DE3633485A1 - Substituted 2-pyri(mi)dyl-2'-pyridyl (thio)ethers - Google Patents

Abstract

The invention relates to novel 2-pyri(mi)dyl-2'-pyridyl (thio)ethers of the formula (I) <IMAGE> in which A represents a (-CH=) group or a nitrogen atom, X represents oxygen or sulphur, Z represents the radical <IMAGE> and R<1>, R<2>, R<3>, R<5>, R<6>, R<7>, R<8>, R<5-1>, R<6-1>, D, B, Y and n have the meanings given in the description, to a plurality of processes for their preparation and for their use as herbicides.

Description

The present invention relates to new 2-pyri (mi) dyl-2'-pyridyl (thio) ethers, several procedures for their Production and their use as herbicides.

It is already known that certain carboxylic anilides possess herbicidal properties (cf. R. Wegler "Chemistry the plant protection and pesticide "Vol. 2, pp. 311-314, Springer-Verlag, Berlin 1970). The Effect of these compounds is good, however low application rates some weeds are not always full detected, the selectivity is not always sufficient.

It is also known that numerous pyrimidyl 2-ether and thioethers are suitable as herbicides (cf. e.g. JP-OS 9,474 / 1967, U.S. Patent No. 31,26,271 and U.S. Patent No. 3,250,775).  

However, the herbicidal potency of these substances is not always sufficient. Herbicidally active benzoic acids are also and their pyri (mi) dyloxy or thio substituted Derivatives known (cf. e.g. EP 1 47 477 and EP 1 187), however, the herbicidal activity is this Substances and their compatibility with important ones Cultivated plants are not always used in all areas satisfactory.

There have now been new substituted 2-pyri (mi) dyl-2'-pyridyl (thio) ether of formula (I) found

in which
R¹, R² and R³ independently of one another each represent hydrogen, halogen, alkyl, alkoxy or alkylthio each having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, amino, alkylamino or dialkylamino each having 1 to 6 carbon atoms in the individual alkyl parts,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, halogen, cyano, alkyl or alkoxy each having 1 to 6 carbon atoms, where Y can be the same or different and
n stands for a number from 1 to 3 and
Z for the rest

or

stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, alkyl or alkoxyalkyl each having 1 to 6 carbon atoms, alkenyl or alkynyl each having 3 to 6 carbon atoms,
R⁵, R⁶ and R⁷ each independently represent hydrogen, halogen, cyano, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms and up to 13 halogen atoms, alkenyl or alkynyl each having 2 to 6 carbon atoms,
R⁴ and R⁵ together with the carbon and the nitrogen to which they are attached form a 3 to 8-membered heterocyclic ring which is optionally mono- or polysubstituted, identically or differently, by halogen, methyl and ethyl and which can contain one or more double bonds .
R⁶ and R⁷ together with the carbon to which they are attached form a 3 to 8-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur atoms as ring members and which, if appropriate, can be mono- or polysilicon or halogen Ethyl is substituted and which may contain one or more double bonds and
R⁸ represents hydrogen, optionally single or multiple, identical or different halogen-substituted alkyl having 1 to 6 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms per alkyl part, alkenyl or alkynyl each having 3 to 6 carbon atoms and
R ^5-1 and R ^6-1 each independently represent alkyl with 1-6 carbon atoms.

It was also found that substituted 2-pyri (mi) dyl-2'-pyridyl (thio) ether of formula (I) get when one

• A) compounds of the formula (II), in which
  R¹, R², R³, A, X, Y and n have the meaning given above,
  either
  • a₁) with acid halides of the formula (IIIa), in which
    R⁵, R⁶, R⁷ have the meaning given above and
    Hal stands for halogen,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    or
  • a₂) with symmetrical carboxylic anhydrides of the formula (IIIb), in which
    R⁵, R⁶ and R⁷ have the meaning given above,
    if appropriate in the presence of a diluent,
    or
  • a₃) with asymmetric acid anhydrides of the formula (IIIc), in which
    R⁵, R⁶ and R⁷ have the meaning given above and
    R represents alkyl or alkylsulfonyl each having 1 to 4 carbon atoms, phenyl or phenylsulfonyl,
    if appropriate in the presence of a diluent,
    or
  • a₄) with compounds of the formula (IIId), in which
    R⁵, R⁶ and R⁷ have the meaning given above
    if appropriate in the presence of a diluent,
    or if you
• B) pyri (mi) din derivatives of the formula (IV), in which
  R¹, R², R³ and A have the meaning given above and
  Hal stands for halogen,
  with acylaminopyridine derivatives of the formula (V), in which
  R⁵, R⁶, R⁷, X, Y and n have the meaning given above,
  in the presence of a diluent and, if appropriate, in the presence of an acid binder,
  or
• C) pyri (mi) din derivatives of the formula (VI), in which
  R¹, R², R³, A and X have the meaning given above,
  either
  • C₁) with 2 halogen nicotinic acid derivatives of the formula (VIIa), in which
    R⁵, R⁶, R⁷, D, Y and n have the meaning given above and
    Hal¹ represents halogen,
    in the presence of a diluent and, if appropriate, in the presence of an acid binder,
    or
  • C₂) with 2-halogen nicotinic acid derivatives of the formula (VIIb), in which
    R ^5-1 , R ^6-1 , Y, n and Hal 1 have the meaning given above,
    in the presence of a diluent and in the presence of a base as acid binder and catalyst, to give the compounds of the formula (Ia₃) or if you
• D) 2-hydroxy (mercapto) nicotinic acid derivatives of the formula (VIII), in which
  R⁵, R⁶, R⁷, D, X, Y and n have the meaning given above,
  with pyri (mi) din derivatives of the formula (IV), in which
  R¹, R², R³ and A have the meaning given above and
  Hal stands for halogen,
  in the presence of a diluent and, if appropriate, in the presence of an acid binder,
  or if you
• E) substituted 2-pyri (mi) dyl-2′-pyridyl (thio) ethers of the formula (Ia), in which
  Z¹ for the rest stands and
  R¹, R², R³, R⁵, R⁶, R⁷, A, D, X, Y and n have the meaning given above,
  with sulfurization reagents, such as phosphorus V-sulfide or 2,4-bis (4-methoxyphenyl) -2,4-dithiono-1,2,3,4-dithia-phosphetane (Lawesson's reagent), to give compounds of the formula (Ib), in which
  Z² for the rest stands and
  R¹, R², R³, R⁵, R⁶, R⁷, A, D, X, Y and n have the meaning given above,
  or if you
• F) the compounds of the formula (Ib), in which D is <NH, prepared by the process (E), with deprotonating bases and compounds of the formula (IX), F-R⁸ (IX) in which
  R⁸ has the meaning given above and
  F represents halogen, alkylsulfonyloxy or phenylsulfonyloxy,
  if appropriate in the presence of a diluent.

Finally it was found that the new ones were substituted 2-pyri (mi) dyl-2'-pyridyl (thio) ether of the formula (I) characterized by excellent herbicidal activity.

Surprisingly, the substituted ones according to the invention 2-pyri (mi) dyl-2'-pyridyl (thio) ether of Formula (I) has significantly better herbicidal properties than the constitutionally similar known substances. Thus, the compounds of the invention Formula (I) much better for weed control use as the 2-phenoxy-4,6-dimethyl-pyrimidine, which is a structurally similar previously known active ingredient is.  

