridyl-thiazoles according to the invention were mentioned as preferred for this radical. X⁴ is preferably chlorine or bromine.  

The carboxylic acid halides of the formula (VI) are known or can be reduced produce known methods.

The when carrying out the method (b, variant γ) as Isocyanates required for reaction components are represented by the formula (VII) generally defined. In this formula, R⁷ is preferably straight-chain or branched alkyl with 1 to 6 carbon atoms, aryl with 6 to 10 carbon atoms or arylsulfonyl having 6 to 10 carbon atoms, each of the two last-mentioned residues in the aryl part single to triple, similar or can be differently substituted by halogen, cyano, nitro, formyl, carboxyl, Carbamoyl, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 Carbon atoms, alkylthio with 1 to 6 carbon atoms, alkylsulfinyl with 1 up to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms, Haloalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or Bromine atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine, Chlorine and / or bromine atoms, haloalkylthio with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, haloalkylsulfinyl with 1 to 4 Carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, Haloalkylsulfonyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or Bromine atoms, alkoxycarbonyl with 1 to 4 carbon atoms in Alkoxy part, hydroximinoalkyl having 1 to 4 carbon atoms in the alkyl part, Alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 Carbon atoms in the alkyl part and / or by double-linked alkanediyl with 3 or 4 carbon atoms, in which one or two (not adjacent) Carbon atoms can be replaced by oxygen and in which the Alkanediyl part can be substituted up to four times, in the same way or differently can by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms.

R⁷ particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, phenyl, naphthyl, phenylsulfonyl or Naphthylsulfonyl, with each of the four last-mentioned residues in the aryl part can be substituted from one to three times, the same or different by fluorine, chlorine, bromine, cyano, nitro, formyl, carboxy, carbamoyl, Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, Ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluor  ethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, tri fluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, Trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, Hydroximinomethyl, hydroximinoethyl, methoximinomethyl, ethoximino methyl, methoximinoethyl or ethoximinoethyl and / or by each optionally up to four times, the same or different from fluorine, Chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl substituted, each doubly linked trimethylene (propane-1,3-diyl), methylenedioxy or Ethylenedioxy.

The isocyanates of the formula (VII) are known or can be prepared according to known ones Establish process.

The when performing the method according to the invention (b, variant δ) as Reaction components required acetals are general by the formula (VIII) Are defined. In this formula, R³ and R⁴ preferably have those meanings already in connection with the description of the invention Pyridyl-thiazoles of the formula (I) were mentioned as preferred for these radicals. R⁸ preferably represents methyl or ethyl.

Suitable diluents for carrying out the process according to the invention Process (a) all customary, inert organic solvents into consideration. Aliphatic, alicyclic or aromatic carbons are preferably usable Hydrogen, such as petroleum ether, hexane, heptane, cyclohexane, Methylcyclohexane, benzene, toluene, xylene or decalin; halogenated coal water substances such as chlorobenzene, dichlorobenzene, dichloromethane, chloro form, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, Diisopropyl ether, methyl t-butyl ether, methyl t-alnyl ether, dioxane, tetrahydro furan, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones, such as acetone, Butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, Propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethyl formamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoric triamide; Esters such as methyl acetate or acetic acid reethylester; Sulfoxides such as dimethyl sulfoxide; Sufone, like Sulfolan.

Suitable acid binders when carrying out the process according to the invention driving (a) all common inorganic or organic bases into question. Preferential  Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as wise sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, Calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or Sodium bicarbonate, also ammonium compounds, such as ammonium hydroxide, ammonium acetate and ammonium carbonate, and also tertiary Amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N- Dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

However, it is also possible to carry out the method according to the invention (a) Work in the absence of additional acid binders.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (a) can be varied within a wide range. In general one works at temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 80 ° C.

Both when carrying out the method (a) and the Process (b) is generally carried out under normal pressure. However, it is each also possible under increased or reduced pressure, for. B. between 0.1 bar and 10 bar to work.

When carrying out process (a) according to the invention, 1 mol is used of haloacetyl-pyridine of the formula (II) in general 0.8 to 10 mol, preferably 1 to 5 mol of thio compound of the formula (III). The Refurbishment is carried out using customary methods.

Suitable diluents for carrying out the process according to the invention Process (b) all customary, inert organic solvents into consideration. In the case of variants (α), (β) and (γ), all can preferably be used those solvents already in the case of the method according to the invention (a) were mentioned as preferred. When performing variant (δ) you can alcohols, such as methanol or ethanol, are also used as diluents will.  

