CA1218366A - Herbicidally active n.sup.1,n.sup.2- disubstituted-n-azolecarboxamidines - Google Patents

Abstract

ABSTRACT

Novel herbicidally active amidinoazoles of the formula

Description

1~8366 The invention relates to new amidinoazoles, an inventive process for their preparation and their use as herbicides.
Various amidinoazole derivatives have been dis-closed as potential herbicides, but have not yet achievedany great importance as agents for combating weeds and/or regulatingthe pLant gro~th (compare German Patent Specification 2,321,330).
Ne~ amidinoazoles of the general formula (I) R~-502-N ~ ,~_R2 (I) and their metal salts in which R1 represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, R2 represents an optionally substituted and/or optionally fused six membered aromatic hetero-cyclic radical containing at least one nitrogen atom and Az represents an optionally substituted azole Z0 radical, that is to say a five-membered aromatic heterocyclic radical containing at least one nitrogen atom, and adducts of compounds of the formula (I) with strong acids, have now been found.
~he general formula (I) represents the individual tautomers of the formulae (IA) and (I~) Rl-502-N ~ ~ N~-R2 tIA) Az Le A 23 309 3~

- 2 -Rl-502-~H ~ ~-R (I~) Az in ~hich R1, R2 and Az have the abovementioned meanings, and mixtures of the tautomers (IA) and (IB).
The mixing ratio (IA)/(IB) depends on factors which determine the state of aggregation, such as, for example, the temperature, solvent and concentration.
The new amidinoazoles of the formula (I) are obtained by an inventive process in which sulphonyl-guanidine derivatives of the formula (II) R1_502_N~`H~ \!-R2 C tII) Rl-502~ 0-R~
in which R1 and R2 have the abovementioned meanings and R3 represents an optionally substituted hydro-15 carbon radical, are reacted with compounds of the formula (III) M-Az (III) in which Az has the abovementioned meaning and M represents hydrogen or one equivalent of a metal, if appropriate in the presence of bases and in the pre-sence of diluents, at temperatures between 0C and 100C, and, if appropriate~ the products of the formula (I~
thereby obtained are treated with metal derivatives or with acids.
The new amidinoazoles of tne formula ~I), their metal salts and their adducts with strong acids are distinguished by a powerful herbicidal activity.

Le A 23 30~

Surprisingly, the new compounds of the formula (I) exhibit a considerably better herbicidal action than the already kno~n amidinoazole derivatives of the same type of action.
It is also to be regarded as surprising that the compounds of the formula tI) according to the invention can be prepared by selective cleavage of sulphonylguani-dine derivatives of the formula (II), since, besides this novel reaction, other cleavage reactions, for example by attack on the sulphonyl groupings, were also to be expected.
~he invention preferably relates to compounds of the formula (I) in which R1 represents the radical ~ R4 wherein R4 and R5 are identical or different and for hydrogen, halogen tsuch as, in particular, fluor-ine, chlorine and/or bromine~, cyano, nitro or C1-C6-alkyl twhich is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-aLkylamino-carbonyl, di-(C1-C4-alkyl)-amino-carbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkYl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C~-C4-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl~, or for C2-C6-alkenyl Cwhich is option-ally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl~, or for C1-C4-alkoxy Cwhich is optionally sub-stituted by fluorine, chlorine, bromine, cyano, arboxyl c1-c4-alkoxY-carbonyl~ C1 C4 a y Le A 23 309 -1~83~

thio, C1-C4-alkylsulphinyl or Cl~C4-alkYl-sulphonyl], or for C3-C6-alkenoxy Cwhich is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl] or C3-C6-alkinoxy, or ~or the radical -StO)p-R6, wherein p represents the numbers zero, 1 or 2 and R6 represents c1-c4-alkYl twhich is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl], C3-C6-alkenYl~
C3-c6-alkinyl~ C1-C4-alkoxy, C1-C4-alkoxy-amino, C1-C4-alkoxy-C1-C4-alkyl-amino, C1-C4-alkylamino or di-(C1-CL-alkyl~-amino, or R4 and R5 represent phenyl or phenoxy, or Cl-C4 alkyl-carbonylamino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-carbonyl-amino or di-(C1-C4-alkyl)-amino-carbonylamino, or the radical -Co-R7 wherein R7 represents C1-C6-alkyl, C1-C6-alkoxy,C3-C6-cycloalkyloxy, C3-C6-alkenoxy, C1-C4-alkylthio, C1-C4-alkylamino, C1-c4-alkoxyamino~ C1-C4-alkoxy C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino Cwhich are optionally substituted by fluorine and/or chlorine~, or wherein R4 and R5 represent Cl-C4-alkylsulphonyloxy or di-(C1-C4-alkyl)-aminosulphonylamino, or the radical -~ =N-R~

uherein R8 represents C1-C6-alkyl ~hich is optionally substituted by fluorine, chlorine, cyano, carbox-yl, C1-C4-alkoxy, carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, or represents benzyl ~hich is optionally substi-tuted by fluorine or chlorine, or represents C3-Le A 23 309 -~Z~3366 Cb-alkenyl or C3-C6-alkinyl, optionalLy sub stituted by fluorin~ or chlorine, or represents phenyl which is optionaLly substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4 alkoxy, trifluoromethyl, trifluoromethoxy or trifluoro-methylthio, ~r represents C1-C6-alkoxy~ C3-C6-alkenoxy, C3-c6-alkinoxy or benzyloxy, option-ally substituted by fLuorine and/or chlorine, or represents amino, C1-c4-alkylamino~ di-(C1-C4-alkyl)-amino, phenylamino, c1-c4-alkYl-carbonyl amino, C1-C4-alkoxy-carbonylamino or C1-C4-alkyl-sulphonylamino, or represents phenylsul-phonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl and R~ represents hydrogen or C1-C4-alkyl;
or wherein, furthermore, R1 represents the radical -CH
R 10 R 1 1~:J
wherein R10 represents hydrogen or C1-C3-alkyl and R11 and R12 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-aLkyl ~which is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy Cwhich is optionally substituted by fluorine and/or chlorine~, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkYlsulphonYl or di-~C1-C~-alkyl)-aminosulphonyl;
or wherein, furthermore, R
R1 represents the radical R
30 wherein R13 and R14 are identical or different and repres-ent hydrogen, fluorine, ch~orine, bromine, nitro, cyano, C1-C4-a~kyl [which is optionally sub-Le A 23 309 ~Z18~6 stituted by fluorine and/or chlorine] or C~-C4-alkoxy Cwhich is optionally substituted by fluorine and/or chlorine];
or wherein, furthermore, R1 represents the radical ~ R