The carbon chain in alkyl, alkoxy, alkoxyalkyl, Is alkylthio, haloalkyl, alkenyl and alkynyl each straight-chain or branched. Halogen stands for fluorine, Chlorine, bromine and iodine.

Preferred compounds of the formula (I) are those in which
R¹, R² and R³ each independently represent hydrogen, fluorine, chlorine, bromine, iodine, alkyl, alkoxy or alkylthio each having 1 to 4 carbon atoms, trifluoromethyl, amino, alkylamino or dialkylamino each having 1 to 4 carbon atoms in the individual alkyl parts ,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, alkyl or alkoxy each having 1 to 4 carbon atoms, where Y can be identical or different,
n represents 1, 2 or 3,
Z for the rest

stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, alkyl or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts, alkenyl or alkynyl each having 3 to 4 carbon atoms,
R⁵, R⁶ and R⁷ each independently represent hydrogen, halogen, cyano, alkyl having 1 to 5 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms or
R⁴ and R⁵ together with the carbon and nitrogen to which they are attached form a 3 to 7-membered heterocyclic ring which is optionally monosubstituted to 12-fold substituted, identically or differently, by fluorine, chlorine, bromine, methyl and ethyl and which one to can contain two double bonds, or
R⁶ and R⁷ together with the carbon to which they are bonded form a 3 to 7-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur as ring members and which may optionally be up to twelve times, the same or different, by fluorine, chlorine, Bromine, methyl and ethyl is substituted and can contain one to three double bonds, and
R⁸ represents hydrogen, optionally mono- to quintuple, identical or different, substituted by fluorine, chlorine and bromine, alkyl having 1 to 5 carbon atoms, alkoxyalkyl having 1 to 4 carbon atoms per alkyl part, alkenyl or alkynyl each having 3 to 4 carbon atoms and
R ^5-1 and R ^6-1 each independently represent alkyl having 1 to 4 carbon atoms.

Those compounds of the formula (I) in which
R¹, R² and R³ each independently represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, amino, methylamino, ethylamino, isopropylamino, dimethylamino, diethylamino,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, where Y can be the same or different,
n represents 1, 2 or 3,
Z for the rest

stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, methyl, ethyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, allyl or propargyl,
R⁵ and R⁶ independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, halogen-C₁-C₄-alkyl having 1 to 5 identical or different fluorine and chlorine atoms,
R⁷ for hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, vinyl, allyl, ethynyl, propargyl, halogen-C₁-C₄-alkyl with 1 to 5 identical or different fluorine and chlorine atoms or
R⁴ and R⁵ together with the carbon and nitrogen to which they are attached form a 3- to 6-membered heterocyclic ring which is optionally monosubstituted or disubstituted by fluorine, chlorine, methyl and ethyl and which one or two May contain double bonds, or
R⁶ and R⁷ together with the carbon to which they are attached form a 3- to 6-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur as ring members and which may optionally be up to ten times the same or different by fluorine, chlorine, Methyl and ethyl is substituted and which can contain one or two double bonds, and
R⁸ represents hydrogen, optionally mono- to triple, identical or different, substituted by fluorine, chlorine and bromine, C₁-C₄-alkyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, allyl or propargyl and
R ^5-1 and R ^6-1 each independently represent methyl, ethyl, n-propyl and isopropyl.

The group of compounds of the formula (I) in which
Z for the rest

stands and
D stands for <NH and
B represents oxygen or sulfur and
R¹, R², R³, R⁵, R⁶, R⁷, A, X, Y and n have the above preferred meaning.

Another group of very particularly preferred compounds of the formula (I) are those in which
Z for the rest

stands and
R¹, R², R³, R⁵, R⁶, R⁷, R⁸, A, X, Y and n have the meaning as particularly preferred above.

The 2-pyri (mi) dyl-2′-pyridyl (thio) ethers of the formula (Ia₁) listed in Table 1 below may be mentioned by way of example:

If 2- (5-amino-pyridyl-2-oxy) -4,6-dimethyl-pyrimidine is used and pivaloyl chloride as starting materials, so can the course of the method according to the invention (A-a₁) can be represented by the following formula:

If 2- (5-aminopyridyl-2-oxy) -4,6-dimethylpyrimidine is used and isobutyric anhydride as starting materials, so can the course of the method according to the invention (A-a₂) represented by the following formula will:

If 2- (5-amino-pyridyl-2-oxy) -4,6-dimethyl-pyrimidine is used and ethyl pivaloyl carbonic acid anhydride as starting materials, the course of the invention Process (A-a₃) by the following formula are reproduced:

If 2- (5-amino-pyridyl-2-oxy) -4,6-dimethyl-pyrimidine is used and O-pivaloyloxydicyclohexyl isourea as starting materials, the course of the invention Process (A-a₄) by the following formula are reproduced:

If 2-chloro-4,6-dimethyl-pyrimidine and N- (6-hydroxy-pyrid-3-yl) -pivaloyl amide are used as raw materials, so can the course of the method according to the invention (B) represented by the following formula scheme will:

If 2-mercapto-4,6-dimethyl-pyrimidine and 6-chloro-nicotinic acid tert-butylamide are used as raw materials, the course of process (C) according to the invention can be represented by the following formula:

If 6-mercapto-nicotinic acid tert-butylamide is used and 2-chloro-4,6-dimethyl-pyrimidine as starting materials, the course of the method (D) according to the invention can be represented by the following formula:

If 2- (5-pivaloylamino-pyridyl-2-thio) -4,6-dimethyl-pyrimidine is used and Lawesson's reagent as raw materials, so can the course of the method according to the invention (E) represented by the following formula scheme will:

If 2- [4,6-dimethyl-pyrimidyl] -6-mercapto-thionicotinic acid tert-butylam-id is used and allyl bromide as Starting materials, the course of the invention Method (F) by the following formula scheme are reproduced:

Formula (II) provides a general definition of the compounds required as starting materials in process (A) according to the invention. In this formula, R.sup.1, R.sup.2, R.sup.3, X, Y and n preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals or this index.

The compounds of formula (II) are known or can be produced by known methods by one

• α ) Pyri (mi) din derivatives of the formula in which
  R¹, R², R³ and Hal have the meaning given above,
  with 2-hydroxy- (mercapto -) - 4-aminopyridines of the formula in which
  X, Y and n have the meaning given above,
  in the presence of an acid binder and, if appropriate, in the presence of a diluent,
  or
• β ) 2- (4-nitro-pyridyl-2-oxy (thio) pyri (mi) din derivatives of the formula in which
  R¹, R², R³, X, Y and n have the meaning given above,
  optionally reduced in the presence of a diluent by customary methods.

Formula (IV) defines the pyri (mi) din derivatives required as starting materials in process ( α ) above. In this formula, R.sup.1, R.sup.2 and R.sup.3 preferably have those meanings which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention. Hal preferably represents fluorine, chlorine or bromine. The pyri (mi) din derivatives of the formula (IV) are known or can be prepared in a simple manner by methods which are known in principle. Thus, pyri (mi) din derivatives of the formula (IV) are obtained, for example, by adding 2-hydroxy-pyri (mi) din derivatives (dihydro-pyri (mi) don-2 derivatives) with inorganic acid halides, such as e.g. B. phosphorus oxychloride or phosphorus pentachloride, or by reacting corresponding 2-amino-pyrimidine derivatives with nitrous acid in the presence of hydrohalic acids.