Suitable acid binders when carrying out the process according to the invention fahrens (b), variants α and β, all acid customary for such reactions acceptors into consideration. Those are preferably usable Acid binders that are already in the case of process (a) according to the invention were preferred.

The separate addition of a catalyst is generally unnecessary Implementation of variants (α) and (β) of method (b) according to the invention.

When carrying out the variants (γ) and (δ) of the invention Process (b) is generally not the addition of an acid binder required.

Catalysts come in carrying out variant (γ) of the invention according to method (b), all the reaction reactions customary for such reactions accelerator in question. Amines such as pyridine can preferably be used. Dimethylaminopyridine and diazabicyclo-undecene (DBU).

Catalysts come when carrying out variant (δ) of the invention according to method (b), all the reaction reactions customary for such reactions accelerator into consideration. Acids such as sulfur can preferably be used acid, hydrochloric acid and toluenesulfonic acid, and also acid Ion exchanger.

When carrying out process (b) according to the invention, the Reaction temperatures can be varied within a wide range. in the generally one works at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

When carrying out process (b) according to the invention, 1 mol is used of aminothiazole of the formula (Ia) in general 0.8 to 15 mol, preferably 1 up to 8 moles of reaction component of the formula (IV), (V), (VI), (VII) or (VIII) on. The processing takes place according to usual methods.

In the preparation of salts of compounds according to the invention, the procedure is as follows general in such a way that a pyridyl-thiazole of the formula (Ib) in one inert organic solvent, such as. As methanol or ethanol, dissolves and  Room temperature or at a slightly elevated temperature with a strong base of the formula (IX). The insulation and any necessary The resulting salts are cleaned by customary methods.

The pyridyl thiazoles of the formula (I) according to the invention can also be in acid addition salts are transferred.

For the preparation of acid addition salts of the compounds of the formula (I) those acids that are already related are preferred with the description of the acid addition salts according to the invention as preferred Acids were called.

The acid addition salts of the compounds of formula (I) can in simpler Way according to usual salt formation methods, e.g. B. by loosening a connection of formula (I) in a suitable inert solvent and adding the Acid, e.g. As hydrochloric acid can be obtained and in a known manner, for. B. by filtration, isolated and optionally by washing with an inert organic solvents can be cleaned.

The active compounds according to the invention have a strong resistance-inducing Effect in plants. They are therefore suitable for creating resistance in Plants against infestation by unwanted microorganisms.

In the present context, resistance-inducing substances include those To understand substances that are able to improve the defense system of plants to stimulate that the treated plants with subsequent inoculation unwanted microorganisms extensive resistance to this microorganism unfold nisms.

In the present case, undesirable microorganisms include phytopathogenic Understand fungi, bacteria and viruses. The substances according to the invention can So used to look after in plants within a certain period of time the treatment becomes resistant to infestation by the named pathogens produce. The period of time within which resistance is established extends generally from 1 to 10 days, preferably 1 to 7 days after Treatment of plants with the active ingredients.  

In addition to the resistance-inducing agents, the active compounds according to the invention Effect also have a strong microbicidal effect and also become direct Combating unwanted microorganisms practically used. The Active ingredients are for use as pesticides, especially as Suitable for fungicides.

Unwanted microorganisms in crop protection include fungi from the Classes Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia orvzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Altemaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoi des.

The good plant tolerance of the active ingredients in the control of the plant necessary concentrations, allows treatment from above plant parts, as well as a treatment of plant and seed and of the floor.

The active compounds according to the invention can be particularly successful to combat cereal diseases, such as erysiphe-  Types, or of diseases in wine, fruit and vegetable growing, such as as against Plasmopara or Venturia species, or rice diseases, such as for example against Pyricularia species. With good success, the active compounds according to the invention also other plant diseases, such as for example Septoria, Cochliobolus, Pyrenophora, and Pseudocercosporella Combat species.

The active ingredients can depend on their respective physical and / or chemical properties are converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, Aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds good, as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by Ver mix the active ingredients with extenders, i.e. liquid solvents Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents Auxiliary solvents can be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene, or methylene chloride, aliphatic hydrocarbons, such as Cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or Glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as Dimethylformamide or dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant such liquids which are gaseous at normal temperature and pressure, e.g. B. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: B. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silica, alumina 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 stalks; as emulsifying and / or foam Generating funds are possible: z. B. non-ionic and anionic Emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; as dispersants come into question: z. B. Lignin sulfite liquor and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers used, such as. B. gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic Phospholipids. Other possible additives are mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine 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 weight percent active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their form also mixed with known fungicides, bactericides, acaricides, Nematicides or insecticides can be used, e.g. B. the effect to broaden the spectrum or to prevent the development of resistance.