wherein R15 and R16 are identicaL or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1 C4-alkyl twhich is optionally substituted by fluorine and/or chlorine] or C1-C4-alkoxy twhich is optionally substituted by fluorine and/or chlorine], or represent C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl twhich are optionalLy substituted by fluorine and/or chlorine], or represent di-(C1-C4-alkyl~-aminosulphonyl or C1-C4-alkoxy-carbonyl;
or wherein, furthermore, R1 represents the radical ~ R

20 wherein R17 and R18 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl C~hich is optionally substituted by fluorine and/or bromine] or C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represent C1-C4-alkylthio, C1-C4-alkylsulphinyl or ~1-C4-alkylsulphonyl twhich are optionally substituted by fluorine and/or chlorine], or represent di-(C1-C4-alkyl)-amino-sulphonyl;
or wherein, furthermore, Le A 23 309 12~3366 R1 represents the radical ~
Z RZ
~herein R19 and R20 are ;dentical or different and represent hydrogen, fluorine, chlorine~ bromine, cyano, nitro, C1-C4-alkyl Cwhich is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is optionally substituted by fluor-ine and/or chlorine], C1-C4-aLkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl [which is optionally substituted by fluorine and/or chlorine~, or di-(C1-C4-alkyl)-amino-sulphonyl or C1-C4-alkoxy-carbonyl and Z represents oxygen, sulphur or the grouping N-~ , 15 wherein z1 represents hydrogen, C1-C4-alkyl Cwhich is optionally substituted by fluorine, chlorine, bromine or cyano~, C3-C6-cycloalkyL, benzyl, phenyl Cwhich is optionally substituted by fluor-ine, chlorine, bromine or nitro], C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl;
and wherein, furthermore, R2 represents the radical ~ R22 ~R 3 25 wherein R21 and R23 are identical or different and represent hydrogen, fluorine, chlorine, bromine, Cl-C4-alkYl ~which is optionally substituted by ~luorine and/or chlorine~ or C1-C4-alkoxy Cwhich is optionally substituted by fluorine and/
or chlorine], with the proviso that at least one of the radicals R21 and R23 is other than Le A 23 309 .

lZ~,836f~

hydrogen, and R2Z represents hydrogen, fluorine, chlorine, brom;ne, cyano or C1-C4-alkyl t~hich is option-ally substituted by fluorine and/or rhlorine];
or wherein, furthermore, 24 R2 represents the radical ~

uherein R24 and R25 are identical or different and repres-ent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl twhich is optionally substituted by fluorine and/or chlorine~, C1-C4-alkoxy [~hich is optionally substituted by fluorine and/or chlorine~ C1-C4-alkyl-amino or di-(C1-C4-alkyl~-amino, with the proviso that at least one of the radicals R24 and R25 is other than hydrogen;
or wherein, furthermore, R26 R2 represents the radical Y/~-R27 N ~

wherein 2û R26 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, C1-C4-alkyl twhich is option-ally substituted by fluorine and/or chlorine~ or C1-C4-alkoxy Cwhich is optionally substituted by fluorine and/or chlorine~, R27 represents hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl twhich is optionally sub-stituted by fluorine and/or chlorine~, cyano, formyl, C1-C4-alkYl-carbonyl or C1-C4-alkoxy-carbonyl and R28 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, C1-54-alkyl twhich is option-ally substituted by fluorine and/or chlorine~, Le A 23 309

3~6 C1-C4-alkoxy Cwhich is optionally substituted by fLuorine and/or chlorine~, amino, C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino, or R27 and R28 together represent C3-C4-alkane-5 diyl;
or wherein, furthermore, R29 N
R2 represents the radicaL ~/ ~N
N ~