Formula (X) defines the compounds which are furthermore required as starting materials in process ( α ) . In this formula, X, Y and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention, preferably for these radicals or for this index.

The compounds of the formula (X) are known or have not been used yourself in principle using known methods Create way.  

All acid acceptors that can usually be used for such reactions can be used as acid binders when carrying out process ( α ) . Alkali and alkaline earth oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, calcium oxide, sodium carbonate and potassium carbonate, are also preferably usable, furthermore alkali alcoholates, amides and hydrides, such as, for. B. sodium methylate, sodium ethylate, potassium tert-butoxide, sodium amide and sodium hydride.

All customary inert organic solvents can be used as diluents when carrying out process ( α ). Hydrocarbons such as gasoline, toluene and xylene, furthermore ethers such as dioxane, glycol dimethyl ether and diglycol dimethyl ether, preferably nitriles such as acetonitrile and also strongly polar solvents such as dimethyl sulfoxide, sulfolane, N-methylpyrrolidone and dimethylformamide are preferred.

The reaction temperatures can be varied within a substantial range when carrying out process ( α ) . In general, temperatures between 0 ° C and 200 ° C, preferably between 50 ° C and 150 ° C.

The reaction according to process ( α ) is generally carried out under normal pressure.

When carrying out process ( α ), the starting materials of the formulas (IV) and (X) are generally reacted in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess. The processing takes place according to usual methods.

The compounds required as starting materials in process ( β ) are defined by the formula (XI). In this formula, R 1, R 2, R 3, X, Y and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention preferably for these radicals or for this index.

The compounds of formula (XI) are known or can be simplified using methods that are known in principle Create a way (see e.g. Eur. J. Med. Chem. 19 (6) 559-565 (1984)). How to get connections to the Formula (XI) e.g. B. by having pyri (mi) din derivatives of the formula

in which
R¹, R², R³, A and Hal have the meaning given above,
with compounds of the formula

in which
X, Y and n have the meaning given above,
in the presence of an acid binder and optionally in the presence of a diluent at temperatures between 0 ° C. and 200 ° C., preferably between 50 ° C. and 150 ° C.,
or that compounds of the formula (VI)

in which
R¹, R², R³, A and X have the meaning given above,
with compounds of the formula (XIIa)

in which
Y has the meaning given above and
Hal² is halogen, preferably chlorine or fluorine,
in the presence of an acid binder and optionally in the presence of a diluent at temperatures between 0 ° C. and 200 ° C., preferably between 50 ° C. and 150 ° C.

Suitable acid binders and diluents here are preferably those substances which have already been mentioned in connection with process ( α ) as acid acceptors and solvents which can preferably be used.

The compounds of formula (XII) and (XIIa) are known Compounds of organic chemistry and leave produce themselves by known methods.

Suitable as reducing agents in process ( β ) are all those substances which are usually used for the reduction of aromatic nitro compounds. Elemental metals such as iron, zinc and tin are preferably usable, furthermore metal compounds in lower valence levels such as iron (II) and tin (II) salts, and also non-metal compounds in low valence levels such as e.g. B. salts of hydrogen sulfide, alkali sulfites and alkalidithionites. Otherwise, the reduction can also be carried out by catalytic hydrogenation with hydrogen in the presence of a catalyst, such as. B. Raney nickel.

Suitable diluents in process ( β ) are all organic solvents which are customary for such reductions. The reaction temperatures can be varied within a substantial range. They correspond to the temperatures used in analog reactions; in general, temperatures between 20 ° -200 ° C, preferably between 40 ° -100 ° C and pressures of 1-200 bar, preferably 10-100 bar.

The reduction is carried out according to process ( β ) and the reaction mixture obtained is worked up using customary methods.

The in the inventive method (A-a₁) as Reaction components required are acid halides clearly defined by the formula (IIIa). In this Formula R⁵, R⁶ and R⁷ preferably have those meanings, the already related to the description the substances of the formula (I) according to the invention were preferably mentioned for these residues. Hal is standing preferably for fluorine, chlorine and bromine.

The acid halides of the formula (IIIa) are known or can be simplified using methods that are known in principle Create way.

As acid binders come in the implementation after The inventive method (A-a₁) all the usual acid acceptors into consideration. Are preferably usable tertiary amines, such as triethylamine, pyridine and N, N-dimethyl-aniline, also alkaline earth metal oxides, such as  Sodium carbonate, potassium carbonate and calcium carbonate. It it is also possible to use the respective compounds of the formula (II) to be used simultaneously as an acid binder. To do this, the connection in question must at least be in be used in such a quantity that the released Hydrogen halide can be bound.

As a diluent in the invention Process (A-a₁) all inert towards acid halides Solvents are used. Preferably used are hydrocarbons such as gasoline, benzene, toluene, Xylene and tetralin, also hydrogen halide, such as methylene chloride, chloroform, carbon tetrachloride, Chlorobenzene and o-dichlorobenzene, also ketones, such as Acetone and methyl isopropyl ketone, further ether, such as Diethyl ether, tetrahydrofuran and dioxane, in addition Carboxylic acid esters, such as ethyl acetate, and also strongly polar ones Solvents such as dimethyl sulfoxide and sulfolane. If the Hydrolysis stability of the acid halide allows it the reaction is also carried out in the presence of water will.

The reaction temperatures can be carried out of the method (A-a₁) within a larger range can be varied. Do you work in the present? a diluent and an acid binder, the reaction temperatures are generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.  

The inventive method (A-a₁) is generally carried out under normal pressure.

When carrying out the method according to the invention (A-a₁) are the starting materials of the formulas (II) and (IIIa) generally in approximately equivalent amounts used. However, it is also possible to use one or the other use other components in a larger excess. The processing then takes place according to the usual Methods. In general, the procedure is to be unusual Salts removed and the remaining reaction mixture by removing the diluent. You work in the presence of water or with water miscible solvents, you can also do this that the reaction mixture is diluted with water, the aspirated mixture or with a little water miscible organic solvent extracted that organic phase washes, concentrates and the remaining Residue, if necessary, the usual cleaning method submits.

The in the inventive method (A-a₂) as Reaction components require symmetrical carboxylic acid anhydrides are clear from the formula (IIIb) Are defined. In this formula, R⁵, R⁶ and R⁷ preferably have those meanings that are already related with the description of the substances according to the invention of formula (I) preferably mentioned for these radicals were.  

The symmetrical carboxylic anhydrides of the formula (IIIb) are known or rely on known in principle Create methods in a simple way.

As a diluent when performing the inventive method (A-a₂) preferably those Thinners are also used the method (A-a₁) are preferably considered. Otherwise, an excess of carboxylic acid anhydride can also be used of the formula (IIIb) simultaneously as a diluent act.

The reaction temperatures can also in the inventive Process (A-a₂) within a larger one Range can be varied. Generally you work at temperatures between -20 ° C and + 150 ° C, preferably between -20 ° C and + 150 ° C, preferably between 0 and 100 ° C.

The process (A-a₂) according to the invention is generally carried out under normal pressure.

