DD299294A5 - NEW PYRIDYL SULFONAMIDE - Google Patents

Abstract

The present invention relates to novel pyridylsulfonamides and to processes for their preparation. The pyridylsulfonamides according to the invention correspond to the formula wherein R 1 is hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkoxy or CF 3; A C1-C6-alkyl or C3-C6-cycloalkyl monosubstituted to trisubstituted by halogen, or C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, C2-C4-alkenyl, C5 -C 6 -cycloalkenyl, amino, C 1 -C 4 -alkylamino, C 1 -C 4 -dialkylamino or C 2 -C 4 -alkynyl substituted C 1 -C 4 -alkyl or C 3 -C 6 -cycloalkyl, where the C 2 -C 4 -alkenyl radical and also the C 5 -C 6 -cycloalkyl Cycloalkenylrest may be substituted once to three times by halogen; or a 4- to 6-membered saturated heterocycle containing one heteroatom selected from the group O, N and SO 2; or C1-C4-alkyl which is substituted by a 4- to 6-membered saturated heterocycle containing a heteroatom selected from the group consisting of O, N and SO2. The erfindungsgemäaeszen compounds are valuable intermediates for the preparation of herbicidally active and plant growth-regulating N-pyridinesulfonyl-N-pyrimidinyl- and -triazinylharnstoffe. Formula (II) {pyridylsulfonamides; Method; manufacture; Intermediate; N-pyridinesulfonyl-N-pyrimidinylharnstoffe; N-pyridinesulfonyl-N-triazinylharnstoffe; herbicidal activity; plant growth-regulating effectiveness}

Description

N ^ * SO ₂ NH-CN- / 'E

The invention relates to novel Fyrdylsulfonamide and process for their preparation. They find use üls valuable intermediates for the preparation of herbicidally active and plant growth-regulating sulfonylureas.

Urinary compounds, triazine compounds and herbicidal pyrimidine compounds are well known.

For example, European patent no. 103543 herbicidally active and plant growth-regulating N-pyridinesulfonyl-N'-pyrimidinyl- and -triazinylureas. The active ingredients disclosed therein can not always meet the requirements regarding potency and selectivity. There is thus a need for more effective and selective active ingredients and thus also for new starting materials or intermediates for their preparation.

New pyridylsulfonamides have now been found which are suitable. To produce sulfonylureas with improved herbicidal and plant growth-regulating properties.

The N-pyridinesulfonyl-N'-pyrimidinyl and -triazinyl ureas prepared from the pyridylsulfonylamides according to the invention, which are not constituents of the present invention, correspond to the formula I,

(I)

R, is hydrogen, halogen, Ci-C ₄ alkyl, C) -C ₄ -alkoxy, C | -C ₄ alkylthio, C, -C ₄ -haloalkoxy or CF _3; R _{2 is} hydrogen or C 1 -C ₄ -alkyl;

A halogen-mono- to tri-substituted Cj-C ₆ alkyl or C ₃ -C ₆ -CyClOaIkYl or by Ci-C ₄ -alkoxy, C _t -C ₄ alkylthio, C, -C ₄ alkylsulfonyl, C, - C ₄ alkylsulfinyl, C ₂ -C ₄ -alkenyl, C ₆ -C ₆ cycloalkenyl, amino, C, _-C4 alkylamino, C, -C ₄ dialkylamino or C ₂ -C ₄ -AIkI (iyi substituted C ) -C ₄ alkyl or Cj-Ce-cycloalkyl, wherein the C ^ -CJ-alkenyl group, and the Cs-Ce cycloalkenyl group may still be one to trisubstituted by halogen; odtjr a 4 to 6 membered saturated heterocycle containing a heteroatom selected from the group O, N and SO ₂ ; or C _{(-C 4} alkyl which is substituted by a 4- to 6-membered saturated heterocycle containing one heteroatom selected from de group O, N and SO _2; XC, -C ₃ alkyl, halogen-one trisubstituted., -C _r alkyl, C | -C ₃ alkoxy or C ₁ -C ₃ alkoxy monosubstituted to trisubstituted by halogen;

Y is halogen, C, -C ₃ alkyl, halogen mono- to tri-substituted C ₃ -alkyl, C] _-C3 -alkoxy, mono- to trisubstituted by halogen, C, -C ₃ alkoxy, cyclopropyl, Methylamino or dimethylamine; and E is nitrogen or the methine group,

and the salts of these compounds.

The C ₁ -C ₄ -alkyl groups occurring as or in the substituents R ₁ , R ₂ and A may be straight-chain or branched and comprise in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl , iso-butyl and tert-butyl. Preferably, the alkyl groups present as or in the substituents R ₁ , R ₂ and A have one to three carbon atoms. For the substituents R ₁ and R ₂ , methyl is particularly preferred.

Haloalkoxy is e.g. Fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

The substituent A comprises as a Ci to Ce alkyl group monosubstituted to trisubstituted by halogen straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, η-butyl, sec-butyl, iso-butyl, tert. Butyl, n-pentyl, the isomeric pentyl, n-hexyl and the isomeric hexyl, which are monosubstituted to trisubstituted by halogen, wherein halogen in detail means fluorine, chlorine, bromine or iodine.

Among these mono- to trisubstituted by halogen-substituted Ct-Ce-alkyl groups mono- to trisubstituted by halogen-substituted C, -C ₄ alkyl groups are preferred. Preferred halogen atoms which may occur as substituents of the C ₂ -C ₆ -alkyl groups are fluorine and chlorine. Especially preferred mono- to trisubstituted by halogen-substituted alkyl groups are trifluoromethyl, 1-fluoroethyl, 1,1-dichloroethyl, 3,3,3-trifluoropropyl, 2-fluoroisopropyl, 3-fluoropropyl, 1,1,1-trichloropentyl, 1-fluoro 3-methylpentyl or 1-bromohexyl. Very particular preference is given to 3-fluoropropyl and 2-fluoroisopropyl.

The occurring in the substituent A C ₂ -C ₄ alkenyl radicals may be in the Z-form (ice) or in the Ε-form (trans) and may be straight-chain or branched. Alkenyl radicals having a chain length of two to three carbon atoms are preferred.

Examples of C ₂ -C ₄ alkenyl radicals are: vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl. Preference is given to vinyl and allyl. In the case of the C ₂ -C ₄ -alkenyl radicals which are monosubstituted to trisubstituted by halogen, halogen in each case represents fluorine, chlorine, bromine and iodine. Preferred halogen atoms which may occur as substituents of the C ₂ -C ₄ -alkenyl radicals are fluorine and chlorine. Among the halo to trisubstituted by halogen C ₂ -C ₄ alkenyl radicals are those which have a chain length of two to three carbon atoms. Specifically, preferred C ₂ -C ₄ alkenyl radicals substituted one to three by halogen are 1-chlorovinyl, 2-chlorovinyl, 3-fluoroallyl and '), 4,4-trifluoro-but-2-en-1-yl. Very particular preference is given to 1-chlorovinyl and 2-chlorovinyl.

The C_-C ₄ -alkynyl radicals occurring in the definitions of the substituent A can be straight-chain or branched.

Alkynyl radicals having a chain length of 2 to 3 carbon atoms are preferred. C 1 -C 4 -alkynyl radicals are, for example, ethynyl, propargyl, 1-propynyl, 3-butynyl or 1-methylpropargyl, with ethynyl and propargyl being particularly preferred.

The occurring in the substituent A, substituted by halogen to trisubstituted Cj-Ce-cycloalkyl groups include, for example, 2-fluorocyclopropy 1,2,3-dif luorcyclopropyl, 2,2-dichlorocyclopropyl, 3-bromocyclopropy 1,2,3,4- Trifluorocyclopentyl or 2,3-dichlorocyclohexyl. Of these C ₃ -C ₆ -cycloalkyl groups, preference is given to the cyclopropyl, cyclopentyl and cyclohexyl groups which are monosubstituted to disubstituted by halogen, where halogen is fluorine, chlorine, bromine and iodine, but in particular fluorine and chlorine.

Further substituted Cr-Ce-cycloalkyl groups are, for example, 2-methoxycyclopropyl, 3-ethylthiocyclobutyl,

2-methylsulfonylcyclopentyl, S-ethylsulfinylcyclohexyl, 4-allylcyclohexyl or S-propargylcyclohexyl.

The C ₅ -C ₆ -cycloalkenyl radicals may be mono- to trisubstituted by halogen. Preferred halogen atoms are fluorine and chlorine. Examples of C ₆ -C _e -cycloalkenyl radicals are 3-cyclopentene, 2-cyclopentene, 4-chloro-cyclopent-3-ene, S-difluorocyclopent-S-ene, 2-cyclohexene, 3-cyclohexene, 4,5-dibromo cyclohex-2-ene or 4,4,5-trifluorocyclohex-2-ene.

Examples of saturated 4- to 6-membered heterocycles are oxotan-3-yl, oxolan-2-yl, oxan-2-yl, azetidin-3-yl, azolidin-3-yl, perhydroazin-4-yl (piperidine-4-yl). yl), dioxothiolan-2-yl, dioxothiethan-3-yl or dioxothian-4-yl. The nitrogen atom in heterocycle may also be substituted by C 1 -C ₄ -alkyl, for example in N-methylporhydroazin-4-yl or

N-lsopropylaüolidin-2-yl.

The C ₁ -C ₃ -alkyl radicals which occur as or in the definitions of the substituents X and Y include in particular methyl, ethyl, n-propyl and isopropyl, and the monosubstituted to trisubstituted by halogen radicals derived from these radicals. Preferably, the alkyl radicals occurring as or in the substituent definitions X and Y have one to

two carbon atoms.

In the mono- to trisubstituted by halogen-substituted C, -C ₃ alkyl groups occurring as or in the definitions of the substituents X and Y, one to three fluoro or chlorine-substituted C, -C _r alkyl groups are preferred. Especially preferred C _1-3 -alkyl radicals which are monosubstituted to trisubstituted by halogen are trifluoromethyl, difluoromethyl, 2-chloroethyl, chlorodifluoromethyl, dichloromethyl, chlorofluoromethyl, 1,1-dichloroethyl.trifluoroethyl. SSS-trifluoropropyl or 2,3-dichloropropyl,

Particularly preferred are fluoromethyl, chloromethyl, difluoromethyl and trifluoromethyl.

The invention also includes the salts containing the compounds of formula I with amines, alkali and alkaline earth metal bases or

can form quaternary ammonium bases.

Among alkali and alkaline earth metal hydroxides as salt formers s ^ d the hydroxides of lithium, sodium, potassium, magnesium or

To emphasize calcium, but especially of sodium or potassium.

