EP0920415A1

EP0920415A1 - Substituted 2-phenylpyridine as herbicide

Info

Publication number: EP0920415A1
Application number: EP97938899A
Authority: EP
Inventors: Peter Schäfer; Michael Rack; Gerhard Hamprecht; Helmut Walter; Karl-Otto Westphalen; Ulf Misslitz; Markus Menges; Cyrill Zagar; Olaf Menke
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1996-08-22
Filing date: 1997-08-13
Publication date: 1999-06-09
Also published as: CA2263093A1; US6448205B1; AU4118397A; AR009305A1; JP2000517303A; DE19633746A1; WO1998007700A1

Abstract

The present invention pertains to substituted 2-phenylpyridine I and the salts thereof of formula (I), where R1 = SH, SO¿2?NH2, C1-C2-alkylthio, C1-C6-alkyl-sulfinyl, C1-C6-akylsulfonyl, C1-C6alkylaminosulfonyl, Di-(C1-C6alkyl)aminosulfonyl; R?1, R3¿ = H, halogen; R4 = CN, OH, halogen, C¿1?-C6-alkoxy, possibly substituted OCH2-phenyl and R?5¿ have the meanings given in the description. The invention also relates to: the use of compounds (I) as herbicides or as plant dessicating/defoliating agents, the herbicides and the plant dessicating/defoliating agents containing compounds (I) as actives substances, the processes for controlling undesirable plant growth and for dessicating/defoliating plants using compounds (I), the processes for producing compounds (I), herbicides and plant dessicating/defoliating agents by compounds (I), as well as the intermerdiate products of formulae (IIa, V and VI).

Description

SUBSTITUTED 2-PHENYLPYRIDINE AS HERBICIDE

description

The present invention relates to new substituted 2-phenylpyridines of the formula I.

R5 in which the variables have the following meanings:

n zero or 1;

R ¹ ercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylsulfonyl, C ₁ -C ₆ -alkylsulfonyl,

Ci-Cö-alkylaminosulfonyl or di - (Ci -C ₆ alkyl) aminosulfonyl;

R ² , R ³ independently of one another are hydrogen or halogen;

R ⁴ cyano, hydroxy, halogen, -CC ₆ alkoxy or phenylmethoxy, where the phenyl ring can be unsubstituted or can carry one to three substituents, each selected from the group consisting of hydroxy, halogen, Ci-Cg-alkyl, Cχ-C ₆ -haloalkyl, -C-C6-alkoxy, Ci-Cβ -haloalkoxy, hydroxycarbonyl, (Cχ-C ₆ -alkoxy) carbonyl and (Cχ-C ₆ -alkoxy) - carbonyl -Cι-C ₆ - alkoxy;

R ⁵ is hydrogen, nitro, cyano, hydroxylamine ino, halogen, Cι-C ₆ -alkyl, C ₆ haloalkyl, -COC1, -CO-OR ^6, -CO-N (R ⁷⁾ R ^8, -CO O- (-C ₄ alkylene) -CO-OR ⁶ ,

-CO-O- (-CC ₄ alkylene) -CO-N (R ⁷ ) R ⁸ , -χ ^l - (C _! -C ₄ alkylene) -CO-R ⁶ ,

-X ¹ - (-C-alkylene) -CO-OR ⁶ ,

-X ¹ - (Ci-Cj-alkylene) -CO-O- (Cχ-C-alkylene) -CO-OR ⁶ ,

-X ¹ - (-CC ₄ alkylene) -CO-N (R ⁷ ) R ⁸ , -χ ^l -R ⁹ , -CH = C (R ¹⁰ ) -CO-OR ⁶ , -CH = C (R ¹⁰ ) -CO-O- (-CC ₄ alkylene) -CO-OR ⁶ , -CH = C (R ¹⁰ ) -CO-N (R ⁷ ) R ⁸ , formyl, -CO-R ⁶ ,

-C (R ⁸ ) = N-OR ¹⁵ , -X ¹ - (C ₁ -C ₄ alkylene) -C (R ⁸ ) = N-OR ¹⁵ , -CH = C (R ¹⁰ ) -C (R ⁸ ) = N-OR ¹⁵ , -CH (Ci -C ₆ alkoxy) ₂ , -N (R ¹⁶ ) R ¹⁷ , -N (R ¹⁶ ) -SO ₂ - (-C-C ₆ alkyl), -N ( R ^lfe ) -CO- (C ± -C ₆ alkyl), chlorosulfonyl, hydroxysulfonyl or - S0 ₂ -N (R ¹⁸ ) R ¹⁹ ;

R ^{6 is} hydrogen, Cχ-C6 alkyl, Cι-C ₆ haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, Ci -C ₆ alkoxy - C _λ -C ₆ alkyl or 3-oxetanyl;

R ^{7 is} hydrogen or Cχ-C ₆ alkyl;

R ⁸ is hydrogen, hydroxy, _Cι-C6 alkyl, hydroxycarbonyl -C -Cβ - alkyl, (Ci -C ₆ -alkoxy) carbonyl -C -C ₆ - alkyl, _Ci-C6 - alkoxy, Cι-C ₆ - Halogenalkoxy, phenyl -C-C ₆ alkoxy, C ₃ -Cg -alkenyloxy or C ₃ -C ₆ -alkynyloxy or

R ⁷ and R ⁸ together form a tetra or pentamethylene chain which can carry a (Ci-Cβ-alkoxy) carbonyl radical;

R ⁹ are hydrogen, C ₆ alkyl, Ci -C ₆ haloalkyl, C ₃ -C ₆ alkenyl, - C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or Cι-C ₆ alkoxy Cχ -C ₆ alkyl;

R ^{10 is} hydrogen, halogen or Ci-Cβ-alkyl;

R ^1X -R ¹⁴ independently of one another are hydrogen, Ci-Cg-alkyl or (Ci-Cβ-alkoxy) carbonyl;

R ¹⁵ are hydrogen, C ₆ alkyl, phenyl -C -C ₆ alkyl, (Cι-C ₆ -alkoxy) carbonyl-Cι-C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ Alkynyl;

R ^{16 is} hydrogen or -CC ₆ alkyl;

R ^{17 is} hydrogen, Ci-Cβ-Al yl, hydroxycarbonyl -Ci -C ₆ - alkyl, (Ci -C _δ alkoxy) carbonyl -Cι-C ₆ - alkyl or -CC ₆ alkoxy;

R ^{18 is} hydrogen or C _x -C ₆ alkyl;

R ^{19 is} hydrogen, -CC ₆ alkyl, hydroxycarbonyl -C-C ₆ alkyl,

(Ci-Ce-AlkoxyJcarbonyl-Ci-Cβ-alkyl or -CC ₆ alkoxy or

R ¹⁸ and R ¹⁹ together form a tetra or pentamethylene chain, which can carry a (-C ₆ alkoxy) carbonyl radical;

X ¹ -X ³ independently of one another oxygen or sulfur, and the agriculturally useful salts of the compounds I with R ⁶ = hydrogen.

The invention also relates to the use of the compounds I as herbicides or for

Desiccation / defoliation of plants, herbicidal agents and agents for desiccation and / or

Defoliation of plants which contain the compounds I as active substances, - methods for combating undesired plant growth and for desiccating and / or defoliation of plants with the

Connections I,

Process for the preparation of the compounds I and herbicidal agents and agents for the desiccation and / or defoliation of plants using the compounds I and

Intermediate products of the formulas Ha, V and VI.

WO 95/02580 describes a large number of herbicidally active 2-phenylpyridines. Some of the present compounds I with R ¹ = C ¹ -C ₄ -alkylthio also fall under the general formula there.

WO 94/05153 relates to herbicidally active benzene compounds which, inter alia, can also carry a pyridine ring substituted by halogen and methylthio. The specific substitution pattern of the present 2-phenylpyridines, however, cannot be found in this publication.

DE-A 19 500 760, DE-A 19 500 758 and DE-A 19 500 911 already describe certain substituted 2-phenylpyridines of the type of the compounds I with mercapto, C 1 -C ₄ -alkylthio, C 1 -C -alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl in the 5 position of the pyridine ring as herbicidal and desiccant / defoliant active ingredients.

However, the herbicidal activity of the known compounds with regard to the harmful plants is not always completely satisfactory. The object of the present invention was therefore to provide new herbicidally active compounds which can be used to control undesirable plants better than before. The task also extends to the provision of new desiccant / defoliant connections.

Accordingly, the substituted 2-phenylpyridines of the formula I defined at the outset with herbicidal activity and new intermediates V and VI for their preparation have been found. Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.

Furthermore, it was found that the compounds I are also suitable for defoliation / desiccation of parts of plants, for which crop plants such as cotton, potatoes, rapeseed, sunflower, bean beans or field beans, in particular cotton and potatoes, are suitable. In this regard, agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with the compounds I have been found.

Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers and are then present as enantiomer or diastereomer mixtures. The invention relates both to the pure enantiomers or diastereomers and to mixtures thereof.

The substituted 2-phenylpyrids I with R ⁶ = hydrogen can be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of such bases come into consideration in which the herbicidal action is not adversely affected in comparison with the free compound I.

Particularly suitable salts are those of the alkali metals, preferably sodium and potassium salts, of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and also ammonium salts in which the ammonium ion, if desired, one to four C 1 -C ₄ -Alkyl-, Hydroxy-Cι-C ₄ alkyl substituents and / or a phenyl or benzyl substituent can wear, preferably diisopropyl ammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl (2-hydroxyethyl) - ammonium salts, furthermore phosphonium salts, sulfomum salts such as preferably tri- (C 1 -C ₄ -alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (Cχ-C ₄ -alkyl) sulfoxonium salts.

The organic molecule parts mentioned for the substituents R ¹ and R ⁴ to R ¹⁹ or as residues on a phenyl ring or on tetra- or pentamethylene represent collective terms for individual lists of the individual group members

Carbon chains, i.e. all alkyl, haloalkyl, phenylalkyl, alkylene, alkoxy, haloalkoxy, phenylalkoxy, alkylthio, Alkylsulfinyl, alkylsulfonyl, hydroxycarbonylalkyl, alkoxycarbonyl, alkylamino, alkenyl, alkynyl, alkenyloxy and alkynyloxy parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms.

Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.