When carrying out the method according to the invention (A-a₂) are the starting materials of the formulas (II) and (IIIb) generally in approximately equivalent amounts used. However, it is also possible to use the carboxylic anhydride use in a larger excess. The Refurbishment is carried out using customary methods.

The general procedure is to use diluents and excess carboxylic acid anhydride and the resulting carboxylic acid by distillation  or by washing with an organic solvent or removed with water.

The in the process (A-a₃) as reaction components required asymmetric acid anhydrides are clearly defined by the formula (IIIc). In this formula, R⁵, R⁶ and R⁷ preferably have those Meanings already related to the Description of the substances of the formula (I) according to the invention were preferably mentioned for these residues. R stands preferably for alkyl with 1 or 2 carbon atoms or phenyl.

The asymmetric acid anhydrides of formula (IIIc) are known or can be known in principle Create methods in a simple way. So you get Compounds of formula (IIIc) in that carboxylic acids of the formula

in which
R⁵, R⁶ and R⁷ have the meaning given above,
with carbonic acid ester chlorides of the formula

in which
R has the meaning given above,
in the presence of a diluent, such as. B. methylene chloride, and in the presence of an acid binder, such as. B. triethylamine, at temperatures between -20 ° C and + 100 ° C, preferably between 0 and 50 ° C. The asymmetric acid anhydrides of the formula (IIIc) are generally not isolated in pure form, but are further processed in the form obtained, if appropriate after the diluent and / or salts have been removed beforehand.

As a diluent when performing the inventive method (A-a₃) preferably those Thinners are also used the method (A-a₁) are preferably considered. In addition, acid anhydride used in excess of the formula (IIIc) simultaneously as a diluent act.

The reaction temperatures can also in the inventive Process (A-a₃) within a larger one Range can be varied. Generally you work at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.  

The process (A-a₃) according to the invention is generally carried out under normal pressure.

When carrying out the method according to the invention (A-a₃) are the starting materials of the formulas (II) and (IIIc) generally in approximately equivalent amounts used. However, it is also possible to use the acid anhydride use in a larger excess. The workup takes place according to usual methods.

The reaction components in the process (A-a erfindungsgemäßen) according to the invention required connections are through the Formula (IIId) clearly defined. In this formula R⁵, R⁶ and R⁷ preferably have those meanings, that already in connection with the description of the invention Substances of formula (I) preferably for these residues were called.

The compounds of formula (IIId) are known or can be done in a simpler manner by methods known in principle Create way. How to get connections to the Formula (IIId) in that carboxylic acids of the formula

in which
R⁵, R⁶ and R⁷ have the meaning given above,
with dicyclohexylcarbodiimide of the formula

implements.

As a diluent when performing the inventive method (A-a₄) preferably those Thinners are also used the method (A-a₁) are preferably considered.

The reaction temperatures can also in the inventive Procedure (A-a₄) within a larger one Range can be varied. Generally you work at temperatures between -20 ° C and + 150 ° C, preferably between 0 and 100 ° C.

The process (A-a₄) according to the invention is generally carried out under normal pressure.

When carrying out the method according to the invention (A-a₄) are the starting materials of the formulas (II) and (IIId) generally in approximately equivalent amounts used. The processing takes place according to usual Methods.

The pyrimidine derivatives of the formula (IV) required as starting materials in process (B) according to the invention have already been dealt with in connection with the description of process ( α ) .

Formula (V) clearly defines the acylaminopyridine derivatives required as starting materials in process (B) according to the invention. In this formula, R⁵, R⁶, R⁷, X, Y and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I), preferably for these radicals or for this index.

The compounds of the formula (V) are known or have not been used produce themselves according to known methods. So obtained acylaminopyridine derivatives of the formula (V) z. B. in that 4-aminopyridine derivatives of the formula

in which
X, Y and n have the meaning given above,
with acid halides of the formula

in which
R⁵, R⁶, R⁷ and Hal have the meaning given above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder. The reaction conditions correspond to those which are also used in carrying out process (A-a₁).

As acid binders can be in the implementation of Process (B) according to the invention includes all customary acid acceptors be used. Preferably used are alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide Magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, also alkali metal and Alkaline earth metal amides and hydrides, such as sodium amide, Sodium hydride and calcium hydride, and moreover Alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide.

As a diluent in the invention Process (B) all customary inert organic solvents be used. Are preferably usable Hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether and on polar solvents, such as dimethyl sulfoxide, sulfolane, Dimethylformamide and N-methyl-pyrrolidone.  

The reaction temperatures can be carried out of the inventive method (B) within a larger range can be varied. In general you work at temperatures between 50 and 200 ° C, preferably between 100 and 180 ° C.

The process (B) according to the invention is generally carried out under normal pressure.

When carrying out the method according to the invention (B) the reaction components of the formulas (IV) and (V) generally in approximately equimolar amounts. However, it is also possible to use one or the other component to use in a larger excess. Furthermore an equimolar amount is generally also used acid-binding agent. However, it can also be beneficial be the acid binder in one to one molar Add excess. One goes in detail generally so that the acid-binding agent to a mixture of the reaction components in a suitable Diluent there. But you can also in proceed in such a way that first of all from the acylaminopyridine derivative of the formula (V) and the acid binder generates a salt and then this with a pyri (mi) din derivative of the formula (IV). Furthermore it is possible from the acylaminopyridine derivative of the formula (V) with an acid binder, separately a salt produce, then isolate and then in the presence of a suitable diluent without further addition of an acid binder with a pyri (mi) din derivative implement the formula (IV). The workup takes place according to the usual methods.  

The starting materials in process (C) according to the invention required 2-hydroxy (mercapto) pyri (mi) din derivatives are clearly defined by the formula (VI). In this formula, R¹, R², R³, A and X preferably have those meanings that are already related to the description of the substances of the formula (I) preferably mentioned for these substituents were.

The compounds of formula (VI) are known or can be produced by known methods by for example, 2-hydroxy-pyri (mi) dine with phosphorus-V-sulfide or the Lawesson reagent or 2-halogenopyri (mi) dine with metal salts of hydrogen sulfide such as sodium sulfide or with alkali metal hydroxides such as sodium hydroxide in in the usual way or by using 1,3-diketones with thiourea in the usual way implements.

The formulas (VIIa) and (VIIb) generally define the 2-halogeno-nicotinic acid derivatives required to carry out the processes (C-C₁) and (C-C₂) as starting materials. In the formulas (VIIa) and (VIIb), R⁵, R⁶, R⁷, R ^5-1 , R ^6-1 , D, Y and n preferably have those meanings which are preferred in the description of the substances of the formula (I) according to the invention for these substituents. Hal¹ is preferably chlorine or bromine.

The 2-halogen nicotinic acid derivatives of the formulas (VIIa) and (VIIb) are known or can be made according to known ones  Manufacture methods by using 2-halogen nicotinic acid Carboxylic acid chlorides such as benzenesulfonyl chloride converted into mixed carboxylic anhydrides and then reacted with alcohols in the usual manner (see manufacturing examples).

As diluents and acid binders, the inventive methods (C-C₁) and (C-C₂) all usual inert organic solvents or acid acceptors be used. Preferably used the diluents and acid binders that already in process (B).

The reaction temperatures can be carried out the inventive method (C-C₁) and (C-C₂) within a wide range can be varied. In general one works at temperatures between 80 to 200 ° C, preferably at 110 to 180 ° C.