Examples of amines suitable for salt formation are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, propylamine, iso-propylamine, the four isomeric butylamines, dimethylamine, diethylamine, diethanolamine, dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine, Piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and iso-quinoline, but especially ethyl, propyl, diethyl or triethylamine, but especially

iso-propylamine and diethanolamine.

Examples of quaternary ammonium bases are generally the cations of haloammonium salts, e.g. B. the Tetramethylammoniumkatioi), the Trimethylbenzylammoniumkation, the Triethylbenz "lammoniumkation, the

Tetraethylammonium cation, dab trimethylethylammonium cation, but also the Arrr niumkation.

Among the compounds of the formula I, preference is given to those in which R, hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy,

C, -C ₄ alkylthio or CF ₃ ;

R _{2 is} hydrogen or C 1 -C ₄ -alkyl;

A halogen-monosubstituted to trisubstituted C ₂ - (VAIkYl; or by C ₁ -C ₄ -alkoxy, Ci-C ₄ alkylthio, Ci-C ₄ alkylsulfonyl, C ₁ -C ₄ -AIkVlSuIfJnYl, C ^ C ^ Alkenyl or C ₂ -C ₄ -alkyl-substituted C 1 -C ₄ -alkyl, where the C ₂ -C ₄ -alkenyl radical is still one to

may be substituted in trisubstituted by halogen; X is C ₁ -C ₃ -alkyl, mono- to trisubstituted by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy or by halogen, mono to tri-substituted C ₁ -C ₃ -alkoxy;

Y is halogen C ₁ -C ₃ -alkyl, mono- to trisubstituted by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, mono- to trisubstituted by halogen, C ₁ -C ₃ -alkoxy, cyclopropyl , Methylamino or dimethylamino; and

E nitrogen or the methine group mean.

Furthermore, among the compounds of formula I, those are preferred in which

a) R _{2 is} hydrogen;

b) R ₁ and R _{2 are} hydrogen;

c) R _{1 is} hydrogen, methyl, methoxy, fluorine or chlorine;

d) X is C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy or monosubstituted by halogen, monosubstituted to trisubstituted C ₁ -C ₃ -alkoxy; and Y is C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, mono- to trisubstituted by halogen, C ₁ -C ₃ -alkoxy or chloro;

e) A is Ct-Ce-alkyl or Cj-Ce-cycloalkyl which is mono- to trisubstituted by halogen; or dC means ₄ alkyl or Cr-Ce-cycloalkyl, which is substituted by C ₄ -alkenyl ₄ -alkoxy, Cs-Ce-cycloalkenyl or Cz-C; wherein the C7-C ₄ alkenyl group, and the Cs-Ce cycloalkenyl group may be up to trisubstituted by halogen or mono-.

Of these compounds, those to be particularly emphasized are those in which

a) A is allyl, methallyl, 3-chloroallyl, methoxyethyl, 2-fluoro-isopropyl or 3-fluoropropyl;

b) R ₁ and R _{2 are} hydrogen;

c) X is methyl, methoxy, ethoxy or difluoromethoxy and Y is methyl, methoxy, ethoxy, difluoromethoxy or chlorine. As a preferred subgroup of compounds of the formula I, the group in which

R ₁ is hydrogen, halogen, C, -C ₂ alkyl, C, -C ₂ alkoxy, C, -C ₂ alkylthio, C, -C ₂ -haloalkoxy or CF _3; R _{2 is} hydrogen or C ₁ -C ₂ -alkyl;

A C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl which is monosubstituted to trisubstituted by halogen or by C ₁ -C ₂ -alkoxy, C ₁ -C ₂ -alkylmethyl,

Ci-Cj-alkylsulfinyl, C ₂ -C ₃ -alkenyl, Cs-Cs-cycloalkenyl, amino, C ^ Cj-alkylamino, C ₁ -C ₄ -dialkylamino or l substituted C ₁ -C ₄ -alkyl or C ₃ -C ₆ - Cycloalkyl, wherein the Cr-Ca-alkenyl radical and the Cs-Cβ-cycloalkyl radical may be monosubstituted to trisubstituted by halogen; or a 4- to 6-membered saturated heterocycle containing a heteroatom selected from the group O, N and SO ₂ ; or C ₁ -C ₂ alkyl which is substituted by a 4- to 6-membered saturated heterocycle containing a heteroatom selected from the group consisting of O, N and SO ₂ , XC ₁ -C ₂ alkyl, by halogen bis- trisubstituted C ₁ -C ₂ -AI ¹ kyi, C, -C ₂ alkoxy or by halogen, mono- to tri-substituted C ₁ -C ₂ -alkoxy;

Y is halogen, C ₁ -C ₂ -alkyl, mono- to trisubstituted by halogen, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, mono- to trisubstituted by halogen-substituted C ₂ -alkoxy, cyclopropyl, Methylamino or Dim nhylamino mean.

Another subgroup of Vorbindungen of formula I is characterized in that

R _{1 is} hydrogen, halogen, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkylthio or CF ₃ ;

R _{2 is} hydrogen or C ₁ -C ₂ -alkyl; A mono- to trisubstituted by halogen-substituted C ₂ -C ₄ alkyl or by C ₁ -C ₂ -alkoxy, C ₂ alkylthio, C ₁ - C ₂ alkylsulfonyl, C ^ CrAlkylsulfinyl, C ₂ -C ₃ - AlkOnYl or Cr-C ₃ alkynyl substituted C, -C ₂ alkyl, wherein the

C ₂ -C ₃ alkenyl radical may be substituted once to three times by halogen;

XC ₁ -C ₂ -AlkYl, by halogen mono- to trisubstituted C ₁ -C ₂ -AlkVl, C ₁ -C ₂ -alkoxy, or by halogen mono- to trisubstituted

C ₁ -C alkoxy;

Y is halogen, C ₁ -C ₂ -alkyl, mono- to trisubstituted by halogen-substituted C ₂ alkyl, C ₁ -C ₂ -alkoxy, halogen-mono- to trisubstituted

substituted C ₁ -C ₂ -alkoxy, cyclopropyl, methylamino or dimethylamino.

Another preferred subgroup of compounds of the formula I is the group in which

R ₁ and R _{2 are} hydrogen;

A halogen-mono- to trisubstituted C ₁ -C ₄ -alkyl or C | -C ₄ alkoxy, C ₅ -C ₆ cycloalkenyl, or C, -C ₂ -alkenyl substituted C | -C ₂ -alkyl or C ₃ -C ₆ -CyClOaIkVl, wherein the C ₂ -C ₃ alkenyl and the C ₅ -C ₆ -Cycloalkenylrest still one to

may be substituted in trisubstituted by fluorine or chlorine; means.

Of this group by their good biological effect especially those compounds in the eye, in which

A is allyl, methallyl, 3-chloroallyl, methoxyethyl, 2-fluoro-isopropyl or 3-fluoropropyl;

X is methyl, methoxy, ethoxy or difluoromethoxy, Y is methyl, methoxy, ethoxy, difluoromethoxy or chloro and

E stands for the methine group.

Preferred individual compounds from the scope of the formula I are:

N-O-allylsulfonyl-pyridine-1-yl-sulfonyD-N'-Ke-dimethoxypyrimidine-y-y-urea, N- (3-methoxyethylsulfonyl-pyridin-2-yl)

sulfonyl) -N '- (4,6-dimethoxypyrimidin-2-yl) urea, N- (3-fluoropropylsulfonyl-pyridin-2-yl-sulfonyl) -N'-

(4,6-dimethoxypyrimidin-2-yl) urea and N- (3-methallylsulfonylpyridine - / '- / 1-sulfonyl) -N' - (4,6-dimethoxypyrimidin-2-yl) -

urea.

According to a first method, the compounds of the formula I can be prepared by reacting an inventive

Pyridylsulfonamide of the formula II,

SO ₂ -A

(II) SO ₂ NH ₂

in which R ₁ and A have the meaning given under formula I, with the proviso that A can not be a-haloalkyl or a-halogenocycloalkyl, in the presence of a base with an N-pyrimidinyl- or N-triazinylcarbamate of the formula IV,

R ₃ OCN - (^ E (IV)

N = / Y

in which X, Y, R ₂ and E have the meaning given under formula I and R _{3 is} C ₁ -C ₄ -alkyl or phenyl which may be substituted by C ₁ -C ₄ -alkyl or halogen; implements.

In a second process, the compounds of the formula I can be prepared by reacting a pyridylsulfonamide of the formula II according to the invention,

SO ₂ -A

SO ₂ NH ₂

in which R ₁ and A have the meaning given under formula I, in the presence of a base with a pyrimidinyl or triazinyl isocyanate of the formula VIII,

X /

ι ₌ c = N - P * E (VIII)

N = / Y

in which E, X and Y have the meaning given under formula i.

According to a third method, the compounds of formula I can be prepared by withdrawing from the European

Patent No. 103543 known compounds of the formula XVI

-6- 293 SA _χ

N, SO ₂ NH-C-Ν-

_(Χνι)

wherein R ₁ , R ₂ , A, E, X and Y have the meaning given under formula I, oxidized by methods known per se. Oxidations of thio compounds to the corresponding sulfonyl compounds are described in US Pat. No. 4,774,337. Suitable oxidizing agents for this reaction are, for example, peracids or hydrogen peroxide. If desired, the obtained ureas of the formula I can be converted into salts by means of amines, alkali metal or alkaline earth metal hydroxides or quaternary ammonium bases. This happens, for example, by reaction with the equimolar amount of base and evaporation of the solvent.

The reactions to compounds of the formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane / nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N- methylpyrrolidinone. The reaction temperatures are preferably between -20 ° C and + 120 ° C. The reactions are generally slightly exothermic and can be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction is expediently heated for a short time to the boiling point of the reaction mixture. The reaction times can also be shortened by adding a few drops of base as the reaction catalyst. Tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo- (2.2.2) -octane, 1,5-diazabicyclo (4.3.0) non-5-ene or 1,5-diazabicyclo (5.4 .0) undec-7-en. As bases but also inorganic bases such as hydrides such as sodium or calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or bicarbonates such as potassium and sodium bicarbonate can be used. The final products of formula I can be isolated by concentration and / or evaporation of the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they do not dissolve well, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons. The pyridylsulfornamides of the formula II according to the invention have been specially developed for the synthesis of the compounds of the formula I. They are the subject of the present invention and correspond to the general formula II

SO ₂ -A

(II) SO ₂ NH ₂

wherein Ri and A have the meaning given under formula I.