In many cases, synergistic effects are observed.

For the mixtures, for example:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxa-nilide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropyl fos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,
Cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb,
Difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenyl amine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropi-morph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, futrianol, flutrianol, flutrianol Furalaxyl, furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,
Methasulfocarb, methfuroxam, metiram, metsuifovax, myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, Triadi menol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosuifan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorflu azuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin,
Clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethopro phos, Etrimphos,
Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate,
Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluv alinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos,
Methamidophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin,
Monocrotophos, moxidectin,
Naled, NC 184, NI 25, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos,
Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat,
Pymetrozine, Pyrachlophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazine, Thuringiensin, Tralomenhrononium, Triomenethriazonium, Tri
Vamidothione, XMC, xylylcarb, zetamethrin.

The active compounds according to the invention can also be used with other known active compounds fen, such as herbicides or with fertilizers and growth regulators to be mixed.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms, such as ready-to-use solutions, suspensions, Spray powder, pastes, soluble powders, dusts and granules are used will. The application is done in the usual way, e.g. B. by pouring, Spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to use the active ingredients according to the ultra-low-volume method apply or the drug preparation or the drug itself in the Inject soil. The seeds of the plants can also be treated will.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied in a larger area:  generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

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

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 wt .-%, preferably from 0.0001 to 0.02 wt .-% at the place of action conducive.

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

Manufacturing examples Example 1

931.5 g (3.46 mol) of 4-bromoacetyl-2,6-dichloropyridine and 318.2 g (4.18 mol) of thio urea are combined in 4.2 liters of acetone with stirring, the Temperature rises to 45 ° C. The mixture is stirred for a further 3 hours. Of the the resulting solid is filtered off, washed with a little acetone and under further suction drying. The product thus obtained is suspended Room temperature in 2 liters of water, by adding concentrated, aqueous sodium hydroxide solution to a pH of 10, in turn sucks off, washes with 3 liters of water and dries at 50 ° C under reduced pressure. The crude product thus obtained is stirred with 30 liters of tert-amyl methyl ether, and the resulting mixture is suctioned off. The filtrate is reduced Concentrated pressure and the remaining residue at 50 ° C under ver dried under reduced pressure. The after suctioning off the tert-amyl methyl ether Mixed isolated solid is dissolved in 1 liter of hot ethanol. The the resulting solution is filtered and then cooled to 5 ° C. The dealt Different solid is also suction filtered and at 50 ° C under reduced Pressure dried. A total of 600.1 g (70.5% of the Theory) on [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] amine as solid substance from Melting point 239 to 247 ° C.  

Production of raw materials

To a solution of 525 g (2.763 mol) of 4-acetyl-2,6-dichloropyridine in 1.37 l first 2 g of aluminum chloride and then 417.6 g (2.613 mol) of bromine are added dropwise with stirring at 30 to 35 ° C within 30 minutes. After finished Addition, the reaction mixture is stirred for a further hour at 35 ° C and then mixed with 1.2 l of water. The organic phase is separated off and successively first with 1.2 l of saturated, aqueous sodium hydrogen carbonate Solution and then washed twice with 1.2 l of water. You dry over Sodium sulfate and then concentrated under reduced pressure. The remaining one The residue is stirred with 2 l of petroleum ether, then filtered off with suction and in portions Washed a total of 1 liter of petroleum ether. The resulting product is at 50 ° C dried under reduced pressure. This gives 592.2 g (79.7% of theory) of 4-bromo-acetyl-2,6-dichloropyridine in the form of a Solid substance.

1 H NMR Spectrum (CDCl₃ / TMS): δ = 4.42 (s, 2H); 7.74 (s, 2H) ppm

1328 g (4.34 mol) of 2,6-dichloro-isonicotinoyl-malonic acid dimethyl ester are in a mixture of 3.45 l of dimethyl sulfoxide and 156.2 g (8.68 mol) of water solved. The reaction mixture is heated to 140 ° C and 30 minutes at this Temperature stirred. The reaction mixture is then cooled to 10 ° C. and then poured into 8.4 l of ice water. The mixture is extracted twice with a total of 3.6 l dichloromethane and washes the combined organic phases once with 1.5 l of saturated aqueous sodium hydrogen carbonate solution. After this Drying over sodium sulfate, the organic phase is under reduced pressure constricted. The remaining residue is distilled under reduced pressure.  