When carrying out the method according to the invention (C) the reaction components of the formulas (VI) and (VIIa) and (VIIb) in general approximately equimolar Quantities. However, it is also possible to use one or other component in a larger excess use. In addition, one generally also uses one equimolar amount of acid-binding agent.

Formula (VIII) provides a general definition of the 2-hydroxy (mercapto) nicotinic acid derivatives required as starting materials in process (D) according to the invention. In the formula (VIII), R⁵, R⁶, R⁷, D, X, Y and n preferably have those meanings which have already been mentioned preferably for these substituents or this index in the description of the substances of the formula (I) according to the invention.

The compounds of formula (VIII) are known or can be produced by known methods. So win man 2-hydroxy and 2-mercaptonicotinic acid esters by esterifying the corresponding free acids with Alcohols in the presence of strong acids according to usual Methods (see e.g. making connections of formula (VII)).

The pyri (mi) din derivatives of the formula (IV) which are furthermore required as starting materials for carrying out process (D) according to the invention have already been dealt with in the description of process ( α ) .

As diluents and acid binders, the method (D) according to the invention all the usual inert organic solvents or acid acceptors be used. It is preferred to use the at Process (B) called diluents and acid binders.

The reaction temperatures can be carried out of the inventive method (D) within a larger range can be varied. In general one works at temperatures between 80 to 250 ° C, preferably at 110 to 180 ° C.  

The processes (C) and (D) according to the invention are described in generally carried out at normal pressure. However, it is also possible to work at increased or reduced pressure.

When carrying out the method according to the invention (D) the reaction components of the formulas (VII) and (IV) generally in approximately equimolar amounts. However, it is also possible to use one or the other component to use in a larger excess. Furthermore an equimolar amount is generally also used acid-binding agent.

The compounds of the formula (Ia) required as starting materials for carrying out process (E) according to the invention are substances according to the invention and can be obtained by processes (A-a₁), (A-a₂), (A-a₃), (A-a₄), (B), (C) and (D). In the formula (Ia), R¹, R², R³, R⁵, R⁶, R⁷, A, D, X, Y and n preferably have those meanings which, when describing the substances of the formula (I) according to the invention, preferably for these substituents or were called this index.

As a diluent for carrying out the invention Process (E) come with inert organic solvents in question. These include in particular aliphatic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene,  Toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, Dichloromethane, chloroform, carbon tetrachloride, Ethers such as diethyl ether, dioxane or tetrahydrofuran. The reaction temperatures can be carried out of the inventive method (E) within a larger range can be varied. Generally works one at temperatures between +20 and + 200 ° C, preferably between 50 and 150 ° C.

The process (E) according to the invention is generally carried out under normal pressure. However, it is also possible to work at increased or reduced pressure.

To carry out process (E) according to the invention is set per mol of compound of formula (Ia) 1.0 to 5.0 moles, preferably 1.0 to 2.0 moles, of sulfurizing agents a.

In the compounds of the formula (Ib) required as starting materials in process (F) according to the invention, D represents <NH and R¹, R², R³, R⁵, R⁶, R⁷, A, D, X, Y and n preferably have the meanings which have already been mentioned in the description of the substances of the formula (I) according to the invention preferably for these substituents or this index. The compounds of formula (Ib) in which D represents -NH are compounds according to the invention and can be obtained by process (E).

The continue in the inventive method (F) Compounds required as starting materials are through the formula (IX) is generally defined. In the formula (IX) R⁸ preferably has the meaning that already at the description of the substances of the formula (I) was preferably mentioned for this substituent. F preferably represents chlorine, methylsulfonyloxy, Ethylsulfonyloxy or phenylsulfonyloxy.

The compounds of formula (IX) are generally known Organic Chemistry Compounds.

As deprotonating bases for carrying out the invention Process (F) come all the usual for bases usable in such reactions. Preferably one uses alkali alcoholates such as Potassium tert-butoxide, sodium methylate, sodium butoxide, Sodium or potassium hydroxide, potassium carbonate, Sodium or lithium hydride.

As a diluent for carrying out the invention Process (F) come with inert organic solvents in question. Alcohols such as are preferably used for example tert-butanol, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, Sulfolan, tetrahydrofuran or dioxane.  

The reaction temperatures can be carried out of the inventive method within a larger range can be varied. Generally works one at temperatures between 0 and 200 ° C, preferably at 20 to 120 ° C.

The process (F) according to the invention is generally carried out at normal pressure. However, it is also possible work at elevated or reduced pressure.

The active compounds according to the invention can be used as defoliants, Desiccants, herbicides and especially as Weed killers are used. Under weeds in the broadest sense, all plants are to be understood that growing up in places where they are undesirable. If she Substances according to the invention as total or selective herbicides work depends essentially on the applied Amount off.

The active compounds according to the invention can, for. B. in the following Plants are used:

Dicotyledon weeds of the genera:
Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convovulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippernia, Rorippa, Rorippa, Rorippa Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledon cultures of the genera:
Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocot weeds of the genera:
Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Spochhenium, Ischatenumum, Ischaeaeaum Agrostis, Alopecurus, Apera.

Monocot cultures of the genera:
Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

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

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and track systems and on paths and squares with and without Tree growth. Likewise, weed control compounds in permanent crops, e.g. B. forest, ornamental wood, Fruit, wine, citrus, nut, banana, coffee, tea, Gum, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annuals Cultures are used.  

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, wettable powders, Suspensions, powders, dusts, pastes, soluble Powders, granules, suspension emulsion concentrates, Active substance-impregnated nature and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, So liquid solvents and / or solid Carriers, optionally using surfactants Agents, i.e. emulsifiers and / or Dispersing agents and / or foaming agents.

In the case of the use of water as an extender e.g. B. also organic solvents as auxiliary solvents be used. As a liquid solvent essentially come into question: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene 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.

The following are suitable as solid carriers: e.g. B. ammonium salts and natural rock powders, such as Kaolins, clays, talc, chalk, quartz, attapulgite,  Montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates, come as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules from organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as Emulsifying and / or foaming agents are possible: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether, 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 can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

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

The formulations generally contain between 0.1 and 95 percent by weight of active 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 ones Find herbicides for weed control, wherein Ready formulations or tank mixes are possible.

Known herbicides such as z. B. 1-Amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) - dione or N- (2-benzothiazoly) -N, N'-dimethyl-urea for weed control in cereals; 4-Amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) - 3-methylthio-1,2,4-triazin-5 (4H) -one for Weed control in soybeans, in question. Some mixes surprisingly also show synergistic Effect.

Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, Protection against bird feed, plant nutrients and Soil improvers are possible.

The active ingredients as such, in the form of their formulations or the one prepared therefrom by further dilution Application forms, such as ready-to-use solutions, Suspensions, emulsions, powders, pastes and Granules can be applied. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, Scatter.

The active compounds according to the invention can be used both before and can also be applied after the plants have emerged.  They can also be worked into the soil before sowing will.

The amount of active ingredient used can be greater Fluctuate range. It essentially depends on the Type of effect desired. Generally lie the application rates between 0.01 and 10 kg of active ingredient per Hectares of soil, preferably between 0.05 and 5 kg per hectare

The production and use of the invention Active ingredients are shown in the following examples.