wherein R29 and R30 are identical or different and represent fluorine, chlorine, bromine, hydroxyl, C1-C4-alkyl twhich is optionally substituted by fluorine and/or chlorine], C3-C5-cycloalkyl, C1-C4-alkoxy [~hich is optionally substituted by fluorine and/Dr chlorine3 or C1-C4-alkylthio, or represent C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino;
and ~herein, furthermore, N -N
R2 represents the radical ~ R3 ~herein R31 and R32 are identical or different and repres-ent hydrogen, methyl or methoxy;
and wherein, furthermore, Az represents a radical from the series compris-ing pyrazole, imidazole and triazole, which is optionally substituted by chlorine, bromine, iodine, nitro, C1-C4-alkyl twhich is optionally substituted by fluorine andJor chlorine], C1-C4-alkoxy twhich is optionally substituted by fluor-ine and/or chlorine], C1-C4-alkYlthio C~hich is optionally substituted by fluorine and/or chlorine] and/or phenyl twhich is optionally sub-stituted by fluorine, chlorine, bromine, iodine, C1-C4-aLkyl, trifluoromethyl, C1-C4-alkoxY, C1-C2-fluoroalkoxy, C1-C4-alkylthio, tri-fluoromethylthio, cyano, nitro or c1-C4-alkoxY-carbonyl].
Le A 23 309 1~8~3~;6 The invention further preferably relates to the alkali salts of the compounds of the formula (I), especially to their sodium and potassium salts, as well as their calcium salts. The metal salts are prepared by reacting the compounds of formula (I) with suitable metal compounds, for example metal alkoxides, especially Cl-C2-alcoholates.
The invention furthermore preferably relates to adducts of compounds of the formuLa (I) - as defined above - with hydrogen halide acids, such as hydrogen fluoride, hydrogen chloride,r hydrogen bromide or hydrogen iodide, with sulphuric acid, with alkanesuLphonic acids ~hich have 1 to 4 carbon atoms and are optionally substi-tuted by fluorine and/or chlorine or benzene- or naphtha-lene-sulphonic acids uhich are optionally substituted by fluorine, chlorine, bromine or methyl.
The invention particularly relates to compounds of the formula (I) in which (A) R1 represents the radical ~herein R4 represents fluorine, chlorine, bromine, methyl, chloromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, methylthio, methylsulphinyl, methylsulphonyl, Cl-C2-alky1aminosul-phonyl, phenyl, Cl-C3-alkoxycarbon~l, C~-C6-cyclall~
oxycarbonyl, difluormethylthio,trifluormethylthio,isopropyl-thio and R5 represents hydroqen;
and wherein, furthermore~ ~ R26 R2 represents the radical ~ R27 wherein R26 represents hydrogen, methyl, hydroxyl, fluorine, chlorine, bromine, methoxy or difluormethoxy, R27 represents hydrogen, chlorine, bromlne or methyl and R28 represents C~-C3-alkyl~ hydroxyl, fluorine, Le A 23 309 3~

chlorine, bromine or c1-c3-alkoxY;
and uherein, furthermore, Az represents a pyrazole or imidazole radical which is optionally substituted by methyl, or in which (B) Az and R1 have the meanings given above under (A) and N _~R
R2 represents the radical ~/ \N

wherein 1û R29 represents fluorine, chlorine, bromine, hydroxyl, methyl, cyclopropyl, methoxy, ethoxy, methylthio or ethylthio and R30 represents fLuorine, chlorine, bromine, hydroxyl, methyl, cyclopropyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino or di-ethylamino.
If, for example, N'-t4,6-dimethyl-pyrimidin-2-yl~ N''-methoxy-N''-N'''-bis-(2-methoxycarbonyl-benzene-sulphonyl)-guanidine and ;midazole are used as starting 2û substances in the process according to the invention, the course of the reaction can be outlined by the following equation:
COOCH3 N _~CH3 HN ~
52 ~ C~ ~ L~ N
52 ~OCH3 ~ ~ 5O2-NH-OCH3 ,COOCH3 N CH3 N ~H~ N~

N
Le A 23 309 33Ç~6 Formula (II) provides a general definition of the sulphonyl~uanidine derivatives to be used as starting substances in the preparation process according to the invention. In this formula, preferably, the radicals R1 and R2 have the same meanings as are mentioned above as preferred in the context of the definition of the corresponding radicals in formula ~I) and R3 preferably represents C1-C4-alkyl or benzyl.
Particularly preferred starting substances of the formula (II) are those in ~hich the radicals R1 and R2 have the same meanings as are mentioned above as particularly preferred in the context of the definition of the corres-ponding radicals in formula (I) and R3 represents methyl.
Examples which may be mentioned of the starting substances of the formula (II) are: N'-t~,6-direthyl-pyrimidin-2-yl)-N''-methoxy-N'',N'''-bis-(2-chloro-benzenesulphonyl)-, -N'',N'''-bis-(2-bromo-benzenesul-phonyl)-, -N'',N'''-bis-(2-fluoro-benzenesulphonyl)-, -N'',N~''-bis-(2-0ethyl-benzenesulphonyl)-, -N'',N'''-bis-(2-trifluoromethyl-benzenesulphonyl)-, -N'',N'''-bis-(2-methoxy-benzenesulphonyl)-, -N'',N'''-bis-(2-phenyl-benzenesulphonyl)- and -N'',N'''-bis-(2-methoxycarbonyl-benzenesulphonyl)-guanidine.
The sulphonyl-guanidine derivatives of the for-mula (II) to be used as starting substances are the sub-ject of a previous Patent -Application by the Applicant ~ompany which does not, however, belong to the previously published prior art (compare DE-OS (German Published Specification) 3,334,455).
The compounds of the formula (II) are obtained by a process in which guanidine derivatives of the formula (IV) Le A 23 30~
.