In this way, 506.0 g (60% of theory) of 4-acetyl-2,6-dichloro are obtained pyridine boiling point 98 ° at 0.5 mbar.

2312 g (24.28 mol) of magnesium chloride are cooled in 18 l of acetonitrile registered. After the exothermic reaction has subsided, the solution becomes Chilled 0 ° C and dropwise with stirring within 32 minutes with 3210 g (24.3 mol) dimethyl malonate added. Then be at 0 ° C 4920 g (48.62 mol) of triethylamine were added dropwise over the course of 1.5 hours. After the addition has ended, the mixture is stirred at 0 ° C. for a further 15 minutes. Subsequently becomes a solution of 4742 g at 0 ° C with stirring within 20 hours (22.53 mol) of 2,6-dichloroisonicotinic acid chloride in 6670 ml of acetonitrile were added dropwise. It is first one hour at 0 ° C and then 16 hours under slow Warm to room temperature afterwards. Then that will Reaction mixture with cooling to 0 to 10 ° C with stirring dropwise 15.9 l of concentrated hydrochloric acid are added. Then it is mixed with stirring 15.9 l dichloromethane and 6.4 l water and then separates the organic phase. The aqueous phase is extracted again with 7.9 l of dichloromethane. The combined organic phases are washed twice with 4 l of water and then concentrated under reduced pressure. The remaining residue is with 9.5 l of water are mixed, then suctioned off and in succession first with 6.3 l of water and then washed twice with 7.9 liters of petroleum ether. The resulting product is dried at 40 ° C under reduced pressure. You get this way 6.17 kg (89.2% of theory) of 2,6-dichloro-isonicotinoyl-malonic acid-dimethyl ester.

1 H NMR Spectrum (CDCl₃ / TMS): δ = 3.68; 3.84; 3.92 and 7.39 ppm.  

Example 2

To a solution of 7.38 g (0.03 mol) of [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] amine in 180 ml of acetonitrile at 75 ° C with stirring 7.53 g (0.03 mol) of 2-tri fluoromethylphenylsulfonyl isocyanate added within 5 minutes. Man the reaction mixture is stirred for a further 3 hours at 75 ° C., then cools down From room temperature, sucks off the precipitated solid, washes twice with 10 ml each of acetonitrile and dried at 45 ° C under reduced pressure. Man receives 14 g (93.9% of theory) of N- [4- (2,6-dichloropyridine-4- yl) -thiazol-2-yl] -N ′ - (2-trifluoromethyl-phenylsulfonyl) urea in the form of a solid substance with a melting point of <280 ° C.

Example 3

7.38 g (0.03 mol) of [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] amine and 70 ml Acetic anhydride are refluxed for 30 minutes, during which time first forms a solution, but then a precipitate fails. You leave that Reaction mixture stand 16 hours at room temperature, then adds 200 ml Add ice water and suction. The residue is first washed several times with water washed, then with 200 ml of 5% aqueous sodium hydrogen carbonate solution digested and suctioned again. The product is reduced at 50 ° C Pressure dried. 8.1 g (93.8% of theory) are obtained in this way N- [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] acetamide in the form of a solid melting point 301 ° C.  

Example 4

To a mixture of 7.38 g (0.03 mol) of [4- (2,6-dichloropyridin-4-yl) thiazol-2- yl] amine and 50 ml of methanol are added at 20 ° C with stirring 3.93 g (0.033 mol) Dimethylformamiddimethylacetal and stirred for 2 hours at 50 ° C. The reaction mixture is then cooled to 10 ° C. and suction filtered. Of the The residue is washed with 10 ml of cold methanol and then at 45 ° C. dried under reduced pressure. 7.5 g (83% of theory) on N- [4- (2,6-dichloropyridin-4-yl) thiazol-2-yl] -N, N'-dimethyl form amidine in the form of a solid with a melting point of 145 ° C.

According to the methods given above, the ones in the table below are also listed compounds of the formula

manufactured.  

Table 1

Examples of use Example A Plasmopara test (vines) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 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 amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation dewy sprayed. After the spray coating has dried on, the Plants inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in a moist chamber at 20 to 22 ° C and 100% for 1 day relative humidity. The plants are then 5 days in Greenhouse set up at 21 ° C and approx. 90% humidity. The plants are then moistened and placed in a moist chamber for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means one Efficiency that corresponds to that of the control during a Efficiency of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are based on the following table.  