The new Pyridylsulfonamide of formula II can be prepared by various methods. These are also part of the present invention. This gives the compounds of the formula Hc

SO ₂ -A '"

(lic) SO ₂ NH ₂

wherein R, the formula! has the meaning given and A "'by C ₂ -C ₄ -alkenyl, C ₁ -C 6 -cycloalkenyl, C ₁ -C ₄ -alkynyl, C ₁ -C ₁ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfonyl or C, -C ₄ alkylsulfinyl substituted C, -C ₄ alkyl or Cj-Ce-cycloalkyl or fluorine-substituted C _t -C ₆ alkyl or C ₃ -C ₆ cycloalkyl, by reacting a 3-fluoropyridin-2-ylsulfonamid the formula purple

(purple) SO ₂ NH ₂

in which Ri has the meaning given under formula I, in the presence of a base with a mercaptan of the formula V A '' '- SH (V)

wherein A '"has the meaning given under formula IIc, and then reacting the compound of formula Vl thus obtained

Π, -4-

S-Λ " ¹

N ^^ SO ₂ NH ₂

(Vl)

wherein Ri has the meaning given under formula I and A '"has the meaning given under formula Hc, oxidized according to methods known per se for the compound of the formula IIIc

 Compounds of the formula II

Π -

SO ₂ -A

N SO ₂ NII ₂

(ID

where R | and A have the meaning given under formula I are also obtained by reacting a 3-mercapto-pyridin-2-ylsulfonamid the formula HIb

π, -nr

SH

N is SO ₂ NH ₂

(IIIb)

wherein R, which has the meaning given under formula I, in the presence of a base with a compound of formula XVIII

Z-A (XVIII)

wherein A has the meaning given under formula I and Z is chlorine, bromine, iodine,

CII ₃ SO ₂ O-OdCr CH ₃

SO ₂ O-

R ₁ -4-

SA

N "SO ₂ NH ₂

(XX)

wherein A has the meaning given under formula I, and then this oxidized to the compound of formula II. The intermediates of formula III

(III)

SO ₂ NH ₂

wherein R _{1 has} the meaning given under formula I and Q is fluorine or SH are, with the exception of the compound in which Ri is hydrogen and Q -SH, new and also form an object of the present invention. The scope of formula III includes the compounds of the subformulae HIa and HIb. The compounds of the formulas IIIa and IIIb can be prepared by methods known per se by, in the case of the compound of the formula IIIa, a 2,3-difluoropyridine of the formula IX

(IX)

wherein R) has the meaning given under formula I, with a mercaptan of the formula XR ₄ SH

(X)

wherein R4 is benzyl or iso-propyl, to a compound of formula Xl

(XI)

SR ₄

wherein Ri has the meaning given under formula I and R _{4 is} benzyl or iso-propyl, then reacted to obtain by chlorination with chlorine gas and reacting with ammonia, the compound of formula HIa.

Compounds of the formula III a can also be prepared by reacting a 3-amino-pyridin-2-yl-sulfonamide of the formula XXI

(XXI)

"N" SO ₂ NH ₂

in the presence of hydrogen fluoride and optionally in the presence of an inert solvent diazotized with a nitrite. Suitable nitrites are, for example, sodium nitrite or potassium nitrite, and dimethylsulfoxide, sulfolane, dimethylformamide or dimethylacetamide are particularly suitable as solvents.

Intermediates of the formula IH b are prepared by reacting a 3-fluoropyridin-2-ylsulfonamide of formol III a with a mercaptide of the formula XIX

(Me) _n ri7-nb ΙλΙλ)

wherein Me is sodium, potassium or lithium and η is 1 or 2, is reacted.

Methods for the preparation of the compounds of the formula IX can be found, for example, in J. Fluorine Chem. 21, 171 (1982) (R _t = H); USP 4,713,109 (R, = Cl) or in Advanc. Heterocycl. Chem. 6, 229 (1966).

Compounds of sub-formula Ha

SO ₂ -A ¹

N is SO ₂ NH ₂

(Ha)

in which R ^{1 has} the meaning given under formula '"and A' is fluorine-substituted C 1 -C ₆ -alkyl or C ₃ -C ₆ -cycloalkyl or C 1 -C ₄ -alkoxy- or C 1 -C ₄ -alkylthio-substituted C 1 -C ₄ -alkyl ₄ alkyl or CH ^ cycloalkyl, can also be heigestellt analogous to a process described in USP 4,774,337 by reacting a compound of formula XII

(XH)

N, SO ₂ -NH-IeM ₁ -C ₄ H ₉

where R | the meaning given under formula I, in the presence of a strong base such as η Buty! lithium or lithium diisopropylamide, with a disulfide of formula XIII

'A-S-S-A' (XIII)

wherein A 'has the meaning given under formula Ha, reacting, the compound of formula XIV thus obtained

in which A 'has the meaning given under formula Ha, the compound of the formula XIV SA ¹ thus obtained reacts

"..Tr

N is SO ₂ -NH-tert-C ₄ H ₉

(XIV)

where R | has the meaning given under formula I and A 'has the meaning given under formula Ha ha, "treated with a suitable acid, such as trifluoroacetic acid, and the resulting sulfonamide of formula XV

S-A '

SO ₂ NH ₂

(XV)

wherein Ri has the meaning given under formula I and A 'has the meaning given under formula II a, then oxidized to the compound of formula i'.

Compounds of the sub-formula Hb ^^ SO ₂ -A-

SO ₂ NH ₂

wherein R _{1 has} the meaning given under formula I and A "for fluorine, chlorine or bromine-substituted C ₂ -C ₄ -Alkyl s.teht, are further obtained by reacting a hydroxysulfonamide of the formula XVII

SO ₂ -R ₅ -OH

(XVII) SO ₂ NH ₂

where R | has the meaning given under I and R5 is C2-C4-alkylene, converted into the corresponding halides.

Such reactions are, for example, in Can. J. Chem. 57, 3193 (1979) or French Patent Specification No. 2509725

described.

The preparation of the mercaptans of the formulas V and X and the disulfide of the formula XIII takes place according to litersturbekannten

Methods. From the large number of published articles are mentioned as representative:

DE 2832977;

J. Am. Chem. Soc. 77, 285 (1955);

J. Am. Chem. Soc. 72, 1687 (1950) and Org. Synth. 35, 66 (1955).

The active compounds of the formula I are generally successfully used at rates of from 0.001 to 5 kg / ha, in particular from 0.005 to 3 kg / ha. The dosage required for the desired effect can be determined by experiment. Fio depends on the type of effect, the stage of development of the crop and the weed, as well as the application

(Location, time, procedure) and may vary within wide ranges due to these parameters.

At lower application rates, the compounds of the formula I are distinguished by growth-inhibiting and herbicidal properties which they are excellently suited for use in crops of useful plants, in particular in cereals, cotton, soybeans,

Rapeseed, maize and rice, with use in maize crops being most preferred.

The active compounds of the formula I produced by means of the pyridylsulfonamides according to the invention are used in herbicidal and plant growth-regulating agents and processes for inhibiting plant growth.

Plant growth regulators are substances which agronomically desirable biochemical and / or in / on the plant

cause physiological and / or morphological changes.

Dio agents contained in the agents influence the plant growth in different ways depending on the application time, dosage, mode of administration. Plant growth regulators of the formula I can, for example, inhibit the vegetative growth of plants. This type of effect is of interest on lawns, in ornamental plants, in orchards, on Straßenböschungen, on sports and industrial plants, but also in the targeted inhibition of secondary drives such as tobacco. In agriculture, the inhibition of vegetative growth in cereals leads to reduced storage via a stalk reinforcement, similar agronomic effects are achieved in rape, sunflower, maize and other crops. Furthermore, by inhibiting the vegetative wax, the number of plants per area can be increased. Another application of growth inhibitors is the selective control of soil-covering plants in plantations or far-row crops by strong growth inhibition without killing these ground cover so that the competition is switched off against the main crop, the agronomically positive effects such as erosion prevention, nitrogen binding and

Soil loosening but preserved.

A plant growth inhibition process is understood to mean a natural evolution of the plant without altering the genetically determined life cycle of the plant as a mutation. The method of growth regulation is applied to a developmental time of the plant to be determined in the individual case. The application of the active compounds of the formula I can take place before or after dome emergence of the plants, for example already on the seeds or the seedlings, on roots, tubers, stems, leaves, flowers or other plant parts.

This can e.g. by applying the active substance itself or in the form of an agent to the plants and / or by treatment

Nutrient medium of the plant (soil) happen.

For the use of the compound of formula I or plant growth regulating agent containing it

various methods and techniques, such as the following:

i) seed dressing

a) seed dressing with a formulated as a wettable powder by shaking in a vessel until evenly distributed on the Samer.oberfläche (dry dressing). It uses up to 4 g of active ingredient of formula I (in a 50% formulation: up to 8.0g spray powder) per 1 kg of seed.

b) dressing the seeds with an emulsion concentrate of the active ingredient or with an aqueous solution of the formulated as a wettable powder active ingredient of the formula I according to method a) (wet pickling).

c) pickling by dipping the seed in a broth with up to 1000 ppm of active compound of the formula I for 1 to 72 hours and optionally subsequent drying of the seeds (immersion dressing, seed soaking).

The seed dressing or the treatment of the germinated seedling are by nature the preferred methods of administration because the treatment of the active ingredient is completely directed to the target crop. As a rule, 4.0 g to 0.001 g of active substance are used per 1 kg of seed, whereby, depending on the methodology which also allows the addition of other active ingredients or micronutrients, the upper limit may be deviated from the stated upper limit concentrations (repeat pickling).

ii) Controlled Drug Administration

The active ingredient is applied in solution to mineral granules or polymerized granules (urea / formaldehyde) and allowed to dry. Optionally, a coating can be applied (coating granules) containing it

allowed to deliver the drug over a certain period of time dosed.

The compounds of the formula I are used in unchanged form or preferably as agents together with the auxiliaries customary in the formulation clinic and are therefore used, for example, in to emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and encapsulations in z. As polymeric materials, processed in a known manner. The application methods such as spraying, · misting, dusting, scattering or pouring are the same as the type of means aen targets and the

selected proportions selected accordingly.

The formulations, d. H. the active substance of the formula I and, if appropriate, a solid or liquid additive-containing agent, preparations or compositions are prepared in a known orphan, for. B. by intimately mixing and / or grinding the active compounds with extenders, such as. With solvents, solid carriers, and optionally

surface-active compounds (surfactants).

Suitable solvents are: Aromatic hydrocarbons, preferably the fractions C ₈ to C, 2, such as

Xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N- Methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized Pf'anzenöle, such as epoxidized

Coconut oil or soybean oil; or water.