1'2~L83t~6 H-N ~ ~ ~ N-R2 ' tIV~
H ~ \ OR~
in uhich R2 and R3 have the abovementioned meanings, are reacted with sulphonic acid chlorides of the formula (V) ~1-S02-Cl (Y) in ~hich R1 has the abovementioned meaning, in the presence of acid acceptors, such as, for example, pyridine or diazabicyclooctane (DABCO), and if approp-riate in the presence of diluents, such as, for example,methylene chloride or chloroform, at temperatures between -20C and +50C, preferably at O to 30C. Working up can be carried out in the customary manner, for example by addition of ~ater to the reaction mixture, acidifica-tion, if appropriate, for example ~ith hydrochloric acid,extraction uith a solvent ~hich is virtually ~ater-immiscible, such as, for example, methylene chloride or chloroform, and ~ashing of the organic phase with uater, drying, filtration and concentration~ The products of the formula (II) which thereby remain in the residue can in general be made to crystallise with organic solvents and, if appropriate, purified by recrystallisation.
The guanidine derivatives of the formula (IV) required as intermediates are also the subject of the abovementioned previous Patent Application by the Applic-ant Company (compare DE-OS (German Published Specifica-t;on) 3,334,455).
These guanidine derivatives are obtained by a process in uhich cyanoamino compounds of the formula (VI) Le A 23 309 1~83t~
~ 14 -NC-NH-R2 (VI) in ~hich R2 has the abovementioned meaning, are reacted with hydroxylamine derivatives of the formuLa S (VII) H2N-oR3 (VII) in ~hich R3 has the abovementioned meaning, or hydrochlorides thereof, if appropriate in the presence of diluents, such as, for example, ethanol or butanol, at temperatures bet~een 20C and 150C, preferably between 50C and 120C, and, if appropriate, the products are then treated with acid acceptors, such as, for example, (aqueous~ ammonia, sodium hydroxide or potassium carbon-ate. The guanidine derivatives (IV) are in gener3lobtained here as crystals.
Some of the cyanoamino compounds of the formula (VI) are known (compare J. Chem. Soc. 1953, 1725 - 1730).
These compounds are essentially obtained by the following two synthesis routes:
(1) generally by reaction of alkali metal or alkaline earth metal salts of cyanamide - such as, for example, sodium cyanamide or calcium cyanamide - with halogen com-pounds of the formula (VIII) Hal1-R2 (VIII) in ~hich R2 has the abovementioned meaning and Hal1 represents fluorine, chlorine, bromine or iodine, in particular chlorine, if appropriate in the presence of inert diluents, such as, for example~ acetone, acetonitrile or dimethylform-Le A 23 309 33~