Table A

Plasmopara test (vine) / protective

Example B Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 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 amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation to dripping wet. After the spray coating has dried on the plants with an aqueous conidia suspension of Apple scab pathogen Venturia inaequalis inoculated and then remain for 1 day 20 ° C and 100% relative humidity in an incubation cabin.

The plants are then grown in a greenhouse at 20 ° C and a relative Humidity of approx. 70% set up.

Evaluation is carried out 12 days after the inoculation. 0% means one Efficiency that corresponds to that of the control during an impact degree of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are based on the following table.  

Table B

Venturia test (apple) / protective

Example C Erysiphe test (barley) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 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 amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate. After the The plants are sprayed with spores from Erysiphe graminis f.sp.hordei pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means one Efficiency that corresponds to that of the control during an impact degree of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are based on the following table.  

Table C.

Erysiphe test (barley) / protective

Example D Erysiphe test (barley) / curative

Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and Emulsifier and dilute the concentrate with water to the desired one Concentration.

To test for curative effectiveness, young plants with spores from Erysiphe graminis f.sp. hordei pollinated. 48 hours after inoculation the plants with the active ingredient preparation in the application rate indicated sprayed.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means one Efficiency that corresponds to that of the control during an impact degree of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are based on the following table.  

Table D

Erysiphe test (barley) / curative

Example E Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 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 amounts of solvent and dilutes the Concentrate with water and the specified amount of emulsifier on the desired concentration.

To test for protective effectiveness, young rice plants are sprayed with the Active ingredient preparation to dripping wet. 4 days after the The plants are sprayed with an aqueous spore suspension of Pyricularia oryzae inoculated. Then the plants are in one Greenhouse at 100% rel. Humidity and 25 ° C.

The disease infestation is evaluated 4 days after the inoculation. Here 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are based on the following table.  

Table E

Pyricularia test (rice) / protective

Example F Pyricularia test (rice) / systemic

Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 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 amounts of solvent and dilutes the Concentrate with water and the specified amount of emulsifier on the desired concentration.

40 ml of the active ingredient are added to test for systemic properties preparation poured onto uniform earth in which young rice plants were grown. 7 days after the treatment, the plants are washed with an aqueous Spore suspension of Pyricularia oryzae inoculated. After that the Plant in a greenhouse at a temperature of 25 ° C and a rel. Air humidity of 100% until evaluation.

The disease infestation is evaluated 4 days after the inoculation. Here 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Active substances, active substance concentrations and test results are based on the following table.  

Table F

Pyricularia test (rice) / systemic

Claims (16)

1. Pyridyl thiazoles of the formula in which
R for alkyl, stands, where
R¹ represents hydrogen or -CO-R⁵,
R² represents hydrogen or -CO-R⁶,
R³ represents hydrogen or alkyl,
R⁴ represents alkoxy or dialkylamino,
R⁵ and R⁶ independently of one another represent alkyl, alkoxycarbonyl, alkylamino, optionally substituted aryl, optionally substituted arylamino or optionally substituted arylsulfonylamino, or
R¹ and R² together with the nitrogen atom to which they are attached represent a cyclic imide of the formula stand where
A represents optionally substituted alkanediyl or optionally substituted alkenediyl,
X¹ represents hydrogen or halogen and
X² represents halogen,
as well as their salts and acid adducts. 2. pyridyl-thiazoles of the formula (I) according to claim 1, in which
R for straight-chain or branched alkyl having 1 to 6 carbon atoms and for the groups stands in what
R¹ represents hydrogen or -CO-R⁵,
R² represents hydrogen or -CO-R⁶,
R³ represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
R⁴ represents alkoxy having 1 to 4 carbon atoms or dialkylamino having 1 to 4 carbon atoms in each alkyl group and
R⁵ and R⁶ independently of one another for straight-chain or branched alkyl with 1 to 6 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, alkylamino with 1 to 6 carbon atoms, aryl with 6 to 10 carbon atoms, arylamino with 6 to 10 carbon atoms or arylsulfonylamino with 6 are up to 10 carbon atoms, each of the last three radicals in the aryl part being monosubstituted to triple, identical or differently substituted by halogen, cyano, nitro, formyl, carboxyl, carbamoyl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 Carbon atoms, alkylthio with 1 to 6 carbon atoms, alkylsulfinyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, haloalkylthio having 1 to 4 carbon atoms and 1 to 5 bottles uor, chlorine and / or bromine atoms, haloalkylsulfinyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, haloalkyl sulfonyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms , Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy part, hydroximinoalkyl with 1 to 4 carbon atoms in the alkyl part, alkoximinoalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part and / or by double-linked alkanediyl with 3 or 4 carbon atoms, in which one or two (non-adjacent) carbon atoms can be replaced by oxygen and in which the alkanediyl part can be mono- to tetrasubstituted, identical or differently substituted by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 or 2 carbon atoms and 1 up to 3 fluorine, chlorine and / or bromine atoms,
or
R¹ and R² together with the nitrogen atom to which they are attached represent a cyclic imide of the formula stand in what
A represents alkanediyl having 2 or 3 carbon atoms or alkenediyl having 2 or 3 carbon atoms, it being possible for the radicals mentioned in each case to be substituted one to four times, in the same way or differently, by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms and / or by haloalkoxy with 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms,
X¹ represents hydrogen, fluorine, chlorine or bromine
and
X² represents fluorine, chlorine or bromine. 3. Process for the preparation of pyridyl-thiazoles of the formula (I) according to Claim 1 and of their salts and acid adducts, characterized in that