Furthermore, for example:

C _! -C ₆ alkyl for: Cx- alkyl such as CH ₃ , C ₂ H ₅ , n-propyl, CH (CH ₃ ) ₂ , n-butyl, CH (CH ₃ ) -C ₂ H ₅ , CH ₂ -CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , or, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethyl - Propyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-diethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl , 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-tnmethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-

1-methylpropyl or l-ethyl-2-methylpropyl, in particular for CH ₃ , C ₂ H ₅ , n-propyl, CH (CH ₃ ) ₂ , n-butyl, C (CH ₃ ) ₃ , n-pentyl or n- Hexyl;

A _Cι-6 alkyl C as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, eg CH ₂ F, CHF _2, CF _3, CH: - Cι-C ₆ -haloalkyl ₂ C1, CH (C1) ₂ , C (C1) ₃ , CHFC1, CF (C1) ₂ , CF ₂ C1, CF ₂ Br, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2 -Iodethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 1,2- Dechloroethyl, 2, 2, 2-trichloroethyl, C ₂ F ₅ , 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, - Dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, CF ₂ -C ₂ F ₅ , 1 - (Fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 5-fluoropentyl, 5-chloropentyl , 5-bromopentyl, 5-iodopentyl, 5, 5, 5-trichlorpe ntyl, undecafluoropentyl, 6-fluorohexyl,

6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 6, 6, 6-trichlorohexyl or dodecafluorohexyl, especially for CH ₂ F, CHF ₂ , CF ₃ , CH ₂ C1, 2-fluoroethyl, 2-chloroethyl, 1, 2 - Dichloroethyl, 2, 2, 2-trifluoroethyl or C ₂ F ₅ ; ϊ Phenyl-C ₆ -C ₆ alkyl for: for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-1-yl, 1-phenylbut -l-yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2 -yl, 4-phenylbut-2-yl, 1- (benzyl) -eth-1-yl, 1- (benzyl) -1- (methyl) -eth-1-yl, 1- (benzyl) -prop-1 -yl or 2-phenyl-hex-6-yl, especially for benzyl or 2-phenyl-ethyl;

C ₃ -C ₆ cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, in particular for cyclopentyl or cyclohexyl;

-C -C alkylene for: -CH ₂ -, -CH (CH ₃ ) -, 1,2-ethylene, 1, 1-propylene, 1, 2-propylene, 1, 3-propylene, -C (CH ₃ ) ₂ -, 1,1-butylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2,2-butylene, 2,3-butylene, 2-methyl-l, 1-propylene, 2 -Methyl-1,2-propylene or 2-methyl-1,3-propylene, preferably for methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene or 2,2-propylene;

Cx-C _δ alkoxy for: e.g. OCH ₃ , OC ₂ H ₅ , n-propoxy, OCH (CH ₃ ) ₂ , n-butoxy, 0CH (CH ₃ ) -C ₂ H ₅ , OCH ₂ -CH (CH ₃ ) ₂ , OC (CH ₃ ) ₃ , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethyl- propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy,

1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy,

2, 3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy or l-ethyl- 2-methylpropoxy, especially OCH ₃ , OC ₂ H ₅ , OCH (CH ₃ ) ₂ or OC (CH ₃ ) ₃ ;

Ci-Cε-haloalkoxy for: -C-C ₆ alkoxy as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example OCH ₂ F, OCHF ₂ , OCF ₃ , 0CH ₂ C1, OCH (CD. ₂ 0C (C1) _3, OCHFC1, 0CF (C1) ₂ 0CF ₂ C1, OCF ₂ Br, 1-fluoroethoxy, 2-fluoroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2 , 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, OC ₂ F ₅ , 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy,

2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy,

3, 3, 3-trifluoropropoxy, 3, 3, 3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, OCF ₂ -C ₂ F ₅ , 1- (CH ₂ F) -2-f luorethoxy, 1- (CHCl) -2-chloroethoxy, 1- (CH ₂ Br) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy or dodecafluorohexoxy;

Phenyl-Cχ-C ₆ -alkoxy for: e.g. benzyloxy, 1-phenylethoxy,

2-phenylethoxy, 1-phenylprop-l-yloxy, 2-phenylprop-l-yloxy, 3-phenylprop-l-yloxy, 1-phenylbut-l-yloxy, 2-phenylbut-l-yl - oxy, 3-phenylbut- l-yloxy, 4-phenylbut-l-yloxy, 1-phenylbut-2-yloxy, 2-phenylbut-2-yloxy, 3-phenylbut-2-yloxy, 4-phenylbut-2-yloxy, 1- (benzyl ) -eth-1-yloxy, 1- (benzyl) -1- (methyl) - eth-1-yloxy, 1- (benzyl) prop-1-yloxy or 2-phenyl-hex-6-yl - oxy, especially for benzyloxy or 2-phenylethoxy;

Cχ-C ₆ -alkoxy-Cχ-C ₆ -alkyl for: substituted by Cχ-C ₆ -alkoxy as mentioned above Cχ-C ₆ ~ alkyl, so for example for

CH ₂ OCH ₃ , CH ₂ OC ₂ H ₅ , CH ₂ OCH ₂ -C ₂ H ₅ , CH ₂ OCH (CH ₃ ) ₂ , CH ₂ OCH CH ₂ -C ₂ H ₅ , (1-methylpropoxy) methyl, ( 2-methylpropoxy) methyl, CH ₂ OC (CH ₃ ) ₃ , CH ₂ 0 (CH ₂ ) ₃ -C ₂ H ₅ , CH ₂ 0 (CH ₂ ) ₄ -C ₂ H ₅ , CH (CH ₃ ) OCH ₃ , CH (CH ₃ ) OC ₂ H ₅ , CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OC ₂ H ₅ , CH ₂ CH ₂ OCH ₂ -C ₂ H ₅ , CH ₂ CHOCH (CH ₃ ), CH ₂ CH ₂ OCH ₂ CH ₂ -C ₂ H ₅ , 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, CH ₂ CH ₂ OC (CH ₃ ) ₃ , CH ₂ CH ₂ 0 (CH ₂ ) ₃ -C ₂ H ₅ , CH ₂ CH ₂ 0 (CH ₂ ) ₄ -C ₂ H ₅ , 2- (0CH ₃ ) propyl, 2- (OC ₂ H ₅ ) propyl, 2- (OCH ₂ -C ₂ H ₅ ) propyl, 2- [OCH (CH ₃ ) ₂ ] propyl, 2- (OCH ₂ CH ₂ -C ₂ H ₅ ) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl , 2- [OC (CH ₃ ) ₃ ] propyl, 3- (OCH ₃ ) propyl, 3- (OC ₂ H ₅ ) propyl,

3- (OCH -C ₂ H ₅ ) propyl, 3- [OCH (CH ₃ ) ₂ ] propyl, 3- (OCH ₂ CH ₂ -C ₂ H ₅ ) propyl, 3- (1-methylpropoxy) propyl, 3 - (2-Methylpropoxy) propyl, 3- [OC (CH ₃ ) ₃ ] propyl, 3- [0 (CH ₂ ) ₃ -C ₂ H ₅ ] propyl, 3- [0 (CH ₂ ) ₄ -C ₂ H ₅ ] propyl, 2- (0CH ₃ ) butyl, 2- (OC ₂ H ₅ ) butyl, 2- (OCH ₂ -C ₂ H ₅ ) butyl, 2- [OCH (CH ₃ ) ₂ ] butyl, 2- (OCH ₂ CH ₂ -C ₂ H ₅ ) - butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- [OC (CH ₃ ) ₃ ] butyl, 3- (OCH ₃ ) butyl, 3- (OC ₂ H ₅ ) butyl, 3- (OCH ₂ -C ₂ H ₅ ) butyl, 3- [OCH (CH ₃ ) ₂ ] butyl, 3- (OCH ₂ CH ₂ -C ₂ H ₅ ) - butyl, 3- (1-methylpropoxy) butyl, 3- (2-methylpropoxy) butyl, 3- [OC (CH ₃ ) ₃ ] butyl, 4- (OCH ₃ ) butyl, 4- (OC ₂ H ₅ ) butyl ,

4- (OCH ₂ -C ₂ H ₅ ) butyl, 4- [OCH (CH ₃ ) ₂ ] butyl, 4- (OCH ₂ CH ₂ -C ₂ H ₅ ) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl, 4- [OC (CH ₃ ) ₃ ] butyl, 4- [0 (CH ₂ ) ₃ -C ₂ H ₅ ] butyl, 4- [0 (CH ₂ ) ₄ -C ₂ H ₅ ] - butyl, 5- (0CH ₃ ) pentyl, 5- (OC ₂ H ₅ ) pentyl, 5- (OCH ₂ -C ₂ H ₅ ) pentyl, 5- [OCH (CH ₃ ) ₂ ] pentyl, 5 - (OCH ₂ CH ₂ -C ₂ H ₅ ) pentyl, 5- (1-methylpropoxy) pentyl, 5- (2-methylpropoxy) pentyl, 5- [OC (CH ₃ ) ₃ ] pentyl, 5- [0 (CH ₂ ) ₃ -C ₂ H ₅ ] pentyl, 5- [0 (CH ₂ ) ₄ -C ₂ H ₅ ] pentyl, 6- (OCH ₃ ) hexyl, 6- (OC ₂ H ₅ ) hexyl, 6- (OCH ₂ -C ₂ H ₅ ) hexyl, 6- [OCH (CH ₃ ) ₂ ] hexyl, 6- (OCH ₂ CH ₂ -C ₂ H ₅ ) hexyl, 6- (1-methylpropoxy) hexyl, 6- ( 2-methyl-propoxy) hexyl, 6- [OC (CH ₃ ) ₃ ] hexyl, 6- [0 (CH ₂ ) ₃ -C ₂ H ₅ ] hexyl or

6- [0 (CH ₂ ) ₄ -CH ₅ ] hexyl, especially for CH ₂ 0CH ₃ , CH (CH ₃ ) OCH ₃ , CH ₃ CH ₂ OCH ₃ or CH (CH ₃ ) CH ₂ OCH ₃ ;

? Hydroxycarbonyl-C -C ₆ -alkyl for: for example CH ₂ COOH, CH (CH ₃ ) C00H, CH ₂ CH ₂ COOH, l- (COOH) prop-l-yl, 2- (COOH) prop-1-yl, 3- (COOH) prop-l-yl, 1- (COOH) but-l-yl, 2- (COOH) but-l-yl, 3- (COOH) but-l-yl, 4- (COOH) but -l-yl, 1- (COOH) but-2-yl, 2- (COOH) but-2-yl, 3- (COOH) but-2-yl, 4- (COOH) but-2-yl, 1 - (CH ₂ COOH) eth-l-yl, 1- (CH ₂ COOH) -1- (CH ₃ ) -eth-l-yl, 1- (CH ₂ COOH) prop-l-yl, 5- (COOH ) ent-1-yl or 6- (COOH) hex-1-yl;

(Cχ-C ₆ -alkoxy) carbonyl for: COOCH ₃ , COOC ₂ H ₅ , n-propoxycarbonyl, OCH (CH ₃ ) ₂ , n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl, OC (CH ₃ ) ₃ , n-Pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethyl-propoxycarbonyl, n-hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl , 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2, 3 -Dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1, 1, 2-trimethylpropoxycarbonyl, 1, 2, 2-trimethylpropoxycarbonyl, 1C ₂ Hs-1-CH ₃ -propoxycarbonyl or IC ₂ H ₅ -2-CH-propoxycarbonyl, in particular for COOCH ₃ , COOC ₂ H ₅ or COOC (CH ₃ ) ₃ ;

(Cχ-C ₆ -alkoxy) carbonyl-Ci-Cβ-alkyl for: C (-Ce-alkyl substituted by (Cχ-C ₆ ~ alkoxy) carbonyl as mentioned above, e.g. for CH ₂ COOCH ₃ , CH ₂ COOC ₂ H ₅ , CH ₂ COOCH ₂ -C ₂ H ₅ , CH ₂ COOCH (CH ₃ ) ₂ , CH ₂ COOCH ₂ CH ₂ -C ₂ H ₅ , (1-methylpropoxycarbonyl) methyl, (2-methylpropoxycarbonyl) methyl, CH ₂ COOC (CH ₃ ) ₃ , CH ₂ COO (CH ₂ ) ₃ -C ₂ H ₅ , CH ₂ COO (CH ₂ ) ₄ -C ₂ H ₅ , CH (CH ₃ ) COOCH ₃ , CH (CH ₃ ) COOC ₂ H ₅ , CH ₂ CH ₂ COOCH ₃ , CH ₂ CH ₂ COOC ₂ H ₅ , CH ₂ CH ₂ COOCH ₂ -C ₂ H ₅ , CH ₂ CH ₂ COOCH (CH ₃ ) ₂ , CH ₂ CH ₂ COOCH ₂ CH ₂ -C ₂ H ₅ , 2- (1-methylpropoxycarbonyl) ethyl, 2- (2-methylpropoxycarbonyl) ethyl,