Manufacturing examples example 1 Process (A-a₁)

3.46 g (16 mmol) of 2- (5-aminopyridyl-2-oxy) -4,6-dimethyl-pyrimidine are dissolved in 50 ml of absolute tetrahydrofuran and 2.24 ml (16 mmol) of triethylamine were added. At 0 ° -5 ° C, 2.78 ml (17.6 mmol) of pivaloyl chloride, dissolved in 5 ml of absolute tetrahydrofuran, added dropwise and Stirred for 15 minutes. The mixture is made up to 250 ml Poured ice water, suctioned off and dried. After recrystallization chloroform / n-hexane gives 2.93 g (61% of theory) 2- (5-pivaloylamino-pyridyl-2-oxy) -4,6-dimethyl-pyrimidine melting point 147 ° C.

Example 2 Process (A-a₁)

4.64 g (20 mmol) -2- (5-aminopyridyl-2-thio) -4,5-dimethyl-pyrimidine are dissolved in 50 ml absolute tetrahydrofuran and 2.8 ml (20 mmol) triethylamine are added. At 0 ° -5 ° C, 2.86 ml (22 mmol) of β- chloropivaloyl chloride are added dropwise and the mixture is stirred at room temperature under thin-layer chromatography. The 2- (5- β- chloropivaloylamino-pyridyl-2-thio) -4,5-dimethyl-pyrimidine obtained after stirring in 250 ml of ice water is dried and recrystallized from chloroform. 5.24 g (75% of theory) of the desired product with a melting point of 175 ° C. are obtained.

Example 3 Procedure (E)

6.33 g (20 mmol) of 2- (5-pivaloylamino-pyridyl-2-thio) -4,6-dimethyl-pyrimidine and 4.4 g (16 mmol) Lawesson's reagent are controlled in 20 ml of absolute toluene Thin layer chromatography heated under reflux. To Cooling to room temperature is followed by column chromatography with cyclohexane / ethyl acetate 1: 2. After Crystallization from ethyl acetate / ether / n-hexane at -78 ° C, 2.58 g (39% of theory) of 2- (5-thiopivaloylamino-pyridyl-2-thio) -4,6-dimethyl-pyrimidine are obtained melting point 97-98 ° C.

Example 4 Process (C)

35.3 g (0.2 mol) of 2-mercapto-4,6-dimethylpyrimidine hydrochloride are in 250 ml of N-methylpyrrolidone under nitrogen with 26.88 g (0.48 mol) of powdered potassium hydroxide added and stirred for 15 minutes. After encore of 42 g (0.2 mol) of 6-chloro-nicotinic acid tert-butylamide is checked under thin layer chromatography Heated to 150 ° C. The reaction mixture is poured onto 1.5 l of ice water poured, extracted with methylene chloride, in vacuo evaporated, taken up with 200 ml of methanol, again stirred in 1.5 l of ice water, suctioned off and with Ether washed. After recrystallization from toluene / n-hexane 30.9 g (49% of theory) of 2 - [(4,6-dimethyl-pyrimidyl) -2-mercapto] -nicotinic acid-tert-butylamide are obtained Melting point 128 ° C.

Example 5 Procedure (E)

28.47 g (90 mmol) 2 - [(4,6-dimethyl-pyrimidyl) -2-mercapto] -nicotinic acid-tert-butylamide- and 19.8 g (49.5 mmol) Lawesson's reagent is submerged in 90 ml of absolute toluene Thin layer chromatography control heated under reflux. After purification using column chromatography (Toluene / acetone 9: 1 and cyclohexane / ethyl acetate 1: 1) 11.84 g (40% of theory) of 2 - [(4,6-dimethyl-pyrimidyl) -6-mercapto] -thionicotinic acid tert-butyl amide are obtained melting point 95 ° C.  

Example 6 Procedure (F)

3.32 g of 2- (4,6-dimethyl-pyrimidyl) -6-mercapto) -thionicotinic acid tert-butyla-mid are in 40 ml of tert-butanol at 50 ° C with 1.35 g (12 mmol) of potassium tert-butoxide and stirred for 15 minutes. After adding 1.05 ml (12 mmol) allyl bromide is added for a further 15 minutes touched. The reaction mixture is in 150 ml of water stirred in, extracted 3 times with toluene, with sodium sulfate dried and evaporated. After cleaning with Column chromatography (cyclohexane / ethyl acetate 2: 1) and subsequent crystallization from n-hexane 2.41 g (65% of theory) of 2 - [(4,6-dimethyl-pyrimidyl) -6-mercapto] nicotinic acid S-allyl tert-b-utylimino ester from melting point 63 ° C.

Example 7 Process (C)

5.3 g (30 mmol) 2-mercapto-4,5-dimethylpyrimidine hydrochloride are in 20 ml of N-methylpyrrolidone under nitrogen submitted with 3.7 g (66 mmol) powdered Potassium hydroxide added and stirred for 15 minutes. To Add 6.82 g (30 mmol) of tert-butyl 6-chloronicotinate is under thin layer chromatography control heated to 150 ° C. The reaction mixture is in Sodium bicarbonate solution poured, vacuumed and chromatographed with cyclohexane / ethyl acetate 2: 1. After crystallization from toluene / n-hexane 6.61 g (69% of theory) of tert-butyl 2- [4,5-dimethyl-pyrimidyl-6-mercapto] nicotinate from the melting point 102 ° C.

According to the previous examples and in the description given methods you also get the in the connections listed in Tables 5-8 of formula (I)

Table 7

Table 8

Table 9

Manufacture of raw materials Example II-1

27 g (0.105 mol) of 2- (5-nitro-pyridyl-2-oxy) -4,6-dimethyl-pyrimidine in 180 ml of dioxane with hydrogen in the presence of 5 g of Raney nickel under a pressure of 50 bar between 20 ° C and 60 ° C exhaustively hydrogenated. To The solvent is filtered off in the Vacuum evaporated and the residue from chloroform / n-hexane recrystallized. 14.12 g (59% of theory) are obtained 2- (5-amino-pyridyl-2-oxy) -4,6-dimethyl-pyrimidine from Melting point 180 ° C.

Production of the preliminary product

47.15 g (0.25 mol) of 2-hydroxy-4,6-dimethylpyrimidine hydrochloride are in 300 ml of isopropanol under nitrogen submitted. 56.1 g (0.5 Mol) potassium tert-butoxide, stirred for 15 minutes and heated after adding 39.61 g (0.25 mol) of 2-chloro-5-nitropyridine 48 hours under reflux.  

After evaporation in vacuo, the residue is with Methylene chloride added, washed with water, with Dried sodium sulfate and concentrated in vacuo. To Column chromatography with cyclohexane / ethyl acetate 2: 1 and recrystallization from toluene / n-hexane 20.6 g (32% of theory) of 2- (5-nitropyridyl-2-oxy) -4,6-dimethylpyrimidine melting point 74 ° C.

Example II-2

90.5 g (0.33 mol) of 2- (5-nitropyridyl-2-thio) -4,6-dimethylpyrimidine are in 1 l of dioxane with hydrogen in Presence of 20 g of Raney nickel under a pressure of 60 bar exhaustively hydrogenated at 20-70 ° C. After filtering of the catalyst and concentration of the solvent it is recrystallized from chloroform / toluene in vacuo. 71.07 g (89% of theory) of 2- (5-aminopyridyl-2-thio) -4,6-dimethylpyrimidine are obtained melting point 187 ° C.