As solid carriers, for. For example, for dust and dispersible powders, normally ground minerals are used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granules are porous types such. Pumice, brick break, sepiolite or bentonite, as non-sorptive support materials e.g. Calcite or sand in question. In addition, a variety of pre-granulated materials of inorganic or organic nature, in particular dolomite or crushed plant residues can be used.

Suitable surface-active compounds, depending on the nature of the active ingredient of formula I, are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Among surfactants are

also to understand surfactant mixtures.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic

be surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C10-C22), such as

z. As the sodium or potassium salts or oleic or stearic acid, or of natural fatty acid mixtures, the z. B. can be obtained from coconut or tallow oil, called. Furthermore, the fatty acid methyltaurine salts are to be mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated

Benzimidazolderivate or Al vylarylsulfonate.

The fatty sulfates or sulfonates are generally present as alkali, alkaline earth or optionally substiuierte ammonium salts and have an alkyl radical having 8 to 22 carbon atoms, wherein alkyl also includes the alkyl moiety of acyl radicals, for. As the Na or Ca salt of lignin, the Dodecylschwefelsäureesars or a fatty alcohol sulfate mixture prepared from natural fatty acids. Here also include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue having 8 to 22C atoms. Alkylarylsulfonates are z. B. the Na, Ca or triethanolamine salts of

Dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates such. B. Salts of the Phosphoric Acid Ester of a p-Nonylphenol- (4-14) -

Äthylenoxid Aclduktes or phospholipids in question.

Suitable nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in the alkyl group of the alkylphenols

can contain.

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups over polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having from 1 to 10 carbon atoms in the alkyl chain

usually 1 to 5 Eihylenglykoleinheiten per propylene glycol unit.

Non-ionic polyethoxyethanols, castor oil polyethylene glycol ethers, polypropylene polyethylene oxide adducts, tributyl phthoxypolyethoxyethanol, polyethylene glycol and octylphenoxy polyethoxyethanol may be mentioned as examples of nonionic surfactants.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and have as further substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylenesulfates, e.g. The stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium brori "> id.

The surfactants commonly used in formulation technology are i.a. described in the following publications:

McCutcheon, Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood, New Jersey, 1981;

H. Stäche, "Tensid-Taschenbuch", 2nd ed., C. Hanser Verlag, Munich, Vienna, 1981; M. and J. Ash. "Encyclopedia of

Surfactants ", Vol. HII, Chemical Publishing Co., New York, 1980-1981.

The agrochemical preparations generally contain from 0.1 to 95%, in particular from 0.1 to 80% of the active ingredient of the formula from 1.1 to

99.9% of a solid or liquid additive and 0 to 25%, especially 0.1 to 25% of a surfactant.

In particular, preferred formulations are composed as follows: (% = wt.%)

Emulsible concentrates:

Active ingredient: 1 to 20%, preferably 5 to 10%

Surface-active MiHoI: 5 to 30%, preferably 10 to 20%

liquid vehicle: 50 to 94%, preferably 70 to 85% ~ "

Dusts:

Active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:

Active ingredient: 5 to 75%, preferably 10 to 50%

Water: 94 to 24%, preferably 88 to 30%

Surfactant: 1 to 40%, preferably 2 to 30%

Wettable powder:

Active ingredient: 0.5 to 90%, preferably 1 to 80%

Surfactant: 0.5 to 20%, preferably 1 to 15%

solid support material: 5 to 99%, preferably 15 to 90%

granules:

Active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%.

While as a commodity rather concentrated funds are preferred, the end user uses: ι the rule diluted funds. The use forms can be diluted down to 0.001% of active ingredient. The application rates are usually 0.001 to 5 kg AS / ha, preferably 0.005 to 3 kg AS / ha.

The compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

Formulation Examples:

Example F 1: Formulation Examples of Formula I (% = wt%)

a) wettable powder a) b) c) active substance no. 1.001

Na ligninsulfonate

Na lauryl sulfate

Na Diisobutylnaphthalinsulfonat

Octylphenolpolyethylenglyko! -

Ether (7-8 moles of AeO)

Highly dispersed silicic acid

kaolin

Sodium chloride - - 59.5%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

b) Emulsion Concentrate a) b) Active Ingredient No. 1.001 10% 1% octylphenol polyethylene glycol

ether (4-5 moles of AeO) 3% 3%

Ca-dodecylbenzenesulfonate 3% 3%

Castor oil polyglycol ether (36 molAeO) 4% 4%

Cyclohexanone 30% 10%

Xylene blend 50% 79%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

20% 50% 0.5 ° / 5% 5% 5% 3% - - - 6% 6% _ 2% 2% 5% 27% 27% 67% 10% _

c) dusts a) b) Active ingredient No. 1,002 0.1% 1 ° / talc 99.9% _ kaolin 99 ° Λ

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding on a suitable mill.

d) Extruder Granul t a) b) Active ingredient No. 1,001 10% 1% Na ligninsulfonate 2% 2% carboxymethylcellulose 1% 1% kaolin 87% 93%

The active ingredient is mixed with the Zusn'jstoffen, ground and moistened with water. This mixture is extruded and then yotrocknet in a stream of air.

e) serving granules

Active ingredient No. 1.001 3%

Polyethylene glycol (MG200) 3%

Kaolin 94%

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way one obtains dusty egg wrapping granules.

f) suspension concentrate active ingredient no. 1.002 ethylene glycol

Nonylphenol polyethylene glycol ether (15MoIAeO) Na lignin sulfonate carboxymethyl cellulose

37% aqueous formaldehyde solution silicone oil in the form of a 75% aqueous emulsion of water

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which any desired concentration can be prepared by dilution with VWisser suspensions.

g) saline

Active ingredient No. 1.002 5%

Isopropylamine 1%

Octylphenol polyethylene glycol ether (78 moles of AeO 3%)

Water 91%

Preparation Examples

Example H1: Preparation of 2-isopropylthio-3-fluoropyridine (intermediate)

.F

a) b) 40% 5% 10% 10% 6% 1% 10% 5% 1% 1% 0.2% 0.2 Ά 0.8% 0.8 ⁰ A 32% 77%

181.2 g of isopropyl mercaptan are added dropwise to a suspension of 324 g of anhydrous potassium carbonate and 335.6 g of 2,3-difluoropyridine in 4500 ml of dimethylformamide over a period of 25 minutes at a temperature of 0 to +2 ° C. After stirring at room temperature for 18 hours, the mixture is poured The organic phase is separated off and washed in each case with ice-water and ethyl acetate The combined organic phases are dried with sodium sulfate and then concentrated by evaporation After purification by column chromatography over silica gel ethyl acetate / n-hexane (1: 9) gives 362.9g 2-isopropylthio-3-fluoro-pyridine in the form of an oil.

Example H2: Preparation of 3-Fluot-pyridin-2-yl-sulfonamide (Compound No. 3.001)

SO ₂ NH ₂

Option A)

In a mixture of 21.4 g of 2-isopropylthio-3-fluoropyridine, 340ml of dichloromethane and 500ml of 1N hydrochloric acid is passed a 36,9g gaseous chlorine at a temperature of -5 ⁰ C within 36 minutes. The mixture is then stirred for 30 minutes at a temperature of ⁰ ° C., during which intensive nitrogen is passed through the solution during the last 10 minutes. The organic phase is separated, washed in each case with ice-water and dichloromethane and dried over sodium sulfate. Subsequently, the combined organic phases at a temperature of -7ü ° C to -5O ⁰ C within 25 minutes to a mixture of 31.8 g of ammonia dissolved in 63.6 ml of dichloromethane added dropwise. After removal of the cooling, the reaction mixture is stirred for 150 minutes and then filtered. After evaporation and chromatographic purification over silica gel ethyl acetate / n-hexane 1: 1), 11.1 g of 3-fluoro-pyridin-2-ylsulfonamide (Compound No. 3,001) with a melting point of +124 to + 125 ° C.

Variant b)

5.3 g (0.030 mol) of 3-amino-pyridin-2-yl-sulfonamide are dissolved in 12 ml of dimethyl sulfoxide and added dropwise at 0 ° C to 14.3 g (0.72 mol) of hydrogen fluoride (exothermic reaction). Then (at ⁰ ° C. 2.4 g are 0,035MoIy> latriumnitrit introduced in portions. After an hour at 7O ⁰ C heated (^ evolution).

After cooling, the reaction mixture is added to an ice / water mixture and extracted after addition of sodium bicarbonate and sodium chloride with tetrahydrofuran and ethyl acetate. The combined extracts are washed with saturated sodium chloride solution, dried with magnesium sulfate, filtered and evaporated. The residue is stirred in diethyl ether / petroleum ether. After filtration, 3.7 g 3-fluoropyridin-2-yl-sulfonamide (compound Nr.3.001) having a melting point of from +124 to + 125 ⁰ C.

Example H3: Preparation of 3-mercapto-pyridin-2-yl-sulfonamide (Compound No. 3.008), 3H

SO ₂ NH ₂

In a mixture of 6.88 g of potassium tert-butoxide and 5 g of 3-fluoropyridin-2-yl-sulfonamide in 90 ml of dimethylfou. Amide is passed under a nitrogen atmosphere at a temperature of + 16 to + 2O ⁰ C 1.06 g of hydrogen sulfide ^. After 4V2stündigem stirring at a temperature of + 5O ⁰ C is added 0.32 g of potassium tert-butoxide and initiates 0.1 g of hydrogen sulfide. After 2 hours of stirring at a temperature of + 50 ° C, the reaction mixture is concentrated in vacuo at a temperature of +75 ⁰ C. The resulting oily residue is triturated with 135 ml of cold, 0.75 N sulfuric acid. After filtration and washing the residue with a little water, the product obtained was dried in vacuo over phosphorus pentoxide. 3.58 g is obtained of 3-mercapto-pyridin-2-yl-sulfonamide with a melting point of +102 to +104 ⁰ C.

Example H4: Preparation of 3- (3-fluoropropylthyl) -pyrldin-2-yl-sulfonamide (intermediate of formula XX)

(XX)

"SO ₂ NH ₂

A mixture consisting of 0,285g 3-mercaptopyridine-2-yl-sulfonamide, 0,455g of potassium carbonate, 5 ml of dry dimethylformamide and 0.23 g of 3-fluoro-1-8rompropan is at a temperature of +25 ⁰ C for 90 minutes in a nitrogen atmosphere touched. Subsequently, the reaction mixture is poured into an ice-water mixture. After adjusting the pH to pH 2 with 2.8 ml of 2N HCl, the reaction mixture is extracted twice with ethyl acetate. The combined organic phases are washed three times with water and then dried over sodium sulfate. Evaporation followed by chromatographic purification of the residue on silica gel ethyl acetate / n-hexane (1: 1) gives 0.12 g of 3- (3-fluoropropylthio) -pyridin-2-yl-sulfonamide having a melting point of +85 to +86 ⁰ C.