CH ₂ CH ₂ COOC (CH ₃ ) ₃ , CH ₂ CH ₂ COO (CH ₂ ) ₃ -C ₂ H ₅ CH ₂ CH ₂ COO (CH ₂ ) ₄ -C ₂ H ₅ , 2- (COOCH ₃ ) propyl, 2- (COOC ₂ H ₅ ) propyl, 2- (COOCH ₂ -C ₂ H ₅ ) propyl, 2- [COOCH (CH ₃ ) ₂ ] propyl, 2- (COOCH ₂ CH ₂ -C ₂ H ₅ ) propyl, 2- (l-methylpropoxycarbonyl) propyl, 2- (2-methylpropoxycarbonyl) propyl, 2- [COOC (CH ₃ ) ₃ ] propyl, 3- (COOCH ₃ ) propyl, 3- (COOC ₂ H ₅ ) propyl, 3- (COOCH ₂ -C ₂ H ₅ ) propyl, 3- [COOCH (CH ₃ ) ₂ ] propyl, 3- (COOCH ₂ CH ₂ -C ₂ H ₅ ) propyl, 3- (1-methylpropoxycarbonyl) ropyl, 3 - (2-Methylpropoxycarbonyl) propyl, 3- [COOC (CH ₃ ) ₃ ] propyl, 3- [COO (CH ₂ ) ₃ -C ₂ H ₅ ] propyl, 3- [COO (CH ₂ ) ₄ -C ₂ H ₅ ] propyl, 2- (COOCH ₃ ) butyl, 2- (COOC ₂ H ₅ ) butyl, 2- (COOCH ₂ -C ₂ H ₅ ) butyl,

2- [COOCH (CH ₃ ) ₂ ] butyl, 2- (COOCH ₂ CH ₂ -C ₂ H ₅ ) butyl, 2- (l-methylpropoxycarbonyl) butyl, 2- (2-methylpropoxycarbonyl) butyl,

β 2- [COOC (CH ₃ ) ₃ ] butyl, 3- (COOCH ₃ ) butyl, 3- (COOC ₂ H ₅ ) butyl, 3- (COOCH ₂ -C ₂ H ₅ ) butyl, 3- [COOCH (CH ₃ ) ₂ ] butyl,

3- (COOCH ₂ CH ₂ -C ₂ H ₅ ) butyl, 3- (1-methylpropoxycarbonyl) butyl, 3- (2-methylpropoxycarbonyl) butyl, 3- [COOC (CH ₃ ) ₃ ] butyl, 4- (COOCH ₃ ) butyl, 4- (COOC ₂ H ₅ ) butyl, 4- (COOCH ₂ -C ₂ H ₅ ) butyl,

4- [COOCH (CH ₃ ) ₂ ] butyl, 4- (COOCH ₂ CH ₂ -C ₂ H ₅ ) butyl, 4- (l-methylpropoxycarbonyl) butyl, 4- (2-methylpropoxycarbonyl) butyl,

4- [COOC (CH ₃ ) ₃ ] butyl, 4- [COO (CH ₂ ) ₃ -C ₂ H ₅ ] butyl,

4- [COO (CH ₂ ) ₄ -C ₂ H ₅ ] butyl, 5- (COOCH ₃ ) pentyl, 5- (COOC ₂ H ₅ ) pentyl, 5- (COOCH -C ₂ H ₅ ) pentyl, 5- [ COOCH (CH ₃ )] pentyl,

5- (COOCH ₂ CH ₂ -C ₂ H ₅ ) pentyl, 5- (1-methylpropoxycarbonyl) pentyl, 5- (2-methylpropoxycarbonyl) pentyl, 5- [COOC (CH ₃ ) ₃ ] pentyl,

5- [COO (CH ₂ ) ₃ -C ₂ H ₅ ] pentyl, 5- [COO (CH ₂ ) ₄ -C ₂ H ₅ ] pentyl,

6- (COOCH ₃ ) hexyl, 6- (COOC ₂ H ₅ ) hexyl, 6- (COOCH ₂ -C ₂ H ₅ ) hexyl, 6- [COOCH (CH ₃ ) ₂ ] hexyl, 6- (COOCH ₂ CH ₂ -C ₂ H ₅ ) hexyl, 6- (l-methylpropoxycarbonyl) hexyl, 6- (2-methylpropoxycarbonyl) hexyl, 6- [COOC (CH ₃ ) ₃ ] hexyl, 6- [COO (CH ₂ ) ₃ - C ₂ H ₅ ] hexyl or 6- [COO (CH ₂ ) -C ₂ H ₅ ] hexyl, in particular for CH ₂ COOCH ₃ , CH ₂ COOCH (CH ₃ ) ₂ or CH (CH ₃ ) COOCH ₃ ;

(Cχ-C ₆ alkoxy) carbonyl-Cχ-C ₆ -alkoxy of: by (Cχ-C ₆ alkoxy) - carbonyl as mentioned above substituted _Cχ-C6 alkoxy, eg for OCH ₂ COOCH _3, OCH ₂ COOC ₂ H ₅ , OCH ₂ COOCH ₂ -C ₂ H ₅ , OCH COOCH (CH ₃ ) ₂ , OCH COOCH ₂ CH ₂ -C ₂ H ₅ , (1-methylpropoxycarbonyl) methoxy, (2-methylpropoxycarbonyl) methoxy, OCH ₂ COOC (CH ₃ ) ₃ ,

OCH ₂ COO (CH ₂ ) ₃ -C ₂ H ₅ , OCH COO (CH ₂ ) ₄ -CH ₅ , OCH (CH ₃ ) COOCH ₃ , OCH (CH ₃ ) COOC ₂ H ₅ , OCH ₂ CH ₂ COOCH ₃ , OCH ₂ CH ₂ COOC ₂ H ₅ ,

OCH ₂ CH ₂ COOCH ₂ -C ₂ H ₅ , OCH ₂ CH ₂ COOCH (CH ₃ ) ₂ , OCH ₂ CH ₂ COOCH CH ₂ -C ₂ H ₅ , 2- (1-methylpropoxycarbonyl) ethoxy, 2- (2- Methylpropoxycarbonyl) ethoxy, OCH ₂ CH ₂ COOC (CH ₃ ) ₃ , OCH ₂ CH ₂ COO (CH ₂ ) ₃ -C ₂ H ₅ ,

OCH ₂ CH ₂ COO (CH ₂ ) ₄ -C ₂ H ₅ , 2- (COOCH ₃ ) propoxy, 2- (COOC H ₅ ) propoxy,

2- (COOCH ₂ -C ₂ H ₅ ) propoxy, 2- [COOCH (CH ₃ ) ₂ ] propoxy,

2- (COOCH ₂ CH ₂ -C ₂ H ₅ ) propoxy, 2- (1-methylpropoxycarbonyl) propoxy,

2- (2-methylpropoxycarbonyl) propoxy, 2- [COOC (CH ₃ ) ₃ ] propoxy, 3- (COOCH ₃ ) propoxy, 3- (COOC ₂ H ₅ ) propoxy, 3- (COOCH ₂ -CH ₅ ) propoxy,

3- [COOCH (CH ₃ ) ₂ ] propoxy, 3- (COOCH ₂ CH ₂ -C ₂ H ₅ ) propoxy,

3- (1-methylpropoxycarbonyl) propoxy, 3- (2-methylpropoxycarbonyl) propoxy, 3- [COOC (CH) ₃ ] propoxy,

3- [COO (CH ₂ ) ₃ -C ₂ H ₅ ] propoxy, 3- [COO (CH ₂ ) -CH ₅ ] propoxy, 2- (COOCH ₃ ) butoxy, 2- (COOC ₂ H ₅ ) butoxy, 2 - (COOCH ₂ -C ₂ H ₅ ) butoxy,

2- [COOCH (CH ₃ ) ₂ ] butoxy, 2- (COOCH ₂ CH ₂ -C ₂ H ₅ ) butoxy, 2- (l-methylpropoxycarbonyldbutoxy, 2- (2-methylpropoxycarbonyl) butoxy, 2- [COOC ( CH ₃ ) ₃ ] butoxy, 3- (COOCH ₃ ) butoxy, 3- (COOC ₂ H ₅ ) butoxy, 3- (COOCH ₂ -C ₂ H ₅ ) butoxy, 3- [COOCH (CH ₃ ) ₂ ] butoxy, 3- (COOCH ₂ CH ₂ -CH ₅ ) butoxy, 3- (1-methylpropoxycarbonyl) butoxy,

3- (2-Methylpropoxycarbonyl) utoxy, 3- [COOC (CH ₃ ) ₃ ] butoxy, 4- (COOCH ₃ ) butoxy, 4- (COOC ₂ H ₅ ) butoxy, 4- (COOCH -C ₂ H ₅ ) butoxy ,

J 4- [COOCH (CH ₃ ) ₂ ] butoxy, 4- (COOCH ₂ CH ₂ -C ₂ H ₅ ) butoxy, 4- (1-methylpropoxycarbonyl) butoxy, 4- (2-methyl ropoxycarbonyl) butoxy,

4- [COOC (CH ₃ ) ₃ ] butoxy, 4- [COO (CH ₂ ) ₃ -C ₂ H ₅ ] butoxy,

4- [COO (CH ₂ ) -C ₂ H ₅ ] butoxy, 5- (COOCH ₃ ) pentoxy, 5- (COOC ₂ H ₅ ) pentoxy, 5- (COOCH ₂ -C ₂ H ₅ ) pentoxy, 5- [COOCH (CH ₃ ) ₂ ] pentoxy,

5- (COOCH ₂ CH ₂ -CH ₅ ) pentoxy, 5- (1-methylpropoxycarbonyl) pentoxy, 5- (2-methylpropoxycarbonyl) pentoxy, 5- [COOC (CH ₃ ) ₃ ] pentoxy,

5- [COO (CH ₂ ) ₃ -C ₂ H ₅ ] pentoxy, 5- [COO (CH ₂ ) 4-C2H5] pentoxy,

6- (COOCH ₃ ) hexoxy, 6- (COOC ₂ H ₅ ) hexoxy, 6- (COOCH ₂ -C ₂ H ₅ ) hexoxy, 6- [COOCH (CH ₃ ) ₂ ] hexoxy, 6- {COOCH ₂ CH ₂ -C ₂ H ₅ ) hexoxy, 6- (l-methylpropoxycarbony1) hexoxy, 6- (2-methylpropoxycarbony1) hexoxy, 6- [COOC (CH ₃ ) ₃ ] hexoxy, 6- [COO (CH ₂ ) ₃ - C ₂ H ₅ ] hexoxy or 6- [COO (CH ₂ ) ₄ -C ₂ H ₅ ] hexoxy, in particular for OCH ₂ COOCH ₃ , OCH ₂ COOCH (CH ₃ ) ₂ , OCH (CH ₃ ) COOCH ₃ or OCH ₂ CH ₂ COOCH ₃ ;