amide, at temperatures between 0C and 150C, preferably between 10C and 100C; after the voLatile components have been distilled off and the residue has been dissolved in water, the cyanoamino compounds of the formula (VI) can be precipitated by acidification, for example with hydrochlori~ acid, and isolated by filtrat;on with suc-tion; or t2) in the case where R2 represents a substituted pyri-midinyl radical, by reaction of cyanoguanidine ("dicyan-1L diamide") with ~-dicarbonyl compounds, such as, for ~xample, acetylacetone, or their derivatives, such as their acetals or enamines, (compare JO Chem. Soc. 1953, 1725-1730), acetoacetic acid ester ~compare J. Prakt. Chem.
77, (1908), 542 and J. Chem~ Soc. 1948, 586) or malonic acid esters (compare German Patent Specification 158,591).
The 2-cyanoamino-4-hydroxy-6-methyl- or -4,6-dihydroxy-pyrimidines obtained from acetoacetic acid esters or malonic acid esters can be converted into corresponding 2-cyanoamino-4-alkoxy-6-methyl- or -4,6-dialkoxy-pyrimi-dines in a known manner by reaction with alkylating agents, such as, for example, dimethyl sulphate or di-ethyl sulphate, if appropriate in the presence of dilu-ents, such as, for example, water, methanol, ethanol, n-or iso-propanol, acetone, dioxane or dimethylformamide, and in the presence of acid-binding agents, such as, for example, sodium hydroxide or potassium hydroxide or sodium carbonate or potassium carbonate. To avoid N-alkylation, acylation is carried out, if appropriate, with an acylating agent, such as, for example, acetic anhydride or acetyl chloride, and, after the alkylation, the product is deacylated again with aqueous acids or bases.
The halogen compounds of the formula (VIII) are known (compare J. Chem. Soc. (C) 1966, 2031; Chem. Pharm.
Bull. 11 (1963)o 1382 - 1388; Arch. Pharm. 295 (1962~, 6~9 - 657).
The hydroxylamine derivatives of the formula Le A 23 309 3~6 (VII) are known or can be prepared by processes which are known per se (compare Chem. Pharm. Bull. 15 (1967), 345 -349; Bull. Soc. Chim. France 1958 664; and Synthesis 1976, 682).
Some of $he sulphonic acid chlorides of the for-mula (V) are known (compare Chemistry Lett. 1978, 951;
European Patent Applications 23,422, 35,893, 42,731, 44,808, 44,8û9, 51,466, 64,804 and 70,û41; U.S. Patent Specifications 2,929~820, 4,282,242 and 4,372,778; and J.
Org. Chem. _ (1968), 2104).
These compounds are essentially obtained by the following two synthesis routes:
(1) by reaction of the corresponding sulphonic acids R1S03H or of alkali metal or alkaline earth metal salts thereof with hydrogenating ayents, such as, for example, phosphorus-V chloride tphosphorus pentachloride), phosphoryl chloride (phosphorus oxychloride), thionyl chloride, phosgene or benzotrichloride, if appropriate in the presence of catalysts, such as, for example, pyridine or dimethylformamide, and if appropriate using inert diluents, such as, for example, methylene chloride, chloroform, acetonitrile, chlorobenzene and/or sulpholane, at temperatures between -20C and +150C, preferably between 0C and +100C; after dilution with water, the sulphonic acid chlorides can be isolated by filtration with suction - where they are obtained as crystals - or purified by extraction with a water-immiscible solvent, such as, for example, methylene chloride, diethyl ether or hexane, washing and drying of the extracts, concentra-tion and recrystallisation or distillation; ort2) in a manner which is known per se (compare J. Org.
Chem. 25 (1960), 1824; DE-OS (German Published Specifica-tion) 2,308,262 and European Patent Application 59,241) by reaction of corresponding amino compounds R1-NH2 hith sodium nitrite and hydrochloric acid, if appropriate in the presence of acetic acid, at temperatures between Le A 23 309 ~8~3~6 -10C and +20C, preferably bet~een -5C and +10C, and subsequently (in situ) ~ith sulphur dioxide or a salt of sulphurous acid, such as, for example, sodium sulphite or sodium b;sulphite, in the presence of a copper com-pound, such as, for example, copper chloride or coppersulphate, as the catalyst, at temperatures between 0C
and 80C, preferably between 10C and 60C.
Working up can be effected in the customary manner: on dilution ~ith water, the sulphonic acid chlorides are in general obtained as crystals and can be isolated by filtration ~ith suction. However, they can also be extracted from the aqueous dispersion ~ith a solvent which is virtually ~ater-immiscible, such as, for example, methylene chloride or diethyl ether, and dried and purified by vacuum distillation.
For0ula (III) provides a general definition of the compounds also to be used as starting substances in the process according to the invention. In this formula, Az preferably has the same meaning as is given above as preferred in the context of the defini-tion of the substituents of formula (I) and M preferably represents hydrogen, lithium, sodium or potassium.
Particularly preferred starting substances of the formula (III) are those in which Az has the same meaning as is mentioned above as particularly preferred in the context of the definition of the substituents of formula (I) and M represents hydrogen.
Examples which may be mentioned of the starting substances of the formula (III) are: pyrazole, 3,5-di-methyl-pyrazole, 4-chloro-pyrazole, 4-bromo-pyrazole, 4-iodo-pyrazole, 4-chloro-3,5-dimethyl-pyrazole, imidazole, 2-methyl-imidazole, 2-ethyl-imidazole, 2-propyl-imidazole, 2-isopropyl-imidazole, 4 methyl-imidazole, 4-ethyl-imidazole, 4-nitro-imidazole, 2-methyl-4-nitro-imidazole, 2-methyl-5-nitro-imidazole, 4-methyl-5-nitro-imidazole, Le A 23 309 3~6 2,4-dime~hyl-imidazole and 1,2,4-tr;azoLe.
The azoLes of the formula (III) to be used as starting substances are kno~n.
The process according to the invention is prefer-ably carried c,ut in the presence of diLuents. Possiblediluents are virtually all the inert organic solvents, but preferably aprotic polar solvents. These include halosenated hydrocarbons, such as, for example, methylene chloride, chloroform, 1,2-dichloroethane and chloroben-zene, ketones, such as, for example, acetone, methylethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as, for example, methyl acetate and ethyl acetate, nitriles, such as, for example, aceto-nitrile and propionitrile, ethers, such as, for example, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, amides, such as, for example, dimethylformam;de and dimethylacetamide, and dimethyl-sulphoxide and sulpholane.
The process according to the invention is prefer-ably carried out in the presence of bases. Possiblebases are the usual arid acceptors, but preferably nucleo-philic nitrogen compounds ~hich have very little or virtually no proton donor properties. These include tri-alkylamines, such as, for example, trimethylamine, tri-ethylamine, tripropylamine and tributylamine, dialkyl-aralkylam;nes, such as, for example, N,N-dimethyl-benzyl-amine and N,N-diethylbenzylamine, dialkyl-arylamines, such as, for example, N,N-dimethylaniline and N,N-diethyl-aniline, and nitrogen-containing heterocyclic compounds, such as, for example, pyridine, 2-methyl-pyridine, 2-methyl-5-ethyl-pyridine, 4-dimethyl-amino-pyridine and diazabicyclooctane tDABC0) .
The reaction temperatures can be varied ~ithin a substantial range in the process according to the inven-tion~ In general, the reaction is carried out between 0C and 100C, preferably between 10C and 80C.Le A 23 309 -The process according to the invention is in general carried out under normal pressure.
For carrying out the process according to the invention, in general between 1 and 5 moles, preferably between 1 and 3 moles, of a compound of the formula (III) and, if appropriate, between 0.01 and 5 moles, preferably between 0.1 and 3 moles, of a base are employed per mole of sulphonylguanidine derivative of the formula (II).
The reaction components are usually brought to-gether at room temperature and the reaction mixture isstirred until the reaction has ended. If the products are obtained as crystals, they can be isolated by filtra-tion uith suction. Otherwise, the mixture is concentra-ted and the residue is made to crystallise with a suit-able solvent.
The active compounds according to the inventioncan be used as defoliants, desiccants, agents for des-troying broad-leaved plants and, especially, as weed-killers. By ~eeds, in the broadest sense, there are to be understood all plants which gro~ in locations where they are undesired~ Whether the substances according to the ;nvention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the follow-ing pLants:
Dicotyledon ~eeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Cheno-podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.
Dicot~ledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lac-Le A 23 309 83~

tuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Bra-chiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agro-pyron, Cynodon, Monochoria, Fimbristylis, Sagittaria~
Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
MonocotyLedon cultures _of the genera: Oryza, Zea, Triti-cum, Hordeum, Avena, Secale, Sorghum~ Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds accord-ing to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the con-centration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings~ Equally, the compounds can be employed for combating ~eeds in peren-nial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
The active compounds according to the invention can be used for selectively combating monocotyledon and dicotyledon ~eeds in monocotyledon and dicotyledon crops, in particular in dicotyledon crops, such as, for example, cotton. CThe active compounds according to the invention also have a fungicidal action against Pyricularia oryzae on rice.~
The active compounds can be converted to the cus-tomary formulations, such as solutions, emulsions, wett-able powders, suspensions, powders, dusting agents, Le A 23 309 pastes, soluble po~ders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in kno~n manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally ~ith the use of surface-active agents, that is emulsify-ing agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of ~ater as an extender, organic solvents can, for example, also be used as auxi-liary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlorinated 3li-phatic hydrocarbons, such as chlorobenzenes, chloroethyl-enes or methylene chloride, aliphatic hydrocarbons, suc~h as cyclohexane or paraffins, for example petroleum frac-tions, mineral and vegetable oils, alcohols, such as butanol or glycol as ~ell as ~heir ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as ~ell as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kao-lins, clays, talc, chalk, quartz, attapulgite, montmoril-lonite or diatomaceous earth, and ground synthetic miner-als, such as highly disperse silicic acid, alumina and silicates, as soLid carriers for granules there are suit-able: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as ~ell as synthetic granules of inorganic and organic meals, and granules of organic mater;al such as sawdust, coconut shells~ maize cobs and tobacco stalks; as emulsi-fying andtor foam-forming agents there are suitable: for Le A 23 309 -12~8~