Production of the preliminary product

84.2 g (0.476 mol) of 2-mercapto-4,6-dimethylpyridine hydrochloride are placed in 1 liter of absolute ethanol, with 53.35 g (0.952 mol) of powdered potassium hydroxide added and stirred for 15 minutes. After adding 75.5 g (0.476 mol) 2-chloro-5-nitropyridine is left for 1 hour heated under reflux. After cooling to room temperature the solid is suctioned off and washed twice with 200 ml each Ethanol after. After changing the template, you wash the Filter residue several times with methylene chloride, that narrows Filtrate and recrystallized from ethanol. Man receives 90.55 g (73% of theory) of 2- (5-nitro-pyridyl-2-thio) -4,6-dimethylpyrimidine melting point 130-133 ° C.

Example II-3

Mp 122 ° C, recrystallization from chloroform / n-hexane

Example II-4

Mp 161-162 ° C, recrystallization from chloroform / n-hexane

Example II-5

Mp 106 ° C, recrystallization from chloroform  

Example VII-1

To 15.75 g (0.1 mol) of 6-chloro-nicotinic acid in 100 ml of absolute Pyridine become 25.6 ml (0.2 mol) of benzenesulfochloride dripped while cooling. Drips after an hour 19.2 ml (0.2 mol) of tert-butanol are added at 0-5 ° C. with 400 mg of 4-N, N'-dimethylaminopyridine, one stirs Hour at room temperature, 6 hours at 60 ° C and above Night at room temperature. The reaction mixture is in 250 ml of H₂O entered, extracted 3 × with toluene, dried evaporated over sodium sulfate and in vacuo. After recrystallization from toluene / n-hexane, one obtains 12.62 g (59% of theory) of the desired product from Melting point 52 ° C.

Example VII-2

69.5 g (0.5 mol) of 6-hydroxy nicotinic acid are dissolved in 110 ml (1.5 mol) thionyl chloride and 0.5 ml dimethylformamide heated under reflux until no more gas evolution is observed. Excess thionyl chloride is in the  Vacuum removed, the residue in 250 ml of absolute Dissolved tetrahydrofuran and at 0-5 ° C to 105 ml (1 mol) tert-butylamine in 300 ml of absolute tetrahydrofuran dripped. The reaction mixture is suctioned off with Washed tetrahydrofuran, the filtrate in vacuo evaporated and the residue recrystallized from toluene / n-hexane. 82.8 g (78% of theory) of 6-chloronicotinic acid tert-butylamide are obtained from the melting point 100 ° C.  

Example A Pre-emergence test

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

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water on the desired concentration.

Seeds of the test plants are sown in normal soil and watered with the active ingredient preparation after 24 hours. The amount of water per unit area is kept expediently constant. The drug concentration in the preparation does not matter, it is crucial only the application rate of the active ingredient per unit area. After three weeks, the degree of damage to the plants rated in% damage compared to development the untreated control. It means:

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

Example B Post emergence test

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

For the preparation of a suitable active ingredient preparation you mix 1 part by weight of active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with Water to the desired concentration.

With the preparation of the active ingredient you inject test plants, which have a height of 5-15 cm so that they each desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 2000 l of water / ha each desired amounts of active ingredient are applied. To The degree of damage to the plants is three weeks rated in% damage compared to development the untreated control. It means:

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

Claims (8)

1. 2-pyri (mi) dyl-2'-pyridyl (thio) ether of the formula (I), in which
R¹, R² and R³ independently of one another each represent hydrogen, halogen, alkyl, alkoxy or alkylthio each having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, amino, alkylamino or dialkylamino each having 1 to 6 carbon atoms in the individual alkyl parts,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, halogen, cyano, alkyl or alkoxy each having 1 to 6 carbon atoms, where Y can be the same or different and
n stands for a number from 1 to 3 and
Z for the rest or stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, alkyl or alkoxyalkyl each having 1 to 6 carbon atoms, alkenyl or alkynyl each having 3 to 6 carbon atoms,
R⁵, R⁶ and R⁷ each independently represent hydrogen, halogen, cyano, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms and up to 13 halogen atoms, alkenyl or alkynyl each having 2 to 6 carbon atoms,
R⁴ and R⁵ together with the carbon and the nitrogen to which they are attached form a 3 to 8-membered heterocyclic ring which is optionally substituted one or more times, identically or differently, by halogen, methyl and ethyl and which may contain one or more double bonds .
R⁶ and R⁷ together with the carbon to which they are attached form a 3 to 8-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur atoms as ring members and which, if appropriate, one or more times, identically or differently, by halogen, methyl and Ethyl is substituted and which may contain one or more double bonds and
R⁸ represents hydrogen, optionally mono- or polysubstituted, identically or differently, by halogen-substituted alkyl having 1 to 6 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms per alkyl part, alkenyl or alkynyl each having 3 to 6 carbon atoms and
R ^5-1 and R ^6-1 each independently represent alkyl having 1 to 6 carbon atoms. 2. 2-pyri (mi) dyl-2'-pyridyl (thio) ether of the formula (I) according to claim 1, in which
R¹, R² and R³ each independently represent hydrogen, fluorine, chlorine, bromine, iodine, alkyl, alkoxy or alkylthio each having 1 to 4 carbon atoms, trifluoromethyl, amino, alkylamino or dialkylamino each having 1 to 4 carbon atoms in the individual alkyl parts ,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, alkyl or alkoxy each having 1 to 4 carbon atoms, where Y can be identical or different,
n represents 1, 2 or 3,
Z for the rest stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, alkyl or alkoxyalkyl each having 1 to 4 carbon atoms in the individual alkyl parts, alkenyl or alkynyl each having 3 to 4 carbon atoms,
R⁵, R⁶ and R⁷ each independently represent hydrogen, halogen, cyano, alkyl having 1 to 5 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms or
R⁴ and R⁵ together with the carbon and nitrogen to which they are attached form a 3 to 7-membered heterocyclic ring which is optionally monosubstituted to 12-fold substituted, identically or differently, by fluorine, chlorine, bromine, methyl and ethyl and which one to can contain two double bonds, or
R⁶ and R⁷ together with the carbon to which they are bonded form a 3 to 7-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur as ring members and which may optionally be up to twelve times, the same or different, by fluorine, chlorine, Bromine, methyl and ethyl is substituted and can contain one to three double bonds, and
R⁸ for hydrogen; represents optionally mono- to pentasubstituted, identically or differently, alkyl having 1 to 5 carbon atoms, substituted by fluorine, chlorine and bromine, alkoxyalkyl having 1 to 4 carbon atoms per alkyl part, alkenyl or alkynyl each having 3 to 4 carbon atoms and
R ^5-1 and R ^6-1 each independently represent alkyl having 1 to 4 carbon atoms. 3. 2-pyri (mi) dyl-2'-pyridyl (thio) ether of the formula (I) according to claim 1, in which
R¹, R² and R³ each independently represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, amino, methylamino, ethylamino, isopropylamino, dimethylamino, diethylamino,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, chlorine, cyano, methyl, ethyl, methoxy or ethoxy, where Y can be the same or different,
n represents 1, 2 or 3,
Z for the rest stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, methyl, ethyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, allyl or propargyl,
R⁵ and R⁶ independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, halogen-C₁-C₄-alkyl having 1 to 5 identical or different fluorine and chlorine atoms,
R⁷ for hydrogen, fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, vinyl, allyl, ethynyl, propargyl, halogen-C₁-C₄-alkyl with 1 to 5 identical or different fluorine and chlorine atoms or
R⁴ and R⁵ together with the carbon and nitrogen to which they are attached form a 3 to 6-membered heterocyclic ring which is optionally monosubstituted or disubstituted by fluorine, chlorine, methyl and ethyl and which has one or two double bonds may contain or
R⁶ and R⁷ together with the carbon to which they are bonded form a 3 to 6-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur as ring members and which may optionally be up to ten times the same or different by fluorine, chlorine, methyl and ethyl is substituted and may contain one or two double bonds, and
R⁸ represents hydrogen, optionally mono- to triple, identical or different, substituted by fluorine, chlorine and bromine, C₁-C₂-alkyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, allyl or propargyl and
R ^5-1 and R ^6-1 independently of one another represent methyl, ethyl and isopropyl. 4. Process for the preparation of 2-pyri (mi) dyl-2′-pyridyl (thio) ethers of the formula (I), in which
R¹, R² and R³ are each independently hydrogen, halogen, alkyl, alkoxy or alkylthio each having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, amino, alkylamino or dialkylamino each having 1 to 6 carbon atoms in the individual alkyl parts,
A represents a (-CH =) group or a nitrogen atom,
X represents oxygen or sulfur,
Y represents hydrogen, halogen, cyano, alkyl or alkoxy each having 1 to 6 carbon atoms, where Y can be the same or different and
n stands for a number from 1 to 3 and
Z for the rest or stands,
in which
B represents oxygen or sulfur,
D stands for <N-R⁴ or oxygen, where
R⁴ represents hydrogen, alkyl or alkoxyalkyl each having 1 to 6 carbon atoms, alkenyl or alkynyl each having 3 to 6 carbon atoms,
R⁵, R⁶ and R⁷ each independently represent hydrogen, halogen, cyano, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms and up to 13 halogen atoms, alkenyl or alkynyl each having 2 to 6 carbon atoms,
R⁴ and R⁵ together with the carbon and the nitrogen to which they are attached form a 3 to 8-membered heterocyclic ring which is optionally mono- or polysubstituted, identically or differently, by halogen, methyl and ethyl and which can contain one or more double bonds .
R⁶ and R⁷ together with the carbon to which they are attached form a 3 to 8-membered ring which, in addition to carbon, can also contain oxygen and / or sulfur atoms as ring members and which, if appropriate, can be mono- or polysilicon or halogen Ethyl is substituted and which may contain one or more double bonds and
R⁸ represents hydrogen, optionally single or multiple, identical or different halogen-substituted alkyl having 1 to 6 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms per alkyl part, alkenyl or alkynyl each having 3 to 6 carbon atoms and
R ^5-1 and R ^6-1 each independently represent alkyl with 1 to 6 carbon atoms,
characterized in that one