Cι-C ₆ alkylthio for: for example SCH ₃ , SC ₂ H ₅ , n-propylthio, SCH (CH ₃ ) ₂ , n-butylthio, 1-methylpropylthio, 2-methylpropylthio, SC (CH ₃ ) ₃ , n-pentylthio , 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio -Methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2,3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio , 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1, 2, 2-trimethylpropylthio, 1-ethyl-l-methylpropylthio or l-ethyl-2-methylpropylthio, in particular for SCH ₃ or SC ₂ H ₅ ;

Cχ-C ₆ ~ haloalkylthio for: a Cχ-C ₆ alkylthio radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for SCH ₂ F, SCHF ₂ , SCF ₃ , SCH ₂ C1, SCH (C1) ₂ , SC (C1) ₃ , SCHFC1, SCF (C1) ₂ , SCF ₂ C1, SCF ₂ Br, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2 , 2-difluoroethylthio, 2,2, 2-trifluoroethylthio, 2, 2, 2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2, 2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, SC ₂ F ₅ , 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2, 2-difluoropropylthio, 2, 3-difluoropropylthio, 2,3-dichloropropylthio 3, 3, 3-trifluoropropylthio,

3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1- (CH ₂ F) -2-fluoroethylthio, 1- (CH ₂ Cl) -2-chloroethylthio, 1- (CH ₂ Br) -2-bromethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorhexylthio or 6-chlorohexylthio, in particular for SCHF ₂ , SCF ₃ or SC (C1) ₃ ; Cχ-C ₆ alkylsulf inyl for: e.g. SOCH, SOC ₂ H ₅ , n-propylsulf inyl, SOCH (CH ₃ ) ₂ , n-butylsulfinyl, 1-methylpropylsulf inyl, 2-methylpropylsulfinyl, SOC (CH ₃ ) ₃ , n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2 -Dimethylpropyl - sulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfyl, 3-methylpentylsulfyl, 4-methylpentylsulfyl, 1, 1-dimethylbutylsulfyl, 1, 2-dimethylbutylsulfyl, 1, 3-dimethylbutylsulfinyl, 2, 2-Dimethylbutylsulf inyl, 2, 3-Dimethylbutylsulfinyl, 3, 3-Dimethylbutylsulf inyl, 1-Ethylbutylsulf inyl, 2-Ethylbutylsulf inyl, 1,1, 2-Trimethylpropylsulf inyl, 1,2, 2-Trimethylpropylsulf inyl, 1- Ethyl-l-methylpropylsulfinyl or l-ethyl-2-methylpropylsulfinyl, in particular for SOCH ₃ or SOC ₂ H ₅ ;

C -C ₆ alkylsulfonyl for: e.g. S0 ₂ CH ₃ , S0 ₂ C ₂ H ₅ , n-propylsulfonyl, S0 CH (CH ₃ ) ₂ , n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, S0 ₂ C (CH ₃ ) ₃ , n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl,

3-methylbutylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n-hexylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentyl-pentylsulfonylsulfonyl, 3 sulfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutyl - sulfonyl, 1, 3-dimethylbutylsulfonyl, 2, 2-dimethylbutyl - sulfonyl, 2, 3-dimethylbutylsulfonyl, 3, 3-dimethylbutyl - sulfonyl, 1-ethylbutylsulfonyl Ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-l-methylpropylsulfonyl or l-ethyl-2-methylpropylsulfonyl, in particular for S0 ₂ CH ₃ or S0 ₂ CHs;

-C-C ₆ -Alkylaminosulfonyl for: for example H ₃ C-NHS0 ₂ -, H ₅ C ₂ -NHS0 ₂ -, n-propyl-NHS0 ₂ -, (CH ₃ ) ₂ CH-NHS0 ₂ -, n-butyl-NHS0 -, 1-methyl-propyl-NHS0 ₂ -, 2-methylpropyl-NHS0 ₂ -, (CH ₃ ) ₃ C-NHS0 ₂ -, n-pentyl-NHS0 ₂ -, 1-methylbutyl-NHS0 ₂ -, 2-methylbutyl -NHS0 ₂ -, 3-methylbutyl-NHS0 ₂ -, 2, 2-dimethylpropyl-NHS0 ₂ -, 1-ethyl-propyl-NHS0 ₂ -, n-hexyl-NHS0 ₂ -, 1, 1-dimethylpropyl-NHS0 ₂ - , 1, 2-Dimethylpropyl-NHS0 ₂ -, 1-methylpentyl-NHS0 ₂ -, 2-methylpentyl-NHS0 ₂ -, 3-methylpentyl-NHS0 ₂ -, 4-methylpentyl-NHS0 ₂ -, 1, 1-dimethylbutyl -NHS0 ₂ -, 1, 2-dimethylbutyl-NHS0 ₂ -, 1,3-dimethylbutyl-NHS0 ₂ -, 2, 2-dimethylbutyl-NHS0 ₂ -, 2, 3-dimethylbutyl-NHS0 ₂ -, 3 , 3-dimethylbutyl-NHS0 ₂ -, 1-ethylbutyl-NHS0 ₂ -, 2-ethylbutyl-NHS0 ₂ -, 1, 1, 2-trimethylpropyl-NHS0 ₂ -, 1,2,2-trimethylpropyl-NHS0 ₂ - , l-ethyl-l-methylpropyl-NHS0 ₂ - or l-ethyl-2-methylpropyl-NHS0 ₂ -, in particular for H ₃ C-NHS0 ₂ - or H ₅ C -NHS0 ₂ -;

// Di - (Cχ-C ₆ -alkyl) aminosulfonyl for: e.g. (CH ₃ ) ₂ N-S0 ₂ -, (C ₂ H ₅ ) ₂ N-S0 ₂ -, N, N-Dipropylamino-S0 ₂ -, N, N-Di (1-methylethyl) amino-S0 ₂ -, N, N-dibutylamino-S0 ₂ -, N, -Di (1-methyl-propyl) amino-S0 ₂ -, N, N-Di (2-methylpropyl ) amino-S0 -, N, N-Di (1, l-dimethylethyl) amino-S0-, N-ethyl-N-methyl - amino-S0 ₂ -, N-methyl-N-propylamino-S0 -, N- Methyl-N- (1-methylethyl) amino-S0 ₂ -, N-butyl-N-methylamino-S0 -, N-methyl-N- (1-methylpropyl) amino-S0 ₂ -, N-methyl-N- ( 2-methyl-propyl) amino-S0 -, N- {1, 1-dimethylethyl) -N-methylamino-S0 ₂ -, N-ethyl-N-propylamino-S0 ₂ -, N-ethyl-N- (1- methylethyl) amino-S0 ₂ -, N-butyl-N-ethylamino-S0 ₂ -, N-ethyl-N- (1-methylpropyl) - amino-S0 ₂ -, N-ethyl-N- (2-methylpropyl) amino -S0 ₂ -, N-ethyl-N- (1, l-dimethylethyl) amino-S0 ₂ -, N- (1-methylethyl) -N-propyl-amino-S0 ₂ -, N-butyl-N-propylamino- S0 ₂ -, N- (1-methylpropyl) -N-propylamino-S0 ₂ -, N- (2-methylpropyl) -N-propylamino-S0 ₂ -, N- (1, 1-dimethylethyl) -N- propylamino-S0 ₂ -, N-butyl-N- (1-methylethyl) amino-S0 ₂ -, N- (1-methylethyl) -N- (1-methyl-propyl) amino-S0 ₂ -, N- (1 -Methylethyl) -N- (2-methylpropyl) - amino-S0 ₂ -, N- (1, 1-dimethylethyl) -N- (1-methylethyl) amino-S0 ₂ -, N-butyl-N- (l- methylpropyl) amino-S0 ₂ -, N-butyl-N- (2-methyl-propyl) amino-S0 ₂ -, N-butyl-N- (1, 1-dimethylethyl) amino-S0 ₂ -, N- (1 -Methylpropyl) -N- (2-methylpropyl) a ino-SC ^ -, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) amino-S0 ₂ - or N- (1, 1- Dimethylethyl) -N- (2-methylpropyl) amino-S0 ₂ -, especially for (CH ₃ ) ₂ N-S0 ₂ -, (C ₂ H ₅ ) ₂ N-S0 ₂ - or N-ethyl -N-methylamino- S0 ₂ -;

C ₃ -C ₆ alkenyl for: for example prop-1-en-l-yl, allyl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3- yl, 1-methylprop-1-en-l-yl, 2-methylprop-l-en-l-yl, l-methylprop-2-en- 1-yl, 2-methylprop-2-en-l- yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-l-en-l-yl, 2-methylbut- l-en-l-yl, 3-methylbut-l-en-l-yl, 1-methylbut-2-en-l-yl, 2-methylbut-2-en-l-yl, 3-methylbut- 2-en-l-yl, l-methylbut-3-en-l-yl, 2-methylbut-3-en-l-yl, 3-methylbut-3-en-l-yl, 1, l- Dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop-1-en-l-yl, 1, 2-dimethyl-prop-2-en-l-yl, 1-ethyl-prop- l-en-2-yl, l-ethylprop-2-en-l-yl, n-hex-1-en-l-yl, n-hex-2-en-l-yl, n-hex-3- en-l-yl, n-hex-4-en-l-yl, n-hex-5- en-l-yl, 1-methyl-pent-l-en-l-yl, 2-methylpent-l- en-l-yl, 3-methylpent-l-en-l-yl, 4-methylpent-l-en-l-yl, 1-methyl-pent-2-en-l-yl, 2-methylpent-2- en-l-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-l-yl, l-methylpent-3-en-l-yl, 2-methylpent-3-en- l-yl, 3-methylpent-3-en-l-yl, 4-methyl-pen t-3-en-l-yl, l-methylpent-4-en-l-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-l-yl, 4-methylpent- 4-en-1-yl, 1,1-dimethyl-but-2-en-1-yl, 1, l-dimethyl-but-3-en-1-yl, 1,2-dimethyl but-1-en-l-yl, 1,2-dimethyl-but-2-en-l-yl, 1,2-di-

II methyl-but-3-en-l-yl, 1, 3-dimethyl-but-l-en-l-yl, 1,3-dimethyl-but-2-en-l-yl, 1, 3- Dimethyl-but-3-en-l-yl, 2,2-dimethyl-but-3-en-l-yl, 2,3-dimethyl-but-l-en-l-yl, 2,3- Dimethyl-but-2-en-1-yl, 2, 3-dimethyl-but-3-en-1-yl, 3,3-dimethyl-but-1-en-1-yl, 3, 3-dimethyl-but-2-en-l-yl, 1-ethyl-but-1-en-l-yl, l-ethylbut-2-en-l-yl, l-ethylbut-3-en-l- yl, 2-ethylbut-l-en-l-yl, 2-ethylbut-2-en-l-yl, 2-ethylbut-3- en-l-yl, 1, 1, 2-trimethyl-prop-2- en-l-yl, 1-ethyl-l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-l-en-l-yl or l-ethyl-2-methyl prop-2-en-l-yl, especially for allyl;