example non-ionic and anionic emulsifiers, such as poly-oxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for exampLe aLkyLaryL poLygLycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for exampLe lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, poLyvinyL aLco-hoL and polyvinyl acetate, as well as natural phospho-lipids, such as cephalins and Lecithins, and synthetic phosphoLipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use coLorants such as ;norganic pigments, for exampLe iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as saLts of iron, man~
ganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain betaeen 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90X.
The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixes being possible.
PossibLe components for the mixtures are known herbicides, such as, for example, N-t2-benzothiazolyl)-N,N'-dimethyl-urea~ 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 4-amino-6-t1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one, 4-amino-6-(1,1-dimethyl-ethyl)-3-ethylthio-1,2,4-triazin-5(4H)-one, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4-t1H,3H)-dione, 4-amino-Le A 23 309 3-methyl~6-phenyl-1,2,~-triazin-5(4H)-one, 2-chloro-4-ethylamino-6-;sopropyl-amino-1,3,5-triazine, the R-enantiomer of (trimethylsilyL)-methyl 2-t4-(3,5 dichloro-pyridin-2-oxy)-phenoxy~-propionate, the R-enantiomer of (2-benzyloxy) ethyl 2-C4-(3,5-dichloropyridyl-2-oxy)-phenoxyJ-propionate, 2,4-dichlorophenoxyacetic acid, 2-~2,4~dichlorophenoxy)-propionic acid, 4-chLoro-2-methyl-phenoxy-acetic acid, 2-(2-methyl-4-chloro-phenoxy)-propionic acid, 3,5-diiodo 4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxy-benzonitrile and diphenyl ethers and phenylpyridazines, such as, for example, pyridates. Sur-prisingly, some mixtures also sho~ a synergistic action.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solu-tions, suspensions, emulsions, powders, pastes and gran-ules. They are used in the customary manner, for example by watering, spraying, atomising or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before so~ing.
The amount of active compound used can vary ~ithin a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are bet~een 0.001 and 10 kg of active compound per hectare of soil surface, preferably bet~een 0.05 and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Le A 23 309 1~183~i6 Preparation Examples Example 1 ~ C~ ~
N

N~ ~ CH~
H,C

A mixture of 5.9 9 (0.01 mole) of N'-(4,6-di-methyl-pyrimidin-2-yl)-N''-methoxy-N'',N'''-(2-methoxy-carbonyl-benzenesulphonyl)-guanidine, 1.1 9 (0.011 mole~
of 3,5-dimethyl-pyrazole, 3.0 9 (0.03 mole) of triethyl-amine and 30 ml of acetone is stirred at 20C for 2 days.
The product obtained as crystaLs is isolated by filtra-tion with suction.
2.7 9 (61X of theory) of the compound of the abovement;oned structural formula of melting point 164C
are obtained.
The compounds of the formula ~I) listed in the follo~ing Table 1 can be prepared analogously:

Le A 23 309 ~.

33~6 Table 1 Exam~le MeltingO
No Rl R2 Az Point t C) (~ ~N~H3 ~ ~JCH3 197 3 ~ ~C H 3 N ~3 21 4 \N~ ~ H ~ C H 3 1 8 4NN ~C H ~ ~ 17 8 ~N--S;; 16 2 ~ 3 ~N~ ~ CH3 Le A 23 309 Table 1 (continuation) MeltingO
Exam~le 1 2 Az Point ( C) No. R _ R _ _ OCHF3 N ~ CH3 ~N CH3 8 ~ (/ ~ ~ ~ 183 N-~ ~ (Zers.) COCCH2CH2cH3 3 CH3 ~ N -~ CH3 ~N ~ C 3 103 11 ~ 3 -~N~N~ ~ 3 166 12 ~ N ~ 3 ~ CH3 OCE~3 13 ~02N (C2H5 ) 2 ~ 3,,~ 3 14 ~ N ~ ~ CH3 I,e A 23 309 ~2~t33~6 Example la C 4N~ X H 2 S 0 4 N ~ CH3 H~

A oixture of 2.9 9 (0,0066 mole) of the product from Example 1, 0.8 9 (0.008 mole) of sulphuric acid and 20 ml of acetone is stirred ~t 20C for 4 hours. The product obt~ined as crystals is then isolated by filtra-tion ~;th suction.
1.8 ~ (51X of theory) of the product of the above~enti~ned for~ul~ of ~elting point 182C are obtained.
Example lb ~ S 2 - N ~` _~ N 4 N

/ ~ CH3 A solution of 0.5 g (O.OOS mole) potassium ethylate in 15 ml of ethanol is added dropwise to a mixture of 2.6 g (0.006 mole) of the product obtained according to Example 1 (above) and 15 ml of ethanol. The reaction mixture is stirred at 20C for about 20 hours, then the product obtained as crystals is isolated by filtration with suction.
1.7 g (60 % of theory) of the product of the abovementioned formula of melting point 143C are obtainedO

Le A 23 309 `` ~21133~6 The following compounds can be prepared analogously:

Example 1c:
COOCH3 Na CH3 N ~ Melting Point:
C ~ N~ tH3 138 C

N ~ CH3 Example 4a:
Br 'H Melting Point:
S2-~ ~,; N 4/ ~ 181C

N ~ CH3 ~3C

Preparation of starting substances of the formula (II) Example (II-1) 2 ~ c~ ~N
~N~