Example H5: Preparation of 3-allylthio-pyridin-2-yl-sulfonamide, S-CH ₂ CH = CH ₂

SO ₂ NH ₂

To a cooled to +5 ⁰ C solution of 17.62 g (0.2 mol) of 3-fluoro-pyridin-2-yl-sulfonamide in 400 ml of acetonitrile are added 33.2 g (0.24 mol) of potassium carbonate, and 1.32 g (0.005 mol) of 18-crown-6 and 15.8 g (0.17 mol) of 80% allyl mercaptan in 50 ml acetonitrile.

After 46 hours of stirring the reaction mixture at room temperature, the resulting precipitate is filtered off. The resulting filtrate is concentrated and purified by chromatography over a silica gel with ethyl acetate / cyclohexane (2: 1). This gives 10 g (50% of theory) of 3-allylthio-pyridin-2-yl-sulfonamide.

Example H6: Preparation of 3-allylsulfonyl-pyridin-2-yl-sulfonamide (Compound No. 2.001 j, SO ₂ CH ₂ CH = CH ₂

'"Ν""SO ₂ NH ₂

To a cooled to +8 ^C C solution of 10g (0,050MoI) of a H of Example 5 obtained 3-allylthio-pyridin-2-ylsulfonamids in 130ml of acetic acid are added dropwise 62.5 g of 40% peracetic acid. Subsequently, the reaction mixture is stirred for 19 hours at a temperature of +8 to + 3O ⁰ C. The reaction mixture is then poured into ice-water and extracted four times with ethyl acetate. The combined organic phases are washed with sodium bicarbonate solution, treated with potassium sulfite and then dried with magnesium sulfate. After filtration and evaporation of the filtrate, the residue obtained is recrystallized in ethyl acetate / n-hexane and then filtered.

After drying the filter residue in vacuo at room temperature, 8.1 g (62% of theory) of 3-allylsulfonyl-pyridin-2-yl-sulfonamide (compound no. 2.001) with a melting point of +178 ⁰ C.

Example H7: Preparation of N - ^ - allylsulfonyl-pyridin-1-yl-sulfonyl-N'-Cl.e-dimethoxypyrimidine] -ylurea (Compound No. 1,001)

0 ^ SO ₂ CH ₂ CH = CH ₂

in ^x SO ₂ NHCONH- ^

UCH ₃

7u of a cooled to + 5 ° C solution of 7.1 g (0.027 mol) of a obtained according to Example MG 3-allylsulfonyl-2-pyridin-2-ylsulfonamide in 90 ml of acetonitrile is added dropwise within 10 minutes, a solution of 4 Add 66 g (0.029 mol) of IS-diazabicycloIoA Alundec S-ene in 15 ml of acetonitrile. After addition of 7.8 g N- (4,6-dimethoxy-pyrimidin-2-yl) is -phe.iylcarbamat the reaction mixture stirred ^2] h hours. After distilling off the acetonitrile under reduced pressure at a temperature of +45 ⁰ C, the residue obtained is mixed with a small amount of ice and then

15ml 2N hydrochloric acid added.

After vigorous stirring with the addition of a small amount of diethyl ether, the crystallization of the product begins. The crystals are filtered off, washed with water and diethyl ether and stirred again with diethyl ether.

After filtering off and drying the residue is finally obtained after recrystallization from ethyl acetate / acetonitrile 8.1 g (68% of theory) of N- (3-allyl-sulfonyl-pyridin-2-yl-sulfonyl) -N '- (4 , 6-dimethoxypyrimidin-2-yl) urea (Compound

No. 1.001) with a melting point of +185 ⁰ C.

In an analogous manner, listed in the attached tables compounds of formula I and the

Compounds of formulas II and III prepared.

_> . _ι . .027 .026 .025 .024 .019 .020 .021 .022 .023 .018 .016 .017 .012 .013 .014 .015 to s> SJ to ηηηη .011 .009 .010 S OO .007 SJ η .006 .004 .005 .003 .002 .001 "Γ ¹ ρ .029 .028 η η ή -CI -CI ήήήήή ή ή ή ή ή Il Il Il ηηηη -Cl ηη ι ηη Il η η η ι ηη -CI -CI η η η ή ή -η ή-η ή-η ►-Η to η IO -η ή-η Ni NJ Ni N) ( ηηηηη IO η to ηη SJ to SJ to NJ η Ni ro ηη SJ η to N) η SJ IO ηη N) η S) η η "T-I OCI IO ή SJ -η ή- E II EU) ("} U) -Γ ¹ Ii E Q W HD = Hurry Il Il Il Il ηηηηη Id = I Il Il ηη η Il η Il Il ηη Id = I Il η Il Il ηη Il η Ν> O Id = I Il η Τ * S) SJ to to Ni N) N) NJ Ν> to to to U SJ Ni ro SJ ι-Μ ο to to 1-U N) ^ sT U) OCI IO SJ IO e T ¹ e - £. »-Ci. · »-Λ ί-Λ ήηήήή 5-CI Cv Cv ήή ^ J η Ξ UUUUUU ^ j U) U ηζζζ η + 185 (Zers.) | X Η · * e e οη ηηηη OCI - Q Q η Q ZZQZZ Q ZZ U N-4U U LA ζ ZZ Z & η ηη η η 00 ο N * O η Z η OCI OCI Idol OCI οη ηηηηη OCI OO ηη οηηζ OO ηη OCI OQ "T-IUi OCI OO ηη ο η OCI I pci OCI U) Jr u ~ U) U U U U U U U U V ^ * «^ * - ' U O O ^ U ÜR $ OCI η Q U O η ηοοηο ΕηηΕη I DO OCI CII, ζ ηη + 181 (Zers.) | OCI OQ CH ₁ OCI OCI O η to ¹¹ U) U) Ui U ^ i U (j ο ¹ " Ui + 166 (Zers.) + 170 (Zers.) + 172 (Zers.) I + 158 to + 159 |

Table 1 (continued)

No. A CH ₃ rr R ₂ Π X Y Melting point I ⁰ C] -CH ₂ -C = CFI ₂ 1030 CH ₃ FI II N OCH ₃ CFI ₃ -CH ₂ -C = CH ₂ 1031 CH ₃ I H H N OC ₂ H ₅ CFI ₃ -CH ₂ -C = CH ₂ 1032 CFI ₃ FI II N OC ₂ II ₅ NFICH ₃ -CH ₂ -C = CH ₂ 1033 CH ₃ FI Fl N OCII ₃ OCFF, -CH ₂ -C = CH ₂ 1034 CFI ₃ FI H N OC ₂ II ₅ C ₃ FI ₅ -cycl. -CH ₂ -C = CH ₂ 1035 CH ₃ FI FI CH OCHF ₂ CH ₃ -CH ₂ -C = CH ₂ 1036 CH ₃ 6-CFI ₃ H CH OCH ₃ OCH ₃ -CH ₂ -C = CH ₂ -CH ₂ -CH = CHCl .037 -CH ₂ -CH = CHCl 5-Cl H CH OCH ₃ OCFI ₃ 1038 -CH ₂ -CH = CHCl H FI CH OCH ₃ OCII ₃ 1039 -CH ₂ -CH = CHCl H H CH OCII ₃ Cl 1040 -CH ₂ -C = CFI ₂ FI H CH OCH ₃ CH ₃ 1041 Cl II H N OCIl ₃ CH ₃ 1042 -CH ₂ -C = CH ₂ H FI CH OCFI ₃ OCH ₃ , Cl 1043 -CH ₂ -C = CFI ₂ H II CFI OCH ₃ OCII ₃ -CH ₂ -C = CH ₂ 1044 -CH ₂ CFkCH ₂ F FI FI CII OCH ₃ Cl 1045 -CH ₂ CH ₂ CH ₂ F H II N OCFI ₃ CH ₃ 1046 -CH ₂ CFI ₂ CFI ₂ F II H CH OCH ₃ OCH ₃ + 156 to + 157 1047 -CH ₂ CH ₂ CH ₂ F FI H CH OCH ₃ Cl 1048 -CH ₂ CH ₂ CH ₂ F H FI CFI OCH ₃ CII ₃ 1049 -CH ₂ CH ₂ HI ₂ F FI H CII OCH ₃ OCHF ₂ 1050 -CH ₂ CH ₂ CH ₂ F FI II CH OCH ₃ OCHF ₂ 1051 H II N OCFI ₃ CH ₃ 1052 H II N OCH ₃ OCFI ₃

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table No. Λ R H R ₂ e X Y Melting point [ ⁰ C] ; 1 (continued) 1091 -Ο " H N OCH ₃ CH ₃ F / H 1092 -egg H CH OCII ₃ CH ₃ Cl H 1093 H CII OCII ₃ CH ₃ br H 1094 H CII OCH ₃ OCH ₃ Cl Cl H 1095 -O H H CH OCH ₃ OCH ₃ 1096 - CH ₂ Y H H CH OCH ₃ OCII ₃ 1097 H H CH OCH ₃ OCH ₃ 1098 -O H CH OCH ₃ OCH ₃ 'OCH ₃ II 1099 H CH OCH ₃ OCH ₃ \ SCH ₃ H 1100  "." * <<] H H CII OCH ₃ OCH ₃ 1101 -CR ₁ -CH ₂ -CH ₂ / "^ II CH CH ₃ CH ₃

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Table 1 (continued)

No. Λ R ₁ R ₂ e X Y melting point ; 1195 -CH ₂ CH = CHBr (Ζ / Ε) H H CH OCH ₃ OCH ₃ + 157 to 158 1,196 1,197 1,198 1,199 1,200 1,201 1,202 1,203 1,204 1,205 1,206 -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) - CH ₂ CH = CHBr (Ζ / Ε) -CH ₂ CH = CHBr (Ζ / Ε) II HH 6-CH ₃ 6-CH ₃ 6-OCH ₃ 6-OCH ₃ 5-CH ₃ 4 -CH ₃ 4 -CH ₃ 4 -CH ₃ H H H II H H H H H H N CH CH CH N CII N CH CH N CII OCH ₃ OCH ₃ OCH ₃ OCII ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ CH ₃ OCHF ₂ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ OCH ₃ N (CH ₃ ) ₂ I / pre j 1207 -CH ₂ -C H H CK OCH ₃ OCH ₃ 1208 H H N OCFI ₃ OCH ₃ 1209 -CH ₂ - 6-CH ₃ H CH OCFI ₃ OCH ₃ 1210 6-CH ₃ H N OCH ₃ OCH ₃ .211 6-OCH ₃ H CII OCH ₃ OCH ₃ 1212 6-OCII ₃ N N OCH ₃ OCH ₃ 1213 - ^ H ₂ - 5-CH ₃ H CH OCH ₃ OCH ₃ 1214 H H CH OCH ₃ OCH ₃  "* -C ) ) ] )