C ₃ -C ₆ alkynyl for: for example prop-1-in-1-yl, propargyl, n-but-1-in-1-yl, n-but-1-in-3-yl, n-but- l-in-4-yl, n-but-2-in-l-yl, n-pent-1-in-l-yl, n-pent-l-in-3-yl, n-pent-l- in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2-in

5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in-l-yl, n-hex-l- in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n-hex-2-in l-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in-l- yl, n-hex-3-in-2-yl, 3-methyl-pent-l-in-l-yl, 3-methyl-pent-l-in-3-yl, 3-methyl-pent-l- in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in-4-yl or 4- Methyl-pent-2-in-5-yl, especially for propargyl;

C ₃ -C ₆ alkenyloxy for: for example prop-1-en-l-yloxy, allyloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n-buten-3-yloxy, 1-methylprop-l-en-l-yloxy, 2-methylprop-l-en-1-yloxy, l-methylprop-2-en-l-yloxy, 2-methylprop-2-en- 1-yloxy, n- Penten-1-yloxy, n-penten-2-yloxy, n-penten-3-yl - oxy, n-penten-4-yloxy, 1-methylbut-l-en-l-yloxy, 2-methyl-but- 1-en-l-yloxy, 3-methylbut-l-en-l-yloxy, l-methylbut-2-en-1-yloxy, 2-methylbut-2-en-l-yloxy, 3-methylbut-2- en-l-yl-oxy, l-methylbut-3-en-l-yloxy, 2-methylbut-3-en-l-yloxy, 3-methylbut-3-en-l-yloxy, 1, l-dimethyl- prop-2-en-l-yloxy, 1, 2-dimethyl-prop-l-en-l-yloxy, 1, 2-dimethyl-prop-2-en-l-yl - oxy, l-ethylprop-l- en-2-yloxy, l-ethylprop-2-en-l-yloxy, n-hex-1-en-l-yloxy, n-hex-2-en-l-yloxy, n-hex-3-en- l-yloxy, n-hex-4-en-l-yloxy, n-hex-5-en-l-yloxy, 1-methyl-pent-l-en-1-yloxy, 2-methylpent-l-en- l-yloxy, 3-methylpent-l-en-l-yloxy, 4-methylpent-l-en-l-yloxy, l-methylpent-2-en-l-yloxy, 2-methylpent-2-en- l-yloxy, 3-methylpent-2-en-l-ylo xy, 4-methylpent-2-en-l-yloxy, l-methylpent-3-en-l-yloxy, 2-methylpent-3-en-l-yloxy, 3-methylpent-3-en-l-yloxy, 4-methylpent-3-en-l-yloxy, l-methylpent-4-en-l-yloxy, 2-methylpent-4-en-l-yloxy, 3-methylpent-4-en-l-yloxy,

4-methylpent-4-en-l-yloxy, 1, l-dimethyl-but-2-en-l-yloxy,

1, l-dimethyl-but-3-en-l-yloxy, 1, 2-dimethyl-but-l-en-l-yloxy, 1,2-dimethyl-but-2-en-l-yloxy, 1,2-dimethyl-but-3-en-1-yloxy,

1,3-dimethyl-but-1-en-1-yloxy, 1,3-dimethyl-but-2-en-1-yloxy,

1,3-dimethyl-but-3-en-l-yloxy, 2,2-dimethyl-but-3-en-l-yloxy,

2,3-dimethyl-but-l-en-l-yloxy, 2,3-dimethyl-but-2-en-l-yloxy, 2,3-dimethyl-but-3-en-l-yloxy, 3,3 -Dimethyl-but-l-en-l -yloxy,

3,3-dimethyl-but-2-en-l-yloxy, 1-ethylbut-l-en-l-yloxy, l-ethylbut-2-en-l-yloxy, l-ethylbut-3-en-l- yloxy, 2-ethyl-but-1-en-1-yloxy, 2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy, 1, 1, 2-trimethyl-prop- 2-en-l-yloxy, 1-ethyl-l-methyl-prop-2-en-l-yloxy, l-ethyl-2-methyl-prop-l-en-l-yloxy or l-ethyl-2- methyl-prop-2-en-l-yloxy, especially for allyloxy;

C ₃ ~ C ₆ -alkynyloxy for: e.g. prop-1-in-l-yloxy, propargyloxy, n-but-1-in-l-yloxy, n-but-l-in-3-yloxy, n-but- l-in-4-yloxy, n-but-2-in-l-yloxy, n-pent-1-in-l-yloxy, n-pent-l-in-3-yloxy, n-pent-l- in-4-yloxy, n-pent-1-in-5-yloxy, n-pent-2-in-1-yl-oxy, n-pent-2-in-4-yloxy, n-pent-2- in-5-yloxy, 3-methyl-but-l-in-3-yloxy, 3-methyl-but-l-in-4-yloxy, n-hex-1-in-l-yloxy, n-hex l-in-3-yloxy, n-hex-l-in-4-yloxy, n-hex-l-in-5-yloxy, n-hex-l-in-6-yloxy, n-hex-2- in-1-yloxy, n-hex-2-in-4-yloxy, n-hex-2-in-5-yloxy, n-hex-2-in-6-yloxy, n-hex-3-in l-yloxy, n-hex-3-in-2-yloxy, 3-methyl-pent-l-in-l-yloxy, 3-methyl-pent-l-in-3-yloxy, 3-methyl-pent- l-in-4-yloxy, 3-methyl-pent-l-in-5-yloxy, 4-methyl-pent-l-ιn-l-yloxy, 4-methyl-pent-2-in-4-yloxy or 4-methyl-pent-2-yn-5-yloxy, especially for propargyloxy.

With regard to the use of the substituted 2-phenylpyridines I as herbicides and / or as desiccant / defoliant compounds, the variables preferably have the following meanings, individually or in combination:

n zero;

R ¹ Cχ-C ₆ alkylsulfonyl, in particular S0 ₂ CH ₃ ;

R ² halogen, especially chlorine;

R ^{3 is} hydrogen, fluorine or chlorine, particularly preferably fluorine or chlorine, in particular fluorine;

R ⁴ cyano or halogen, particularly preferably cyano or chlorine, especially chlorine;

/, R ^{5 is} hydrogen, nitro, cyano, hydroxylamino, Cχ-C ₆ alkyl

(in particular CH ₃ ), Cχ-C ₆ -haloalkyl (especially halogen - methyl), -COC1, -CO-OR ⁶ , -CO-O- (Cχ-C ₄ -alkylene) -CO-OR ⁶ , -0- (Cχ-C ₄ -alkylene) -CO-OR ⁶ , -0- (Cχ-C -alkylene) -CO-O- (Cχ-C ₄ - alkylene) -CO-OR ⁶ , -OR ⁹ , for yl, -CH = N-OR ¹⁵ or -NH ₂ ;

R ^{6 is} hydrogen, Cχ-C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl or -C-C ₆ alkoxy-C -C ₆ alkyl;

R ^{9 is} hydrogen, Cχ-C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

R ¹⁵ Cχ-C ₆ alkyl.

l The compounds of the formula Ia (I with n = zero; R ¹ = methylsulfonyl; R ² and R ⁴ = chlorine; R ³ = fluorine) are very particularly preferred, in particular the compounds of Table 1:

Table 1

lo

7

/ δ

2Ό

2ι

U

22 »

2 «f

2t

1

78

1Λ

ID

3ι

31

Furthermore, the substituted 2-phenylpyridines of the formulas Ib, Ic, Id, Ie and If are very particularly preferred, in particular

the compounds Ib.l to Ib.662, which differ from the corresponding compounds la.l to Ia.662 only in that R ^{3 is} chlorine:

the compounds Ic.l to Ic.662, which differ from the corresponding compounds la.l to Ia.662 only in that R ^{3 is} hydrogen:

the compounds Id.l to Id.662, which differ from the corresponding compounds la.l to Ia.662 only in that R ^{4 is} cyano:

the compounds Ie.l to Ie.662, which differ from the corresponding compounds la.l to Ia.662 only in that R ^{3 is} chlorine and R ^{4 is} cyano:

the compounds If.l to If .662, which differ from the corresponding compounds la.l to Ia.662 only in that R ^{3 is} hydrogen and R ^{4 is} cyano:

3 * 1 The substituted 2-phenylpyridines of the formula I can be obtained in various ways, for example by one of the following processes:

Aj method

Oxidation of substituted 2-phenylpyridines of the formula I, in which n is zero and R ¹ and R ⁵ contain no oxidizable sulfur, in a manner known per se {cf. e.g. A. Albini & S. Pietra, Heterocyclic N-Oxides, CRC-Press Inc., Boca Raton, USA 1991; HS Mosher et al., Org. Synth. Coll. Vol. IV 1963, page 828; EC Taylor et al., Org. Synth. Coll. Vol. IV 1963, page 704; TW Bell et. al. , Org. Synth. ü_9_, page 226 (1990)}:

oxidation

I (n = 0) ► I (n = l)

Among the conventionally used for the oxidation of the pyridine oxidizing agents is exemplified on peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, Monopermalein- acid, magnesium monoperphthalate, sodium perborate, oxone ^® (contains peroxydisulfate), pertungstic acid and hydrogen peroxide, referred.

Suitable solvents are e.g. Water, sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid and halogenated hydrocarbons such as dichloromethane and chloroform.

The oxidation is usually successful at temperatures from 0 ° C to the boiling point of the reaction mixture.

The oxidizing agent is normally used in at least equimolar amounts, based on the starting compound. In general, an excess of oxidizing agent has proven to be particularly advantageous.

Procedure B>

Oxidation of substituted 2-phenylpyridines of the formula I in which R ^{1 is} Cχ-C ₆ -alkylthio or Cχ-C ₆ -alkylsulfinyl and the substituent R ^{5 contains} no oxidizable sulfur, in a manner known per se {cf. e.g. CS Giam et al., Org. Prep. Proced. Int. 11 (2), p. 137 (1981); SG Woods et al., J. Heterocycl. Chem. ZI, 97-101 (1984); SG Woods, U.S. 4,616,087; N. Finch et al., J. Med. Chem. 21 (12), 1269-1274 (1978); H. Ban Oganowska, Pd. J. Chem. £ 1 (9), 1609-1613 (1993); AD Dünn & R. Norrie, J. Prakt. Chem. / Chem. - Currently 3_3>, 269-272 (1993)}:

I (R ¹ = alkylthio) KR '- ^ alkylsulfinyl)

R = Cι-C alkyl _fi

I (R '= alkylsulfonyl)

With regard to suitable solvents and reaction temperatures, reference is made to the information given in process A>. In addition to the oxidizing agents mentioned in process A), alkali metal hypohalides such as sodium and potassium hypochlorite are also suitable here.

For the production of valuable products I with R ¹ = alkylsulfinyl, it is advisable not to use more than about 1.1 equivalents of the oxidizing agent. To prepare I with R ¹ = alkylsulfonyl, it is necessary to use at least one equivalent or at least two equivalents of the oxidizing agent, depending on whether one starts from the corresponding compounds I with R ¹ = alkylthio or with R ¹ = alkylsulfinyl.

Process C)

Transition metal-catalyzed cross-coupling reaction of 2-halopyridines II (Hai = chlorine or bromine) with organometallic compounds of the formula III in a manner known per se {cf. e.g. WO 95/02580 and the literature cited there on pages 21 and 22}:

ή M ¹ stands for B (OH) ₂ , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, lithium, copper or tin tri (Cx-C -alkyl), preferably for B. (OH) ₂ , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br or Zn-J.