C~

Le A 23 309 133~6 A mixture of 29.4 9 (0.15 mole) of N'-(4,6-di-methyl-pyrimidin-2-yl)-N''-methoxy-guanidine, 63~6 9 (0.3 mole) of 2-chlorobenzenesulphonyl chloride and 150 ml of pyridine is stirred at 20C for 2 days. After most of the pyridine has been distilled off under a ~aterpump vacuum, 200 ml of ~ater are added to the residue and the mixture is extracted with 200 ml of methylene chloride.
The organic phase is separated off, dried and concentra-ted. The residue is made to crystallise by digestion with ethanol.
41.2 9 t51X of theory) of N'-(4,6-dimethyl-pyri-midin-2-yl)-N''-methoxy-N''-N'''-bis-(2-chloro-benzene-sulphonyl)-guanidine of melting point 164C to 166C are obtained.
The compounds of the formula (II) listed in the following Table 2 can be prepared analogously:

R1-S02-N~_,jN-R
(I I) Rl -52~ ~ o~R3 Le A 23 309 33~6 Table 2 E ~ ~ _ ~ --II-2 ~ OCH3 ~ H3 CH3 165 II-3 ~ 3 ~ N ~ tH3 CH3 129 Il-4 ~ ~ NN ~ ~H3 CH3 171 CF3 ~ ~ CH3 121 II-5 ~ N CH3 II-6 ~ CH3 147 II-7 ~ N ~ CH3 CH3 166 OCH3 ~ ~ CH3 1 9b II-8 ~ \N ~ CH3 OCF34 N ~ CH3 C~3 158 II-9 ~_ N=~CH3 OCHF~4 N ~ CH3 CH3 163 II-10 ~_ N=~CH3 Le A 23 309 12~8366 Table 2 - Continuation _.

Example 1 2 R3 Point ( C) No. R _ _ _R _ _ _ _ _ _ _ 11-11 ~ H3 ~ CH3 CH3 155 50^N(CH3~2 N ~ CH3 CH3 138 II-13 ~ OOC~H54N ~ CH3 CH3 106 II-14 ~ OOC4Hg(-n)~ ~ CH3 CH3 104 II-15 ~ oc3H7(-n)~ ~ CH3 134 N ~ CH3 CH3 155 3 7 ( CH3 II-17 ~ ~/ ~ CH3 65 II-18 ~ CH3 182-183 Le A 23 309 1~L83~i~

Pre aration of startin substances of the formula (IY) P _ _ ~ _ _ ExampLe (IV-1) ~ CH3 H-~H ~
I ~H3 ~N~

A mixture of 109 9 (0.67 mole) of O-methylhydrox-ylamine hydrochloride, 99 9 (0.67 moLe) of 2-cyanoamino-

4,6-dimethyl-pyrimidine and 600 ml of ethanol is heated at the boiling point under reflux for 7 hours. The alcohol is then distilled off under a waterpump vacuum, the residue is dissolved in hot water and this solution is added to 100 ml of concentrated ammonia. The product which has crystallised out is filtered off with suction and recrystallised from ethanol.
71.8 9 ~55X of theory3 of N'-(4,6-dimethyl-pyri-midin-2-yl)-N''-methoxy-guanidine of melting point 134C
to 136C are obtained.
Preparation of starting substances of the formula ~V~
Example (V-1~
C l ~SO~Cl 295 ml of phosphoryl chloride ("phosphorus oxy chloride") are added dropwise to a mixture of 172 9 (0.8 mole~ of sodium 2-chloro-benzenesulphonate, 300 ml of acetonitrile and 300 ml of sulpholane at 20C to 30C.
The reaction mixture is stirred at 70C for 4 hours and then cooled to 5C and diluted with ice-water~ After extraction with petroleum ether, ~ashing of the extrac-tion solution with water, drying, filtration and concen-tration, the product which remains in the residue is Le A 23 309 1~83~

purified by vacuum distillation.
117 9 (70~ of theory) of 2-chloro-benzenesul-phonyl chloride of boiling point 110C/1.1 mbar are obtained.
Example (V-2) ~COOCH3 ~S02C ~

75.5 9 (0.5 mole~ of methyl 2-aminobenzoate are dissolved in 176 ml of concentrated hydrochloric acid and 100 ml of acetic acid. A solution of 34.4 9 of sodium nitrite in 70 ml of water is added dropwise at ~C. After the reaction mixture has been subsequently stirred for 15 minutes, it is slowly added to a saturated solution, cooled to 0C, of sulphur dioxide in 450 ml of acetic acid. After the cooling bath has been removed, the mixture is stirred until the evolution of gas has ended, 10 9 of copper-II chloride being introduced in portions. After dilution with ice-uater, extraction with methylene chloride, washing of the extraction solution with water, drying, filtration and concentration, the product which remains in the residue is purified by vacuum distillation.
45 9 (38X of theory) of 2-methoxycarbonyl-benzene-sulphonyl chloride of boiling point 150C/1.33 mbar are obtained.
The compounds of the formula (V~ listed in the following Table 3 can be prepared analogously:

R1 _ S02 - C l (V) Le A 23 309 lZ3L8366 Table 3 Example No. R] BoiLing point/pressure V -3 ~ H, distillation) V -~ ~ CE, rMelting point: 100C
V-S ~_ (il) V -6 ~ 142C/4 mbar V -7 OC~3 10c,C/4 mbar V -8 ~ ¦Meltir,g point: 32C]

V -9 ~ CH~2 (OiL, decomposition on distillation) 02N(CH3)2 V -lO ~ tMelting point: 103C~

V -11 ~ distillation) SCH(cH3)2 V -l2 ~ 90C/1.33 mbar V -13 ~ H2S02CH3 rMelting point: 120 C]

V -l4 ~ o0C2Hs 155C/5.32 mbar Le A 23 309 121~3~

Table 3 (continuation) Exam~le No R Boilinq Point/Pressure ~ CC3H7(-n) V-15 ~

~ CoOC3H7(-i) V-16 ~

V-17 ~ 41-43C

Le A 23 309 Example A
Pre-emergence test Solvent: 5 parts by ~eight of acetone Emulsifier: 1 part by ~eight uf alkylaryl poLyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emul-sifier is added and the concentrate is diLuted ~ith water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, ~atered wi~h the preparation of the active compound. It is expedient to keep the amount of water per unit area constant. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
û~ = no action ~like untreated control) 100X = total destruction In this test, for example, the following compounds from the preparation examples exhibit an excellent activity:
~1), (2), (4~ and (5).