Table 1 (continued)

No. A -CH ₂ - R R ₂ H X Y Melting point ( ⁰ CI 1215 -CH ₂ - H H N OCH ₃ OCH ₃ 1216 -CH ₂ - H H CH OCH ₃ OCH ₃ 1217 -CH ₂ - H H CH OCH ₃ OCHF ₂ 1218 -CH ₂ - 6-CII ₃ II CH OCH ₃ OCH ₃ 1219 -CH ₂ - 6-CH ₃ H CH OCH ₃ OCH ₃ 1220 CH - 6-OCHF ₂ II CH OCH ₃ OCH ₃ 1221 - < 5-CH ₃ II CH OCH ₃ OCH ₃ 1222 - < H H CH OCH ₃ OCH ₃ 1223 · - < H H N OCH ₃ OCH ₃ 1224 - < H H CH OCH ₃ CH ₃ 1225 - < 6-CH ₃ H CH OCH ₃ OCH ₃ 1226 - < 6-OCH ₃ H CH OCH ₃ OCH ₃ 1227 - < II H CH OCH ₃ OCHF ₂ 1228 O 5-Cl H CH OCH ₃ OCH ₃ O O O O O y y y y y

Table 1 (continued)

No. A - ^ 7 ° R R ₂ e X Y melting point 1229 H H CH OCH ₃ OCH ₃ 1230 -CH ₂ - <) 0 H H N OCH ₃ OCII ₃ 1231 -CH ₂ - ^ O H H CH OCH ₃ CH ₃ 1232 -CH ₂ ^) ₀ 6-CH ₃ H CH OCH ₃ OCH ₃ 1233 -CH ₂ -Oo 6-OCH ₃ II CH OCH ₃ OCH ₃ 1234 PU s Π H H CH OCH ₃ OCHF ₂ 1235 -υΠρ ---- f \ J 6-OCHF ₂ H CH OCH ₃ OCH ₃ 1236 -OMo C ν H H CH OCH ₃ OCH ₃ 1237 Ο '' H H N OCH ₃ OCH ₃ 1238 -CH ₂ J ^ H H CH OCH ₃ CH ₃ 1239 6-CH ₃ H CH OCH ₃ OCH ₃ 1240 6 JH ₃ H CH OCH ₃ OCH ₃ 1241 II II CH OCH ₃ OCHF ₂ 1242 6-OCHF ₂ II CH OCH ₃ OCH ₃ 1243 H H CH OCH ₃ OCH ₃ + 138 to +139 1244 H H N OCH ₃ OCH ₃

Table 1 (continued)

No. A -CH ₂ -IJ ^N CT R R ₂ e X Y melting point 1245 ² ~ u H H CH OCH ₃ CH ₃ 1246 -CH ₂ -L ^ J H H CH OCH ₃ OCHF ₂ 1247 -CH ₂ -φ 6-CH ₃ H CH OCH ₃ OCH ₃ 1248 -CH ₂ -C ₀ ) 6-OCH ₃ H CH OCH ₃ OCH ₃ • 1249 -CH ₂ X ₀ ) H H CH OCH ₃ OCH ₃ 1250 -CH ₂ -Q II H N OCH ₃ OCII ₃ 1251 -CH ₂ -1 ^ J H II CH OCH ₃ CH ₃ 1252 -CH ₂ -J ^ J H H CH OCH ₃ OCIIF ₂ 1253 - JO 6-CH ₃ H CH OCH ₃ OCH ₃ 1254 -CH ₂ X) 6-OCH ₃ H CII OCH ₃ OCH ₃ 1255 6-OCHF ₂ H CH OCH ₃ OCH ₃ 1256 H H CH OCH ₃ OCH ₃ 1257 H II N OCH ₃ OCII ₃

Table 1 (continued)

No. A -O Ri R ₂ e X Y Melting point [ ⁰ Cl 1258 II H CH OCH ₃ OCII ₃ 1259 H H CH OCH ₃ OCIIF ₂ 1260 ^) ₅ O ₂ 6-CH ₃ H CH OCH ₃ OCH ₃ 1261 ^ N-CH ₃ 6-OCII ₃ H CH OCH ₃ OCH ₃ • 1262 ( N-CH ₃ 5-CH ₃ II CH OCH ₃ OCH ₃ 1263 Zn-CH ₃ 4-CH ₃ H CH OCH ₃ OCH ₃ 1264 { N-CH ₃ 6-OCHF ₂ H CH OCH ₃ OCH ₃ 1265 { N-CH ₃ H H CH OCII ₃ UCH ₃ 1266 H H N OCH ₃ OCH ₃ 1267 SO ₂ H H CH OCH ₃ CH ₃ 1268 6-CH ₃ H CH OCH ₃ OCH ₃ 1269 SO ₂ 6-OCH ₃ H CH OCH ₃ OCH ₃ 1270 H II CH OCH ₃ OCII ₃ SO ₂ 1271 H H N OCH ₃ OCH ₃ 1272 H H CH OCH ₃ CH ₃

Table 1 (continued)

No. A -O rl R ₂ e X Y Melting point m 1273 SO ₂ H H CII OCH ₃ OCII ₃ 1274 SO ₂ 6-CII ₃ II CH OCH ₃ OCH ₃ 1275 SO ₂ 6-OCH ₃ II CH OCH ₃ OCII ₃ 1276 SO ₂ 6-OCIIF ₂ H CH OCH ₃ OCH ₃ -CH ₂ - (3 SO ₂ 1277 -CH ₂ - () SO ₂ II II CH OCH ₃ OCH ₃ 1278 -CH ₂ - /) H H N OCH ₃ OCH ₃ 1279 SO ₂ H H CH OCII ₃ CH ₃ -CH ₂ -C> ^ SO ₂ 1280 -CH ₂ -C) ^ SO ₂ 6-CH ₃ H CH OCH ₃ OCH ₃ 1281 -CHF ₂ 6-OCH ₃ H CH OCH ₃ OCH ₃ 1282 -CIIF ₂ H H CH OCH ₃ OCH ₃ 1283 -CHF ₂ H H CH OCH ₃ CII ₃ 1284 -CHF ₂ H H N OCH ₃ CH ₃ 1285 -CF ₂ CHF ₂ II H N OCH ₃ OCH ₃ 1286 -CF ₂ CHF ₂ H H N OCH ₃ OCII ₃ 1287 -CF ₂ CHF ₂ H H N OCH ₃ CH ₃ 1288 -CF ₂ CHF ₂ H H CH OCH ₃ CH ₃ 1289 -CF ₂ CHF ₂ H II CH OCH ₃ OCH ₃ 1290 -CH ₂ CH ₂ N (CH ₃ ) ₂ H H CH CH ₃ CH ₃ 1291 -CH ₂ CH ₂ N (CH ₃ ) ₂ II II CH CH ₃ CII ₃ 1292 -CH ₂ CH ₂ N (CH ₃ ) ₂ II H CH OCH ₃ OCH ₃ 1293 -CH ₂ CH ₂ N (CH ₃ ) ₂ H II N OCH ₃ OCH ₃ 1294 H H N OCH ₃ CH ₃

Melting point J ⁰ C] ο c n n n c K t t t t t t t UK UK UK UK UK UK UK UK UK OCH ₃ + 136 to +138 OCH ₃ CH ₃ CH ₃ CH ₃ + 133 to + 137 +166 to +168 +145 to +148 OCH ₃ C U U U OCH ₃ Cl C) Cl Cl Cl u K ¹ K ¹ G uu K ¹ K ¹ K ¹ U ouuooouuuo OCH ₃ X KKKKKK UUUUUU oooooo CH ₃ OCH; ^: HDO CH ₃ OCH; OCH HDO OCH OCH; a KKKKK UUUUUZ Z OCH; K U Z U U uuuuuuuuuu oooooooooo OCII; Z Z U U KKKKKK K U K K K K KK KK uuzzzzzzuu U K K K K C-T KKKKKK K K cn K U νό JP Ö νό K K KKKKKKKKKK IWH K K K _ (S CM Ol »η υ-) m ei ei KKKKKK ZZZZZZ Ol CS O) O) Ol O) KKKKKK UUUUUU O) Ol CS O) O) O) [CH ₂ OCH ₃ K CH ₂ OCH ₃ CH ₂ OCH ₃ CH ₂ OCH ₃ cn K U K * m U XXX UUU ΚΚΚΚΚΚΚνόνόνό K O ₄ cn U U CS K O U CH ₂ OCH ₃ U O) K U oil No. KKKKKU UUUUUU I I I I I ►J- Uh U-U I CH ₂ OCH ₃ - Uh U-U κ χ UU Uh K U-U K K U-U cn m cn cn OOOOIIIIIE 0) 0) 0) 0) 01010101010) KKKKKKKKKK uuuuuuuuuu O) O) O) OlOlO) OlO) O) O) cn U U-U U-U 3- K U-U t -CH IO VO Γ ^ OO On O On On On On ^ 1301 U-U I 1303 1304 1305 1306 KKKKKKKKK uuuuuuuuuu I I I I I I I 1 U-U 1318 1319 1320 | l.321 1302 cncncocncncncncncncn 1317

Table 2

(H)

No. A R. Melting point [ ⁰ CJ 2001 -CH ₂ CH = CH ₂ H +178 2002 -CH ₂ CH ₂ OCH ₃ H 2003 -CH ₂ CH = CH ₂ 6-CH ₃ 2004 -CH ₂ CH = CH ₂ 5-CH ₃ 2005 -CH ₂ CH = CH ₂ 4-CII ₃ CH ₃ J ^J 2006 -CH ₂ -C = CH ₂ H +180 CH ₃ 2007 -CH ₂ -C = CH ₂ 6-CH ₃ CH ₃ 2008 -CH ₂ -C = CH ₂ 5-Cl 2009 -CH ₂ CH = CH ₂ 5-Cl + 193bis + 195 (Zcrs.) 2010 -CHjCH = CHCl H Cl I 2011 -CH ₂ -C = CH ₂ II 2012 -CH ₂ CH ₂ CH ₂ F II 2013 -CH ₂ CH ₂ CH ₂ F 6-CH ₃ 2014 -CH ₂ CH ₂ CH ₂ F 6-OCH ₃ 2015 -CH ₂ CH ₂ CH ₂ F 6-F 2016 -CH (CH ₃ ) CH ₂ F 6-F 2017 -CH (CH ₃ ) CH ₂ F 6-CH ₃ 2018 -CH (CH ₂ F) C ₂ H ₅ i " 2019 -CH (CH ₂ F) C ₂ H ₅ 6-CH ₃ 2020 -CH (CH ₂ F) CH ₂ F H 2021 -CH (CH ₂ F) CH ₂ F 6-CH ₃ 2022 -CH ₂ CH = CHCl (E) 6-OCHF ₂ 2023 -CH ₂ CH = CHCl (E) 5-CH ₃ 2024 -CH ₂ CH = CHCl (E) 4-CH ₃ 2025 -CH ₂ CH-CH-CF ₃ H 2026 -CH ₂ CH = CHBr H + 188 to + 190 2027 -CH ₂ CH = CHBr 6-CH ₃ 2028 -CH ₂ CH = CHBr 6-OCH ₃ 2029 -CH ₂ CH = CHBr 5-CH ₃ 2030 -CH ₂ CH = CHBr 4-CH ₃ 2031 H )