• a) Haloacetyl pyridines of the formula in which
  X¹ and X² have the meanings given above and
  x³ represents halogen,
  with thio compounds of the formula in which
  R has the meaning given above,
  if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder,
  or
• b) aminothiazoles of the formula in which
  X¹ and X² have the meanings given above,
  either
• α) with carboxylic anhydrides of the formulas in which
  R⁵ has the meaning given above,
  or in which
  A has the meaning given above,
  or
• b) with carboxylic acid halides of the formula in which
  R⁵ has the meaning given above and
  X⁴ represents halogen,
  or
• γ) with isocyanates of the formula R⁷-N = C = O (VII) in which
  R⁷ represents alkyl, optionally substituted aryl or optionally substituted arylsulfonyl,
  or
• δ) with acetals of the formula in which
  R³ and R⁴ have the meanings given above and
  R⁸ represents alkyl,
  if appropriate in the presence of a diluent, if appropriate a catalyst and if appropriate in the presence of an acid binder,

and optionally then the compounds of the thus obtained Reacts formula (I) with an acid or base. 4. Means for protecting plants against attack by unwanted Microorganisms, characterized by a content of at least one Pyridyl-thiazole of formula (I) according to claim 1 or a salt or Acid adduct of a pyridyl thiazole of the formula (I). 5. Use of pyridyl-thiazoles of the formula (I) according to claim I or of their salts or acid adducts for protecting plants against Infested by unwanted microorganisms. 6. Process for protecting plants against infestation by unwanted Microorganisms, characterized in that pyridyl thiazoles Formula (I) according to claim 1 or its salts or acid adducts on the Brings out microorganisms and / or their habitat. 7. Process for the preparation of means for protecting plants against Infestation by unwanted microorganisms, characterized in that pyridyl thiazoles of the formula (I) according to Claim 1 or salts thereof or acid adducts with extenders and / or surfactants mixed.   8. Haloacetyl pyridines of the formula in which
X² represents halogen,
X⁵ represents halogen and
X⁶ represents chlorine, bromine or iodine. 9. A process for the preparation of haloacetyl-pyridines of the formula (IIa) according to claim 8, characterized in that

• c) acetylpyridines of the formula in which
  X² and X⁵ have the meanings given above,
  with halogenating agents, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst.

10. Acetylpyridines of the formula in which
X² represents halogen and
X⁵ represents halogen. 11. A process for the preparation of acetylpyridines of the formula (X) according to claim 10, characterized in that

• d) malonic ester derivatives of the formula in which
  X² and X⁵ have the meanings given above,
  R⁹ represents alkyl and
  R¹⁰ represents alkyl,
  with water if appropriate in the presence of a diluent.

12. Malonic ester derivatives of the formula in which
X² represents halogen,
X⁵ represents halogen,
R⁹ represents alkyl and
R¹⁰ represents alkyl. 13. A process for the preparation of malonic ester derivatives of the formula (XI) according to claim 12, characterized in that

• e) isonicotinic acid halides of the formula in which
  X² and X⁵ have the meanings given above and
  X⁷ represents halogen,
  with malon esters of the formula in which
  R⁹ and R¹⁰ have the meanings given above,

optionally in the presence of a diluent and given if in the presence of an acid binder and optionally in In the presence of a catalyst. 14. Use of malonic ester derivatives of the formula (XI) according to claim 12 and their salts and acid adducts for protecting plants against infestation by unwanted microorganisms.