Alternatively, the boroxins IV can also be used instead of the boronic acids III {M ¹ B (OH) ₂ }.

Palladium catalysts such as tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride and 1,4-bis (diphenylphosphino) butane-palladium (II) chloride come in particular as catalysts , 1,2 -Bis (diphenylphosphino) ethane palladiu dl) chloride, palladium (II) acetate + triphenylphosphine, palladium dl) acetate + tri - (o-tolyl) phosphine or palladium on activated carbon, and nickel catalysts such as Bis- (triphenyl-phosphine) -nickel (II) chloride, 1,3-bis (diphenylphosphino) propane-nickel (II) chloride or nickel (II) acetylacetonate.

Procedure D)

Reduction of 5-nitro-2-phenylpyridines of the formula V to 5-amino-2-phenylpyridines VI, diazotization of the amino group and reaction of the diazonium salts with a symmetrical aliphatic disulfide of the formula VII in a manner known per se:

5} Implementations of this type are generally known, for example from the following publications:

- Reduction of nitropyridines with hydrogen: F. Janssens et al., J. Med. Chem. 2. (12), p. 1943 (1985);

- Reduction of nitropyridines with iron:

B.A. Fox et al., Org. Synth. ., P. 34 (1964);

- Reduction of nitropyridines with tin (II) chloride:

L.A. Perez-Medina et al. , J. Am. Chem. Soc. 6__, p. 2574 (1947); - Reduction of nitropyridines with hydrazine:

G. J. Clark et al. , Aust. J. Chem. M, p. 927 (1981);

- Reduction of nitropyridines with tin:

K. Wojciechowski et al. , Synthesis, 651-653 (1986);

- Reduction of nitropyridines with low-valent titanium compounds: M. Malinowski, B. Soc. Chim. Belg. 9_7 (1), 51-53 (1988);

- Reduction of nitropyridines with baker's yeast:

M. Takeshita et al. , Heterocycles 11 (12), 2201-2204 (1990);

- Reduction of nitropyridines with zinc:

K. Goerlitzer et al., Arch. Phar. 121 (10), 785-796 (1991); - Reduction of nitropyridines with sodium dithionite: F.G. Fischer et al., Ann. Chem. £ 5_1, p. 49 (1962);

- Diazotization of aminopyridines with isoamyl nitrite and reaction of the diazonium salts with dimethyl disulfide or diphenyl disulfide: C.S. Giam et al., J. Chem. Soc, Chem. Commun. £ 1, p. 756 (1980);

T. Yasumitsu et al., J. Org. Chem. 4 £., 3564-3567 (1981).

2- (4-Chloro-3-methoxyphenyl) -5-nitropyridine, 2- (4-Chloro-3-methoxyphenyl) -3-chloro-5-nitropyridine, 5-amino-2- (4-chloro-3-methoxy - Phenyl) pyridine and 5-amino-2 - (4-chloro-3-methoxyphenyl) -3-chloro-pyridine are already known from WO 95/02580. Apart from these compounds, the 5 -nitro-2-phenylpyridines V and the 5 -amino-2 -phenylpyridines VI are new. V is expediently prepared analogously to process C> by transition metal-catalyzed cross-coupling reaction of 2 -halogen-5-nitropyridines of the formula VIII (Hai = chlorine or bromine) with organometallic compounds of the formula IX {cf. e.g. M.B. Mitchell et al. , Tetrahedron Lett. 21. 2273-2276 (1991)}:

3S M ² stands for B (OH), Zn-Cl, Zn-Br, Zn-J, copper or tin tri (Cχ-C ₄ alkyl).

The catalysts specified under process C) are also suitable here.

Procedure E>

Diazotization of 5-amino-2-phenylpyridines of the formula VI and reaction of the diazonium salts with S0 ₂ in the presence of copper (II) chloride {cf. e.g. US 4,784,684 and Gilbert in Synthesis 1969,

Reaction of I (R ¹ = S0 ₂ C1) with ammonia, primary or secondary amines leads to the corresponding compounds I with R ^l = H ₂ N-S0 ₂ , alkyl-NH-S0 ₂ or (alkyl) ₂ N-S0 ₂ {see. e.g. C. Naegeli et al., Helv. Chim. Acta 21, 1485 (1942); M. Yasuhiro et al., J. Med. Chem. 21, 1376-1380 (1980); JF Liegeois et al. , Helv. Chim. Acta IA, 8, 1764-1772 (1991) and P. De Tullio et al., Tetrahedron H, 11, 3221-3234 (1995}

I (Cχ-C ₆ alkyl) NH ₂

(R ¹ Cl- S0 ₂ ) I {R ¹ = (Cχ-C ₆ alkyl) -NH-S0 ₂ }

I {R ¹ = (C -C ₆ alkyl) ₂ N-S0 ₂ }

(Cχ-C ₆ alkyl) ₂ NH

The substituted 2 -phenylpyridines I with R ¹ = chlorosulfonyl can also be hydrolyzed to the corresponding compounds I with R ¹ = hydroxysulfonyl.

The substituted 2-phenylpyridines I can normally be prepared by one of the synthesis processes mentioned above. For economic or procedural reasons, however, it may be more expedient to prepare some compounds I from similar 2-phenylpyridines, but which differ in the meaning of a radical.

3 1 The compounds of the formula Ha

are new. 2 -Chlor - 5 -methylthiopyridm is for example from J. Med.

Chem. 16., 319-327 (1973). For 2-chloro-5-methyl-sulfinyl and 2-chloro-5-methylsulfonylpyridine see. J. Med.

Chem. 2i <427-433 (1986); regarding 2 -Brom- 5 - ter. -butyl thiopyridine is on Bull. Soc. Chim. Belg. 9_5_, 1009-1020 (1986).

In general, the preparation of the 2 -halopyridines II can be carried out, for example, by diazotizing the corresponding 5 -Am opyridme X ^1] - preferably with a nitrous acid ester such as tert. -Butyl nitrite and isopentyl nitrite - and subsequent reaction of the diazonium salt with a symmetrical aliphatic disulfide VII {see. e.g. J. Chem. Soc, Chem. Commun. 1980, pp. 756/757}: 1. Diazotization _{2 (Cι, C6, alkyl),} s " (C, -C ₆ alkyl) -S

X VII

The diazotization can also take place in the presence of disulfide VII.

It is preferable to work in an anhydrous system, for example in glacial acetic acid which contains hydrogen chloride, in dioxane, absolute ethanol, tetrahydrofuran, acetonitrile or in acetone.

The reaction temperature is usually (-30) to 80 ° C.

The components of the diazotization reaction are usually used in an approximately stochiometric ratio, but an excess of one of the components, e.g. with a view to implementing the other component as completely as possible. The nitrite is preferably used in excess, up to about 2 times the molar amount, based on the amount of X.

The disulfide VII is expediently used in approximately equi olar amounts or in excess, based on the diazonium salt. In general, a large excess of disulfide VII (up to about 5 times the molar amount), based on the amount of diazonium salt, has proven to be particularly advantageous.

- ⁾ for their production see J Med. Chem. 16, 319-327 (1973) The 2 -halopyridines II with R ¹ = Cx-Cβ-alkylthio can then be oxidized to the corresponding compounds with R ¹ = Cχ-C ₆ -alkylsulfinyl or Cx -C ₆ -alkylsulfonyl, as described under process B> for the compounds I with R ¹ = Ci -C ₆ alkylthio has been described.

Unless otherwise stated, all of the processes described above are expediently carried out at atmospheric pressure or under the autogenous pressure of the respective reaction mixture.

The reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and then isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable one organic solvents and working up the organic phase towards the product.

The substituted 2-phenylpyridines I can be obtained in the preparation as isomer mixtures, which, however, if desired, can be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.

Agricultural salts of the compounds I can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride.

Salts of I, the metal ion of which is not an alkali metal ion, can also be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and harmful

hι grasses without significantly damaging the crops. This effect occurs especially at low application rates.

Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for removing undesired plants. The following crops are possible, for example: Alliu cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodonine dactis , Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypiu arboreum, Gossypium herbaceu, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culitaticonersusum, lens culitatissusum , Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisu sativ m, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triti cum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.

Furthermore, the substituted 2-phenylpyridines I are also suitable for the desiccation and / or defoliation of plants.

As desiccants, they are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables fully mechanical harvesting of these important crops.

Also of economic interest is the ease of harvesting, which is made possible by the temporally concentrated drop or decrease in the adhesive strength on the tree for citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, that is, the promotion of the formation of separating tissue between the fruit or leaf and sprout part l of the plants is also essential for a well controllable defoliation of useful plants, especially cotton.

In addition, the shortening of the time interval in which the individual cotton plants ripen leads to an increased fiber quality after the harvest.

The compounds I or the compositions comprising them can be sprayed, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules. Nebulization, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as

Kerosene and diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oldispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare active substances, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or existing concentrates which are suitable for dilution with water.

The surfactants (adjuvants) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene

<ι3 or the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensate oil, polyoxyethylene ethoxylated alcohol ethoxylated ethoxylated alcohol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethylene glycol ethoxylated ethoxylated ethylene glycol ethoxylated alkoxylated ethoxylated ethoxylated ethoxylated ethoxylated ethoxylated alcohol, , Lignin sulfite liquor or methyl cellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. In general, the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The following formulation examples illustrate the preparation of such preparations:

I. 20 parts by weight of compound no. Ia.181 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 Parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. II. 20 parts by weight of compound no. Ia.384 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone,

30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the additive of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

III. 20 parts by weight of active ingredient No. Ia.402 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

IV. 20 parts by weight of active ingredient No. 2 are with

3 parts by weight of the sodium salt of diisobutyl-naphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel are mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

V. 3 parts by weight of active ingredient No. 3 are with

97 parts by weight of finely divided kaolin mixed. In this way, a dust is obtained which contains 3% by weight of the active ingredient.

VI. 20 parts by weight of active ingredient No. 7 are with

2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

VII. 1 part by weight of active ingredient No. 10 is in a

Dissolved mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and

There are 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained. T VIII. 1 part by weight of active ingredient No. 13 is in a

Mixture made up of 80 parts by weight of cyclohexanone and

(fr

20 parts by weight of Wettol ^J EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG). A stable emulsion concentrate is obtained.

The active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients on the leaves underneath are growing undesirably Plants or the uncovered floor area (post-directed, lay-by).

The application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.

To broaden the spectrum of activity and to achieve synergistic effects, the substituted 2-phenylpyridines I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1,2,4-thiazadiols, 1,3,4-thiadiazoles, amide, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzo, come as mixing partners - thiadiazinone, 2 - (hetaroyl / aroyl) - 1, 3 -cyclohexanedione, heteroaryl-aryl-ke one, benzylisoxazolidinones, meta-CF-phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3 -dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyl-uracils, imidazoles, imidazylones, 3-one , 4, 5, 6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridine car bonic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

It can also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

Manufacturing examples

Example 1 (Compound Ia.384 in Table 1):

12.1 g (2,3-dichloro-5-mechylsulfonylpyridine, 11.05 g 4-chloro-2-fluoro-5-methoxybenzeneboronic acid, 13.6 g sodium hydrogen carbonate and 2.0 g tetrakis (triphenylphosphine) palladiu (0) were heated to reflux temperature for 120 hours in 360 ml of a tetrahydrofuran / water mixture (1: 1). After cooling to room temperature, the mixture was extracted three times with 200 ml each of methyl tert-butyl ether (MTB) ml of water, then dried over sodium sulfate and finally evaporated in. The crude product was purified by column chromatography on silica gel (mobile phase: cyclohexane / MTB = 10: 1 → 7: 3 → 1: 1). The white crystals obtained (5.8 g) were further purified by stirring with MTB / petroleum ether (1: 1) Yield: 5.2 g (27%), mp: 184-185 ° C.