Table 2 (continued) Λ -CH ₂ -I _n ^ X) R ₁ Melting point [ ⁰ CJ -O 6-CH ₃ No. X) 6-OCH ₃ 2032 ] X) 5-CH ₃ 2033 ] -ο H 2034 ) 6-CH ₃ 2035 6-OCH ₃ 2036 6-OCHF ₂ 2037 5-CH ₃ 2038 4-CH ₃ 2039 H 2040 6-CH ₃ 2041 6-OCH ₃ 2042 5-Cl 2043 2044

Table 2 (continued) A -C + R ₁ Sclimelzpuiikt [ ⁰ CJ ~ ^{civ <} 0 ^o 5-CH ₃ No. - CH ₂ - <^ \> H 2045 -CH ₂ - ^ O 6-CH ₃ 2046 -OH ₂ Oo 6-OCH ₃ 2047 6-OCHF ₂ 2048 -CH ₂ -I _x J H 2049 6-CH ₃ 2050 -CH ₂ -Q 6-OCH ₃ 2051 -CH ₂ -Q 6-OCHF ₂ 2052 H 2053 6-CH ₃ 2054 6-OCH ₃ 2055 H 2056 6-CH ₃ 2057 2058

Table 2 (continued)

No. A -CH ₂ -Q Ri Melting point [ ⁰ CJ 2059 -CH ₂ -Q 6-OCH ₃ 2060 -O 6-OCHF ₂ 2061 II 2062 6-CH ₃ 2063 -O 6-OCH ₃ 2064 SO ₂ 5-CH ₃ 2065 ^s so ₂ H 2066 SO ₂ 6-CH ₃ 2067 OH -Π SO ₂ ...... y 6-OCH ₃ 2068 ^ < _s ) ₂ H 2069 -CH-O-CH ₂ -C. J SO ₂ 6-CH ₃ 2070 <^ N-CH ₃ 6-OCH ₃ 2071 H

Table 2 (continued)

No. Λ R Melting point [ ⁰ C] 2072 / N-CH ₃ 6-CH ₃ 2073 ί N-CH ₃ 6-OCH ₃ 2074 -CH ₂ -CBr = CH ₂ H +158 to +159 2075 -CH ₂ -CCl = CH ₂ H +172 to +173 2076 -CH ₂ CH = CHCl (Z) H +196 to +197 2077 -CH ₂ CH = CHCl (Z) 6-CH ₃ 2078 -CH ₂ CH = CHCl (Z) 6-OCH ₃ CH ₃ 2079 -CHCH ₂ OCH ₃ H +232 to +234 CH ₃ 2080 -CHCH ₂ OCH ₃ 6-CH ₃ 2081 -CH ₂ CH ₂ SO ₂ CH ₃ H +105 to + 110 2082 -CHCH ₂ Cl II +185 to +188 CH ₃ 2083 -CH ₂ CH ₂ CH ₂ Cl H +194 to +195 2084 -CH ₂ CH ₂ CHoCl 6-CH ₃ 2085 -CH ₂ CH ₂ CH ₂ Cl 6-OCH ₃ 2086 -CHF ₂ H 2087 -CF ₂ CHF ₂ H 2088 -CH ₂ CH ₂ N H Vh ₃ 2089 -CH ₂ CH ₂ N (C ₂ H ₅ ) 2 -CH ₂ CH ₂ NHCH ₃ H 2090 -CH ₂ CH ₂ NHCH ₃ H 2091 -CH ₂ CH ₂ N (CH ₃ ) ₂ 6-CH ₃ 2092 -CH ₂ CH = CH ₂ 6-CH ₃ 2093 -CH ₂ CH = CH ₂ 6-OCH ₃ 2094 -CH ₂ C = CH 6-OCHF ₂ 2095 -CH ₂ C = CII H +164 to +165 2096 -CH ₂ C = CH 6-CH ₃ 2097 -CH ₂ CF = CHCH ₃ 6-OCH ₃ 2098 -CH ₂ CH ₂ CH = CH ₂ H +116 to +118 (cc.) 2099 -CH ₂ CH ₂ CH = CH ₂ H 2100 -CH ₂ CH ₂ CH = CH ₂ 6-CH ₃ 2101 -CH ₂ CH ₂ CH = CH ₂ 6-OCH ₃ 2102 5-CH ₃

Table 2 (continued)

No. Λ rl Melting point [ ⁰ C] 2,103 2,104 -CH ₂ CH ₂ CH = CH ₂ -CH (CH ₃ ) CH = CH ₂ 4-CH ₃ H +176 (dec.) 2105 -CH (CH ₃ ) CH = CH ₂ 6-CH ₃ 2106 -CH (CH ₃ ) CH = CH ₂ 6-OCH ₃ 2107 -CH (CH ₃ ) CH = CH ₂ 5-CH ₃ 2108 -CH (CH ₃ ) CH = CH ₂ 5-Cl 2109 -CH (CH ₃ ) CH = CH ₂ 4-CH ₃ 2110 -CH ₂ CH = CHCH ₃ H 2111 -CH ₂ CH = CHCH ₃ 6-CH ₃ 2112 -CH ₂ CH = CHCH ₃ 6-OCH ₃ 2113 -CH ₂ CH = CHCH ₃ 5-CH ₃ 2114 -CH ₂ CH = CHCH ₃ 4-CH ₃ 2115 -CH ₂ CsC-CH ₃ H 2116 -CH ₂ CsC-CH ₃ 6-CII ₃ 2117 -CH ₂ ChC-CH ₃ 6-OCH ₃ 2118 -CH ₂ C = C-CH ₃ 6-OCHF ₂ 2119 -CH ₂ ChC-CH ₃ 5-CH ₃ 2120 -CH ₂ ChC-CH ₃ 5-Cl 2121 -CH ₂ ChC-CH ₃ -CH ₂ CH ₂ ChCH 4-CH ₃ 2122 -CH ₂ CH ₂ CHCH H 2123 -CH ₂ CH ₂ CHCH 6-CH ₃ 2124 -CH ₂ CH ₂ OCH 6-OCH ₃ 2125 CH ₂ CH ₂ CHCH 6-OCHF ₂ 2126 -CH ₂ CH ₂ CHCH 5-CH ₃ 2127 -CH ₂ CH = CHCl (E) 4-CH ₃ 2128 -CH ₂ CH = CHCl (E) H +230 (Zers.) 2129 -CH ₂ CH = CHCl (E) 6-CH ₃ 2130 -CH ₂ CH = CHCl (Z) 6-OCH ₃ 2131 -CH ₂ CH = CHCl (Z) 6-OCHF ₂ 2132 -CH ₂ CH = CHCl (Z) 5-CH ₃ 2133 -CH ₂ CH = CHCl (Z) 5-Cl 2134 4-CH ₃

Table 3

SO ₂ NH ₂

No. Ri Q Melting point [ ⁰ C] 3001 H F +121 to + 123 3002 5-Cl F +119 to +122 3003 5-CH ₃ F 3004 6-F F 3005 6-CH ₃ F 3006 6-OCH ₃ F 3007 4-CH ₃ F 3008 H SH +102 to +104 3009 6-CH ₃ SH 3010 6-OCHF ₂ F 3011 6-OCHF ₂ SH

Biological examples

Example B1: Pro-eminent herbicidal action

In the greenhouse, immediately after sowing the test plants in seed trays, the soil surface is treated with an aqueous spray mixture corresponding to an application rate of 4 kg of active substance / hectare. The seed trays are in

Greenhouse maintained at 22-25 ⁰ C and 50-70% relative humidity.

After 3 weeks, the herbicidal action with a nine-stage (1 = complete damage, 9 = no effect)

Rating scheme compared in an untreated control group.

Boniturnotes of 1 to 4 (especially 1 to 3) indicate a good barbicidal activity for bonuses of 6 to 9 months

(especially from 7 to 9) indicate a good tolerance (especially in crops).

In this experiment, the compounds of Table 1 show strong herbicidal action.

Example B2: Post-environmental herbicidal action (contact herbicide)

A number of weeds, SJWPhl monocots such as dicotyledons, were grown after emergence (at the 4- to 6-leaf stage) with an aqueous drug mixture; In a dosage of 4 kg of active substance per hectare, the plants are sprayed onto the plants and kept at 24 ° C.-26 ° C. and 45-60% relative humidity 15 days after the treatment, the test is evaluated Table 1 good herbicidal action.

Example B 3: Water-borne herbicidal action (paddy) The water weeds echinochloa er galli and monocharia vag. are sown in plastic cups (60cm ² surface, 500 ml volume). After sowing, make up to the surface with water. 3 days after sowing, the water level is raised slightly above the surface (3-5mm). Application takes place 3 days after sowing by spraying the test substances onto the vessels. The dose used corresponds to a quantity of active ingredient of 4 kg AS per hectare. The plant cups are then placed in the greenhouse under optimal growth conditions for the rice weeds, ie at 25 ° C-30 ° C and high humidity.

The evaluation of the experiments takes place 3 weeks after application. The compounds of Table 1 damage the weeds, but not the rice.

Example B4: Growth inhibition in tropical ground cover legumes (cover crops)

The experimental plants Centrosema pubescens and Psophocarpus palustris are propagated in 4 cm peat pots with soil (45%), peat (45%) and zonolite (10%) by cuttings. The cultivation takes place in the greenhouse at a daytime temperature of 27 ⁰ C and a nighttime temperature of 23 ° C. The lighting duration is at least 14 hours / day with an intensity of at least

Approximately 50 days after cultivation of the cuttings, the pots are placed in 13 cm pots, 4-5 Pflanzan / pot. After another 60 days, the plants are cut back to about 15 cm height and applied. They are using 0.1 to 300 g of active ingredient / ha (usually

25% formulated) sprayed in aqueous spray mixture. The amount of water used is about 200l / lia.