• A) compounds of the formula (II), in which
  R¹, R², R³, A, X, Y and n have the meaning given above,
  either
  • a₁) with acid halides of the formula (IIIa), in which
    R⁵, R⁶, R⁷ have the meaning given above and
    Hal stands for halogen,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    or
  • a₂) with symmetrical carboxylic anhydrides of the formula (IIIb), in which
    R⁵, R⁶ and R⁷ have the meaning given above,
    if appropriate in the presence of a diluent,
    or
  • a₃) with asymmetric acid anhydrides of the formula (IIIc), in which
    R⁵, R⁶ and R⁷ have the meaning given above and
    R represents alkyl or alkylsulfonyl each having 1 to 4 carbon atoms, phenyl or phenylsulfonyl,
    if appropriate in the presence of a diluent,
    or
  • a₄) with compounds of the formula (IIId), in which
    R⁵, R⁶ and R⁷ have the meaning given above,
    if appropriate in the presence of a diluent,
    or that one
• B) pyri (mi) din derivatives of the formula (IV), in which
  R¹, R² and R³ and A have the meaning given above and
  Hal stands for halogen,
  with acylaminopyridine derivatives of the formula (V), in which
  R⁵, R⁶, R⁷, X, Y and n have the meaning given above,
  in the presence of a diluent and, if appropriate, in the presence of an acid binder,
  or that one
• C) pyri (mi) din derivatives of the formula (VI), in which
  R¹, R², R³ and X have the meaning given above,
  either
  • C₁) with 2-halogen nicotinic acid derivatives of the formula (VIIa), in which
    R⁵, R⁶, R⁷, D, Y and n have the meaning given above and
    Hal¹ represents halogen,
    in the presence of a diluent and, if appropriate, in the presence of an acid binder,
    or
  • C₂) with 2-halogen nicotinic acid derivatives of the formula (VIIb), in which
    R ^5-1 , R ^6-1 , Y, n and Hal 1 have the meaning given above,
    in the presence of a diluent and in the presence of a base, converted to the compounds of the formula (Ia₃) in which
    R¹, R², R³, A, X, Y, n , R ^5-1 and R ^{6-1 have} the meaning given above,
    or that one
• D) 2-hydroxy (mercapto) nicotinic acid derivatives of the formula (VIII), in which
  R⁵, R⁶, R⁷, D, X, Y and n have the meaning given above,
  with pyri (mi) din derivatives of the formula (IV), in which
  R¹, R², R³ and A have the meaning given above and
  Hal stands for halogen,
  in the presence of a diluent and, if appropriate, in the presence of an acid binder,
  or that one
• E) substituted 2-pyri (mi) dyl-2′-pyridyl (thio) ethers of the formula (Ia), in which
  Z¹ for the rest stands and
  R¹, R², R³, R⁵, R⁶, R⁷, A, D, X, Y and n have the meaning given above,
  with sulfurization reagents such as phosphorus-V-sulfide or 2,4-bis- (4-methoxyphenyl) -2,4-dithiono-1,2,3,4-dithia-phosphetane (Lawesson's reagent) to give compounds of the formula (Ib), in which
  Z² for the rest stands and
  R¹, R², R³, R⁵, R⁶, R⁷, A, D, X, Y and n have the meaning given above,
  or that one
• F) the compounds of the formula (Ib), in which D is <NH, prepared by the process (E), with deprotonating bases and compounds of the formula (IX), F-R⁸ (IX) in which
  R⁸ has the meaning given above and
  F represents halogen, alkylsulfonyloxy or phenylsulfonyloxy,
  if appropriate in the presence of a diluent.

5. Herbicidal agents, characterized by a content on at least one 2-pyri (mi) dyl-2'-pyridyl (thio) ether of formula (I) according to claims 1 to 4. 6. Weed control method, thereby characterized in that 2-pyri (mi) dyl-2'-pyridyl (thio) ether of formula (I) according to claims 1 to 4 on the weeds and / or their habitat can act. 7. Use of 2-pyri (mi) dyl-2'-pyridyl (thio) ethers of formula (I) according to claims 1 to 4 to control weeds. 8. Process for the preparation of herbicidal compositions, characterized in that 2-pyri (mi) dyl-2'-pyridyl (thio) ether of the formula (I) according to the Claims 1 to 4 with extenders and / or surface-active substances mixed.