Precursor α: 2,3-dichloro-5-ethylthio-pyridine

To a solution of 56.6 g (0.6 mol) of dimethyl disulfide and 46.7 g (0.45 mol) of tert. -Butyl nitrite in 320 ml of dry methylene chloride, a solution of 50.6 g (0.3 mol) of 3-amino-5, 6 -dichloropyridine in 700 ml of methylene chloride was slowly added at 40 ° C. The mixture was then stirred at 40 ° C. for 1 hour and then at about 20 ° C. for a further 15 hours, after which 500 ml of ice water were added to the reaction mixture. The separated organic phase was washed once with 1N hydrochloric acid and once with water, dried over sodium sulfate and finally concentrated. After stirring the crude product with n-hexane, 21 g of a dark solid (94% purity according to GC) were obtained. After concentrating the hexane solution, 21.3 g of valuable product with a purity of 77% remained (according to GC). Overall yield: 62%; Mp: 66-67 ° C; ¹ H-NMR (in d ⁶ -dimethyl sulfoxide): δ [ppm] = 2.6 (s, CH ₃ ); 8.1 and 8.3 (2xd, Pyr-H).

Precursor β: 2,3-dichloro-5-ethylsulfinyl-pyridine

8.9 g (0.052 mol) of m-chloroperbenzoic acid were added in portions to a suspension of 10 g (0.052 mol) of 2, -dichloro-5-methylthio-pyridine in 60 ml of methylene chloride. After stirring for 2 hours at about 20 ° C., the mixture was mixed with a further 0.9 g (5 mmol) m-chloroperbenzoic acid. The mixture was then heated to the reflux temperature for a further 2 hours. After cooling, the solids fraction was separated off, after which the organic phase was washed once with sodium hydrogen sulfite, once with sodium hydrogen carbonate and once with water. After drying over sodium sulfate, the mixture was concentrated. The crude product obtained as a red oil was purified by means of "flash chromatography" on silica gel (mobile phase: cyclohexane / ethyl acetate = 1: 1). Yield: 6.3 g (58%) as a brown oil; * H NMR (in d ⁶ -dimethylsulfoxide): δ [ppm] = 2.9 (s, CH ₃ ); 8.4 and 8.7 (2xd, Pyr-H).

Precursor γ: 2,3-dichloro-5-methylsulfonyl-pyridine

6.2 g (0.02 mol) of Na ₂ WO ₄ -2H ₂ O were added to a solution of 73.7 g (0.38 mol) of 2,3-dichloro-5-methylthiopyridine in 380 ml of glacial acetic acid. After heating to 40-50 ° C, the mixture was carefully mixed with 95 g of hydrogen peroxide (30%). The mixture was then stirred at about 20 ° C for 1 hour. Then the mixture was poured into 300 ml of water. The product was separated from the suspension obtained, washed with water and n-pentane and dried under reduced pressure. Yield: 60 g (70%) as a brown powder; Mp: 129-130 ° C; * H-NMR (in d ⁶ -dimethyl sulfoxide): δ [ppm] = 3.4 (s, CH ₃ ); 8.7 and 8.9 (2xd, Pyr-H).

Example 2 (Compound Ia.383 in Table 1):

4.15 g of the compound Ia.384 obtained according to Example 1 and 10.2 g of pyridine hydrochloride were heated to 200 ° C. for four hours under a nitrogen atmosphere. After cooling, the reaction was taken up in 100 ml of 10% hydrochloric acid. The product was then extracted five times with 90 ml of dichloromethane each. The combined organic phases were washed with 100 ml of water, dried over sodium sulfate and finally concentrated. The crystals obtained were purified by stirring with MTB / petroleum ether (1: 1). After separation and drying, 3.6 g (90%) of white crystals were obtained; M.p .: 176-178 ° C.

Example 3 (Compound Ia.402 in Table 1):

0.52 g of propargyl bromide was added dropwise to 1.2 g of the compound Ia.383 prepared according to Example 2 and 0.99 g of potassium carbonate in 80 ml of anhydrous dimethylformamide. After stirring for 12 hours at 23 ° C., the mixture was diluted with 200 ml of water. Then the product was extracted four times with 100 ml MTB each. The combined organic phases were washed with 100 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by stirring with n-hexane / Diethyl ether (10: 1). After separation and drying, 0.9 g (67%) of white crystals were obtained; M.p .: 182-183 ° C.

Example 4 (Compound Ia.182 in Table 1; (R) -enantiomer):

To 2.4 g of the compound Ia.383 prepared according to Example 2 and 1.97 g of potassium carbonate in 100 ml of anhydrous dimethylformamide were added dropwise 1.05 g of methyl (S) -2-chloropropionate. After stirring for sixty hours at 23 ° C., the mixture was diluted with 300 ml of water. Then the product was extracted four times with 80 ml MTB each. The combined organic phases were washed with 100 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by chromatography on silica gel (mobile phase: cyclohexane / MTB = 5: 1 → 7: 1). Yield: 2.6 g (86%) of a colorless oil. iH-NMR (200 MHz; in CDC1 ₃ ): δ [ppm] = 1.70 (d, 3H), 3.20 (s, 3H), 3.77 (s, 3H), 4.78 (q, lH), 7.00 (d, 1H), 7.28 (d, lH), 8.33 (s.lH), 9.07 (s, lH).

Example 5 (Compound Ia.181 in Table 1; (R) -enantiomer):

1.2 g of the compound Ia.182 prepared according to Example 4 were in a mixture of 25 ml of glacial acetic acid and 10 ml of 2M hydrochloric acid

4 hours at 70 to 80 ° C and then stirred for 16 hours at 23 ° C. After dilution with 100 ml of water, the mixture is extracted five times with 60 ml of MTB each time. The combined organic phases were washed twice with 60 ml of saturated aqueous sodium chloride solution, then dried over sodium sulfate and finally concentrated. The crude product was purified by stirring with n-hexane / diethyl ether (2: 1). Yield: 0.75 g (65%) of white crystals; mp: 161-164 ° C.

Example 6: 3-chloro-2- (4-chloro-2-fluo-5-methoxyphenyl) -5-methylsulfinylpyridine

4.6 g of 2,3-dichloro-5-methylsulfinylpyridine, 4.5 g of 4-chloro-2-fluoro-5-methoxybenzeneboronic acid, 5.5 g of sodium hydrogen carbonate and 1.0 g of tetrakis (triphenylphosphine) palladium (O) were heated in a mixture of 100 ml of water and 100 ml of tetrahydrofuran at reflux temperature for 180 hours. After the tetrahydrofuran had been evaporated, the mixture was extracted four times with 70 ml of MTB each. Then the combined organic phases were dried over sodium sulfate and finally concentrated. The oil obtained was purified by chromatography on silica gel (mobile phase: cyclohexane / MTB = 7: 3 → 1: 1 and cyclohexane / ethyl acetate = 2: 1). By stirring the oil thus purified with diethyl ether, 2.2 g (30%) of white crystals were obtained; M.p .: 117-118 ° C.

^ Example 7

Preparation of the intermediate 2, 3-dichloro-5-ethylsulfonyl-pyridine:

Analogously to Example 1, precursor γ, 5 g (0.024 mol) of 2,3-dichloro-5 5-ethylthio-pyridine with 0.4 g (1.2 mol) of Na ₂ WO-2H ₂ 0 and 6 g

Hydrogen peroxide (30%) implemented in 25 ml glacial acetic acid. After working up, 5.1 g of valuable product were obtained as a white solid. Yield: 88.5%; Mp : 141-142 ° C; ⁱ -H NMR (in d ⁶ -dimethyl sulfoxide): δ [ppm] = 1.2 (t, CH ₃ ); 3.5 (q, CH _2); 8.6 and 8.8 (2xd, Pyr-H). 10

Precursor α: 2, 3-dichloro-5-ethylthio-pyridine

Analogously to Example 1, precursor α, 24.45 g (0.15 mol) of 3-amino-5, 6-dichloropyridine in 280 ml of methylene chloride with 36.6 g (0.3 mol) of 15 diethyl disulfide and 23.2 g ( 0.225 mol) tert. -Butylnitri implemented in 130 ml methylene chloride. After working up and then washing out the crude product with ethanol, 13.3 g of valuable product were obtained. Yield: 42%; ¹ H NMR (in d ⁶ -dimethyl sulfoxide): δ [ppm] = 1.25 (t, CH ₃ ); 3.10 (d, CH ₂ ); 8.15 and 8.3 (2xd, Pyr-H).

20th

Precursor β: 2, 3-dichloro-5-ethylsulfinyl-pyridine

Analogously to Example 1, precursor β, 4 g (0.02 mol) of 2,3-dichloro-5-ethylthio-pyridine were mixed with 3.47 g (0.02 mol) of m-chloroperbenzoic acid

25 30 ml of methylene chloride reacted. After purification of the crude product by means of flash chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate = 2: 1), 1.9 g of valuable product were obtained in the form of white crystals. Yield: 42%. Mp: 78-79 ° C; iH-NMR (d ⁶ -dimethyl sulfoxide): δ [ppm] = 1.1 (t; CH ₃ ); 3.0 and 3.2

30 (2xm, CH ₂ ); 8.35 and 8.6 (2xs, Pyr-H).

Example 8

Preparation of the intermediate 2, 3-dichloro-5-isopropylsulfonylpyridine:

35

Analogously to Example 1, precursor γ, 15 g (0.068 mol) of 2,3-dichloro-5-isopropylthio-pyridine (crude product) with 1.11 g (3.6 mmol) of NaW0 * 2H ₂ 0 and 17 g of hydrogen peroxide (30 %) implemented in 80 ml of acetic acid. After processing and additional training

40 stirring of the crude product with ethanol gave 3.5 g of valuable product as a light powder. Yield: 20%; Mp: 146 ° C; ⁱ H-NMR (in d ⁶ -dimethylsulfoxide): δ [ppm] = 1.2 (d, 2xCH ₃ ); 3.65 (m, CH); 8,6 and 8, 8 (2xd, Pyr-H).

45 Precursor α: 2,3-dichloro-5-isopropylthio-pyridine

Analogously to Example 1, precursor α, 13.1 g (0.08 mol) of 3-amino-5, 6-dichloropyridine in 120 ml of methylene chloride with 25 g (0.16 mol) of diisopropyl disulfide and 12.4 g (0.12 mol) tert. -Butyl nitrite implemented in 70 ml methylene chloride. 30 g of a dark oil (approx. 40% product of value) were obtained, which was reacted further without further purification. ¹ H-NMR (in d ⁶ -dimethylsulfoxide): δ [ppm] = 1.25 (d, 2xCH ₃ ); 3.7 (m, CH); 8.2 and 8.3 (2xd, Pyr-H).