4 weeks after the application, the new growth in weight is determined and in% to the average of the untreated

Controls shown. The necrotic damage is listed in% to the total leaf area.

The new growth of the treated plants proves to be significantly lower than that of the untreated controls.

Example B 5: Growth control on soybeans Williams varieties are sown in 11 cm clay pots with soil (45%), peat (45%) and zonolite (10%) and in the climatic chamber at a daily temperature of 24 ⁰ C and a Night temperature of 19 ⁰ C attracted. The illumination duration is 16 hours per day with an intensity of approx. 350 microinstein.

Approximately 24 days after sowing repotting is done in 18 cm pots, 2 plants / pot. After another 12 days and in the stage of 5-6 Trifolia leaves, the application takes place with 0.1 to 300 g of active ingredient / ha, usually formulated at 25% and in aqueous Spritzbfühe. The amount of water used is about 200l / ha.

Approximately 4 weeks after the application the evaluation takes place. Here, the height of the new growth is measured and displayed in% of the average of the untreated controls. The necrotic damage is listed in% of the total leaf area

 The treated plants show a significantly lower new growth than the untreated controls.

Example B 6: Growth inhibition in cereals

Test plants (Iban spring barberries) are sown in 15 cm plastic pots with sterile soil and grown in the climatic chamber at a daily temperature of 10-15 ° C and a nighttime temperature of 5-10 ° C. The

Lighting duration is 13.5 hrs per day with an intensity of approximately 25000Lux.

Ce. 34 days after sowing and Gern thinning on 4 plants / pot, the application is carried out with 0.1 to 300g active ingredient / ha, usually formulated 25% and in aqueous spray mixture The amount of water used is about 500 l / ha. After application, the plants are placed in the greenhouse at a daytime temperature of at least 10 ° C. The lighting time is at least 13.5

Stjnden / day.

Approximately 28 T.'go after the treatment, the evaluation takes place. Here, the amount of new growth in% is shown as the average of unexposed checks. The necrotic damage is listed in% to the total leaf area.

The treated plants show a reduction of new growth compared to untreated controls.

Example B7: Growth inhibition in grasses

A mixture of grasses (eg Poa, Festuca, Lolium, Bromus, Cynosurus) and clover (Trifolium pratense / repens) is sown in 15 cm plastic pots with sterile soil and in the greenhouse at a daily temperature of 21 ⁰ C and a Night temperature of 17 ⁰ C attracted. The lighting duration is 13.5 hours / day with a light intensity of at least 7000 lux.

After casserole, the plants are cut back weekly to about 3cm height. About 42 days after sowing and 1 day after the last cut, the application is carried out with 0.1 to 300 g of active ingredient / ha, usually formulated at 25% and in aqueous

Spray mixture. The amount of water used is about 500l / ha.

Approximately 3 weeks after the treatment, the evaluation takes place. Here, the height of the new growth is measured and displayed in% of the average of the untreated controls. The necrotic damage is in% to the total leaf area '

listed.

The tested compounds of Table 1 cause a reduction of new growth compared to the untreated

Control.

Claims (15)

(ID Ri is hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₁ -CJ -alkoxy, Ci-Cj-alkylthio, C ₁ -C ₄ -haloalkoxy or A halogen-mono- to trisubstituted C ₁ -C ₆ -alkyl or Ca-Co cycloalkyl, or by C ₁ -C ₄ -alkoxy, Ci-C ₄ alkylthio, C ^ C alkylsulfonyl, C ^ CrAlkylsulfinyl, C2 C ₄ alkenyl, C ₅ -C ₆ cycloalkenyl, amino, C ^ Cj-alkylamino, C ^ Cj-dialkylamino or _C2-C4 alkynyl substituted C ₁ -C ₄ -alkyl or C ₃ -C ₆ -CyClOaJkYl, wherein the Cr-Q-alkenyl radical and the Cs-Ce-cycloalkenyl radical may be monosubstituted to trisubstituted by halogen; or a 4- to 6-membered saturated heterocycle containing a heteroatom selected from the group O, N and SO ₂ ; or C ₁ -C ₄ alkyl which is substituted by a 4- to 6-membered saturated heterocycle containing a heteroatom selected from the group O, N and SO ₂ ; mean. 2. Compounds of formula II according to claim 1, characterized in that R, hydrogen, halogen, C, -C ₄ alkyl, C, -C ₄ alkoxy, C, -C ₄ alkylthio or CF ₃ ; A halo to trisubstituted by halogen C ₂ -C ₆ alkyl; or by C ₁ -C ₄ -alkoxy, C ₁ -C ₄ alkylthio, C ^ C alkylsulfonyl, C ^ C alkylsulfinyl, Cr-C ^ AIkenyl or C ₂ -C ₄ -AIkJnYl substituted C ₁ -C ₄ - AIkYl, wherein the C ₂ -C ₄ alkenyl radical may be substituted once to three times by halogen; mean. 3. Compounds of formula II according to claim 1, characterized in that R _{1 is} hydrogen, methyl, methoxy, fluorine or chlorine. 4. Compounds of formula II according to claim 1, characterized in that AC ₁ -C ₆ alkyl or C ₃ -C ₆ cycloalkyl which is mono- to trisubstituted by halogen; or C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl which is substituted by C ₁ -C ₄ -alkoxy, C ₅ -C ₆ -cycloalkyl or C ₂ -C ₄ -alkenyl; where the C ₂ -C ₄ -alkenyl radical and the C ₅ -C ₆ -cycloalkenyl radical may be substituted once to three times by halogen. 5. Compounds of formula II according to claim 1, characterized in that A halo to trisubstituted by halogen C ₂ -C ₆ alkyl; or C ₁ -C ₄ -alkyl substituted by C ₁ -d-aikoxy or C ₂ -C ₄ -alkenyl, where the C ₁ -C ₄ -alkenyl radical may be substituted by one to three halogen atoms. 6. Compounds of formula II according to claim 5, characterized in that R _{1 is} hydrogen. 7. Compounds of formula II according to claim 1, characterized in that A allyl, methallyl, 2-methylpropenyl, 3-chloroallyl, methoxyethyl, fluorine- or chlorine-substituted C ₃ -C ₆ -cycloalkyl or 3-fluoropropyl. 8. Compounds of formula II according to claim 7, characterized in that R _{1 is} hydrogen. 9. Compounds of formula II according to claim 1, characterized in that R ₁ is hydrogen, halogen, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₂ -AIkYHhJo, C ₁ -C ₂ -haloalkoxy or CF _3; A mono- to trisubstituted by halogen-substituted C ₁ -C ₄ -alkyl or C ₃ -C ₆ -cycloalkyl, or by C ₁ -C ₂ -alkoxy, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkyl-sulfonic, C ₁ -C -alkylsulfinyl, C ₁ -C -alkenyl, C ₅ -C ₆ -cycloalkenyl, amino, C ₁ -C ₂ -alkylamino, C 1 -C ₃ -dialkylamino or C ₂ -C ₃ -alkyl ^- substituted C ₁ -C ₂ -alkyl or C ₃ -Inyl -C ₆ -CyClOaIkYl, where the C; rC ₃ alkenyl radical and the Cs-Ce-cycloalkenyl radical may be substituted one to three by halogen; or a 4- to 6-membered saturated heterocycle containing a heteroatom selected from the group O, N and SO ₂ ; or C ₁ -C ₂ alkyl which is substituted by a 4 to 6 membered saturated heterocycle containing a heteroatom selected from the group consisting of O, N and SO ₂ ; Lt; mean.. 10. Compounds of formula II .lach claim 1, characterized in that R _{1 is} hydrogen, halogen, C ₁ -C ₂ alkyl, C ₁ -C ₂ -AIkYUtIiO or CF ₃ ; A mono- to trisubstituted by halogen-substituted C ₂ -C ₄ -alkyl or by C ₁ -C ₂ -alkoxy, C ₁ -C ₂ -alkylthio, C ₁ -C ₂ -AlkYlSuIfOnYl, C -C -alkylsulfinyl, C ^ CrAlkenyl or C2 C ₃ alkynyl-substituted C ₁ -C ₂ alkyl, where the C ₁ -C -alkenyl radical may be substituted once to three times by halogen; mean. 11. Compounds of formula II according to claim 1, characterized in that R _{1 is} hydrogen; A halogen-mono- to trisubstituted C ₁ -C ₄ -alkyl or by C ₁ -C ₄ -alkoxy, C ₅ -C ₆ cycloalkyl or C ₂ -C ₄ alkenyl substituted C ₁ -C ₂ -A ^ yI or C ₃ -C ₆ -cycloalkyl, where the C ₂ -C ₄ -alkenyl radical and the C ₅ -C ₆ -cycloalkenyl radical may be monosubstituted to trisubstituted by fluorine or chlorine. 12. Compounds of formula II according to claim 8, characterized in that A is allyl, methallyl, 3-chloroallyl, methoxyethyl, 2-fluoroisopropyl or 3-fluoropropyl. 13. Compounds of formula II according to claim 1, characterized in that R _{1 is} hydrogen; A halogen AIN to trisubstituted C ₂ -C ₄ alkyl or by C ₁ -C ₄ -alkoxy or C ₂ -C ₄ alkenyl substituted C ₁ -C ₂ -alkyl, wherein the C ₂ -C ₄ alkenyl may be mono- to trisubstituted by fluorine or chlorine, means. 14. Compounds of formula II according to claim 8, characterized in that A is allyl, methallyl, 3-chloroallyl, methoxyethyl, or 3-fluoropropyl. 15. Process for the preparation of pyridylsulfonamides of the formula II according to one of claims 1 to 14, characterized in that a 3-mercaptopyridin-2-yl-sulfonamide of the formula IHb, (IHb) SO ₂ NII ₂ wherein R _{1 has} the meaning given under formula II in claim 1, in the presence of a base with a Compound of the formula XVIII, Z-A (XVIII) wherein A has the meaning given under formula II and Z is chlorine, bromine, iodine, CH ₃ SO ₂ O- or CH ₃ -σ \ -SO ₂ O-, to the compound of the formula XX, N is SO ₂ NH ₂ wherein A has the meaning given under formula II, and then this oxidized to the compound of formula II.
16. Compounds of the formula III, SO ₂ NH ₂ wherein R _{1 is} as defined under formula II and Q is fluoro or-SH, with the proviso that that Q is not -HS when R _{1 is} hydrogen.