Precursor β: 2, 3-dichloro-5-isopropylsulfinyl-pyridine

Analogously to Example 1, precursor β, 10 g (0.045 mol)

2, 3-dichloro-5-isopropylthio-pyridine (as crude product) with 7.8 g (0.045 mol) of m-chloroperbenzoic acid in 60 ml of methylene chloride. After purification of the crude product by means of flash chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate = 1: 1), 1.7 g of valuable product were obtained. Yield: 16%; M.p .: 62-64 ° C; ^X H NMR (in d ⁶ -dimethyl sulfoxide): δ [ppm] = 1.0 and 1.25 (2xd, 2xCH ₃ ); 3.2 (m, CH); 8.3 and 8.5 (2xd, Pyr-H).

The following Table 2 lists further substituted 2-phenyl ^• pyridines I:

Table 2

57

Examples of use (herbicidal activity)

The herbicidal activity of the substituted 2-phenylpyridines I was demonstrated by the following greenhouse tests:

Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

In pre-run treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.

For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for post-emergence treatment was 0.0313 or 0.0156 kg / ha a.S. (active substance).

The plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.

S ^~ 2 Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

The plants used in the greenhouse experiments are composed of the following types:

At application rates of 0.0313 and 0.0156 kg / ha a.S. Compound No. Ia.384 showed a very good herbicidal activity against the above-mentioned broad-leaved plants in the post-emergence process.

Examples of use (desiccative / defolian effectiveness)

Young, 4-leaf (without cotyledons) cotton plants served as test plants, which were grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature 27/20 ° C.).

The young cotton plants were dripping wet with aqueous preparations of the active ingredients (with an addition of 0.15 wt -.% Of the fatty alcohol alkoxylate Plurafac LF 700 ^® ^2), based on the

Spray broth) treated with leaves. The amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

No leaf fall occurred in the untreated control plants.

²⁾ a low-foaming, nonionic surfactant from BASF AG

$ 3

Claims

claims

Substituted 2 - phenylpyridines of the general formula I

in which the variables have the following meanings:

n zero or 1;

R ¹ mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, Ci -C ₆ alkylthio, C _x -C ₆ alkylsulfinyl, Cι -C ₆ alkylsulfonyl, Ci - C $ alkylaminosulfonyl or di- (Ci -C ₆ alkyl) ) aminosulfonyl;

R ² , R ³ independently of one another are hydrogen or halogen;

R ⁴ cyano, hydroxy, halogen, -CC ₆ alkoxy or phenyl - methoxy, where the phenyl ring can be unsubstituted or can carry one to three substituents, each selected from the group consisting of hydroxy, halogen, Ci-Cβ-alkyl, Ci -C ₆ - haloalkyl, Ci -C _Ö alkoxy, Ci-C _δ -haloalkoxy, hydroxycarbonyl, (-C-C ₆ alkoxy) - carbonyl and (CI-C _Ö alkoxy) carbonyl -Ci -C ₆ - alkoxy;

R ⁵ is hydrogen, nitro, cyano, hydroxylamino, halogen, Cι-C ₆ -alkyl, C ₆ haloalkyl, -COCl, -CO-OR ^6, -CO-N (R) R ^a, -CO-O- (-C-C alkylene) -CO-OR ⁶ , -CO-O- (-C-C ₄ alkylene) -C0-N (R ⁷ ) R ^e , -X ¹ - (Ci -C ₄ alkylene) - CO-R ⁶ , -X ¹ - (-C-C ₄ alkylene) -CO-OR ⁶ , -X ¹ - (Cι-C ₄ alkylene) - CO-O- (C _! -C alkylene) -CO -OR ⁶ , -X ¹ - (-C-alkylene) - CO-N (R ⁷ ) R ^θ , -X ^ R ⁹ , -CH = C (R ¹⁰ ) -CO-OR ⁶ , -CH = C (R ¹⁰ ) -CO-O- (-C-alkylene) -CO-OR ⁶ , -CH = C (R ¹⁰ ) -CO-N (R ⁷ ) R ⁸ , formyl, -CO-R ⁶ ,

^f ι -C (R ⁸ ) = N-OR ¹⁵ , -X ¹ - (-Cι-C ₄ -alkylene) -C (R ⁸ ) = N-0R ¹⁵ , -CH = C (R ¹⁰ ) -C (R ⁸ ) = N-OR ¹⁵ , -CH (C _λ -C ₆ alkoxy) ₂ , -N (R ¹⁶ ) R ¹⁷ , -N (R ¹⁶ ) -S0 ₂ - (Cx-Ce-alkyl), -N (R * ⁶ ) -CO- (Cα ^' -Cβ-alkyl), chlorosulfonyl, hydroxysulfonyl or - S0 ₂ -N (R ¹⁸ ) R ¹⁹ _;

R ⁶ are hydrogen, C ₆ alkyl, _Ci-C6 haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, Cι-C alkoxy-Cι ₆ -C ₆ alkyl or 3-oxetanyl;

R ^{7 is} hydrogen or -CC ₆ alkyl;

R ⁸ is hydrogen, hydroxy, _Cι-C6 alkyl, hydroxycarbonyl -Cι-C ₆ alkyl, (Cι-C ₆ -alkoxy) carbonyl -C -C ₆ alkyl, C -C _ß alkoxy, _Ci-C6 -Halogenalkoxy, phenyl -Ci -C ₆ alkoxy, C ₃ -C ₆ alkenyloxy or C ₃ -C ₆ alkynyloxy or

R ⁷ and R ^θ together form a tetra or pentamethylene chain which can carry a (Ci -C _δ alkoxy) carbonyl radical;

R ^{9 is} hydrogen, -CC ₆ alkyl, Ci -C ₆ - haloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or Ci-C _ö alkoxy-Ci -C _δ alkyl;

R ^{10 is} hydrogen, halogen or Ci-C _ö alkyl;

Riι. ^ 14 independently of one another hydrogen, -CC ₆ alkyl or (Ci -C ₆ alkoxy) carbonyl;

R ^{15 is} hydrogen, -CC ₆ alkyl, phenyl -C _! -C ₆ alkyl, (Cι-C ₆ alkoxy) carbonyl -Cι-C ₆ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

R ^{16 is} hydrogen or Ci -C ₆ alkyl;

R ^{17 is} hydrogen, -CC ₆ alkyl, hydroxycarbonyl -C ₆ alkyl, (Ci-C _ß alkoxy) carbonyl -C ₆ alkyl or Ci -C _δ alkoxy;

R ^{18 is} hydrogen or Ci -C ₆ alkyl;

R ^{19 is} hydrogen, -CC ₆ alkyl, hydroxycarbonyl -C ₆ -C ₆ alkyl, (Ci - C ₆ alkoxy) carbonyl -C -C ₆ alkyl or CI-C _Ö alkoxy or

X ^x -X ³ independently of one another oxygen or sulfur,

5T and the agriculturally useful salts of the compounds I with R ⁶ = hydrogen.

2. Substituted 2-phenylpyridines of formula I and their salts, according to claim 1, wherein

R ⁵ for hydrogen, nitro, cyano, hydroxylamino, Ci-Cβ-alkyl, -C-C ₆ -haloalkyl, -C0C1, -CO-OR ⁶ , -CO-O- (-C-C-alkylene) -CO-OR ⁶ , -O- (Cχ-C -alkylene) -CO-OR ⁶ , -0- (C! -C ₄ -alkylene) -CO-O- (C! -C ₄ -alkylene) -CO-OR ⁶ , - OR ⁹ ,

Formyl, -CH = N-OR ¹⁵ or -NH;

R ⁶ are hydrogen, C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ -Alkmyl or Cι-C6-alkoxy-Cι-C alkyl _δ;

R ⁹ for hydrogen, -CC ₆ alkyl, C ₃ -C _fa alkenyl or C ₃ -C ₆ alkynyl and

R ^{15 represent} -C ₆ alkyl.

3. Use of the substituted 2-phenylpyridines of the formula I and the agriculturally useful salts of I, according to claim 1, as herbicides or for desiccation and / or defoliation of plants.

4. Herbicidal composition containing a herbicidally effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one surfactant.

5. Agent for the desiccation and / or defoliation of plants, containing a desiccant and / or defoliantly effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one surface-active substance.

6. A process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, mixes at least one surfactant. st

7. A process for the preparation of desiccant and / or defoliant agents, characterized in that a desiccant and / or defoliant amount of at least one substituted 2-phenylpyridine of formula I or an agriculturally useful salt of I, according to claim 1, and mixes at least one inert liquid and / or solid carrier material and, if desired, at least one surface-active substance.

8. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, is allowed to act on plants, their habitat or on seeds.

9. A process for the desiccation and / or defoliation of plants, characterized in that a desiccant and / or defoliantly effective amount of at least one substituted 2-phenylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, is allowed to act on plants .

10. The method according to claim 9, characterized in that cotton is treated.

11. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, in which n is 1 and R ¹ and R ⁵ do not contain any oxidizable sulfur, characterized in that the corresponding substituted 2-phenylpyridines in which but n means zero, oxidized in an inert solvent / diluent.

12. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, in which R ^{1 is} C ¹ -C ₆ -alkylsulfinyl or Ci-Cβ-alkylsulfonyl and the substituent R ^{5 contains} no oxidizable sulfur, characterized in that that the corresponding substituted 2-phenylpyridines, but in which R ^{1 is} Ci-Cβ-alkylthio or Ci-Cβ-alkylsulfinyl, is oxidized in an inert solvent / diluent.

13. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, characterized in that a 2-halopyride of the formula II

where shark represents chlorine or bromine, in the presence of a transition metal catalyst with an organometallic compound of the formula III

where M ^{1 is} B (0H) ₂ , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, lithium, copper or tin tri (-C-C ₄ alkyl), or with a boroxin of formula IV

implements.

14. The method according to claim 13, characterized in that II is reacted with an organometallic compound of the formula III, where M ¹ for B (0H), Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br or Zn-J stands.

15. A process for the preparation of substituted 2-phenylpyridines of the formula I according to claim 1, in which R ^{1 is} Ci-Cβ-alkylthio, characterized in that 5-nitro-2-phenylpyridines of the formula V

V,

where n and R ² to R ^{5 have} the meanings given in claim 1, the resulting 5-amino-2-phenylpyridines of the formula VI are reduced

diazotized and finally the diazonium salts with symmetrical aliphatic disulfides of the formula VII

(-C-C ₆ alkyl) -SS- (Ci-Ce alkyl VII

15 implements

16. 15-nitro-2-phenylpyridines of the formula V

25 where n is 0 or 1 and the substituents R ² to R ^{5 have} the meanings given in claim 1, except 2 - (4-chloro-3-methoxyphenyl) -5-nitropyridine and 2 - (4-chlorine -3 - methoxyphenyl) -3-chloro-5 -nitropyridine.

30 17. 5-Amino-2-phenylpyridines of the formula VI

where n is 0 or 1 and the substituents R ² to R ^{5 have} the meanings given in claim 1, 0 except 5-amino-2 - (4-chloro-3-methoxyphenyl) pyridine and 5 -amino-2 - ( 4-chlorine -3-methoxyphenyl) -3-chloropyridine.

5

η

18. 2 halopyridines of the formula Ila

wherein shark is chlorine or bromine and R ^{1 has} the meaning given in claim 1.

i