Le A 23 309 Example B
Post-emergence test Solvent: 5 parts by weight of acetone EmuLsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation o~ ac~ive com-pound, 1 part by ~eight of active compound ;s m;xed uith the stated amount of sclvent, the stated amount of emulsi-fier is added and the concentrate is diluted with water to the desired concentration.
Test plants ~hich have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a uay as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 l of watertha. After three ~eeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control. The figures denote:
OX = no action (like untreated control) 100X = total destruction In this test, for example, the following compouncls from the preparation examples exhibit an excellent activity:
(1), (2), (4) and (5).

Le A 23 309

Claims (22)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An amidinoazole of the formula I

(I) in which R1 represents the radical wherein R4 and R5 are identical or different and for hydrogen, fluorine, chlorine, bromine, cyano, nitro or C1-C6-alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylaminocarbonyl, di-(C1-C4-alkyl)-amino-carbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkyl-amino-carbonyloxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl], or for C2-C6-alkenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl, or phenyl], or for C1-C4-alkoxy [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl], or for C3-C6-alkenoxy [which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-represents benzyl which is optionally substituted by fluorine or chlorine, or represents C3-C6-alkenyl or C3-C6-alkinyl, optionally substituted by fluorine or chlorine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluorom-ethoxy or trifluoromethylthio, or represents C1-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, optionally substituted by fluorine and/or chlorine, or represents amino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C4-alkoxycarbonylamino or C1-C4-alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl and R9 represents hydrogen or C1-C4-alkyl;
or wherein, furthermore, R1 represents the radical - wherein R10 represents hydrogen or C1-C3-alkyl and R11 and R12 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylsulphonyl or di-(C1-C4-alkyl)-aminosulphonyl;

alkoxy-carbonyl] or C3-C6-alkinoxy, or for the radical -S(O)p-R6, wherein p represents the numbers zero, 1 or 2 and R6 represents C1-C4-alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, or C1-C4 alkoxy-carbonyl], C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkylamino, C1-C4-alkylam-ino or di-(C1-C4-alkyl)-amino, or R4 and R5 represent phenyl or phenoxy, or C1-C4-alkyl-carbonylamino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-carbonyl-amino or di-(C1-C4-alkyl)-amino-carbonylamino, or the radical -CO-R7, wherein R7 represents C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkyloxy, C3-C6-alkenoxy, C1-C4-alkylthio, C1-C4 alkylamino C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino [which are optionally substituted by fluorine, and/or chlorine], or wherein R4 and R5 represent C1-C4-alkysulphonyloxy or di-(C1-C4-alkyl)-aminosulphonylamino, or the radical wherein R8 represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkylthio, C1-C4-alkysulphinyl, or C1-C4-alkysulphonyl, or or wherein, furthermore, R1 represents the radical wherein R13 and R14 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine]
or C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine];
or wherein, furthermore, R1 represents the radical wherein R15 nd R16 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine] or C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represent C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkysulphonyl [which are optionally substituted by fluorine and/or chlorine], or represent di-(C1-C4-alkyl)-aminosulphonyl or C1-C4-alkoxy-carbonyl;
or wherein, furthermore, R1 represents the radical wherein R17 and R18 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl [which is optionally substituted by fluorine and/or bromine] or C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], or represent C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl [which are optionally substituted by fluorine and/or chlorine], or represent di-(C1-C4-alkyl)-aminosulphonyl; or wherein, furthermore, R1 represents the radical wherein R19 and R20 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl [which is optionally substituted by fluorine and/or chlorine], or di-(C1-C4-alkyl)-amino-sulphonyl or C1-C4-alkoxy-carbonyl and Z represents oxygen, sulphur or the grouping N-Z1, wherein Z1 represents hydrogen, C1-C4-alkyl [which is optionally substituted by fluorine, chlorine, bromine, or cyano], C3-C6-cycloalkyl, benzyl, phenyl [which is optionally substituted by fluorine, chlorine, bromine or nitro], C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl;
and wherein, furthermore, R2 represents the radical wherein R21 and R23 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine] or C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], with the proviso that at least one of the radicals R21 and R23 is other than hydrogen, and R22 represents hydrogen, fluorine, chlorine, bromine, cyano or C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine]; or wherein, furthermore, R2 represents the radical wherein R24 and R25 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino, with the proviso that at least one of the radicals R24 and R25 is other than hydrogen;
or wherein, furthermore, R2 represents the radical wherein R26 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, C1-C4-alkyl[which is optionally substituted by fluorine and/or chlorine] or C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], R27 represents hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], cyano, formyl, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl and R28 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], amino, C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino, or R27 and R28 together represent C3-C4-alkane-diyl;
or wherein, furthermore, R2 represents the radical wherein R29 and R30 are identical or different and represent fluorine, chlorine, bromine, hydroxyl, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], C3-C5-cycloalkyl, C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine] or C1-C4-alkylthio, or represent C1-C4-alkyl-amino or di (C1-C4-alkyl)-amino;
and wherein, furthermore, R2 represents the radical wherein R31 and R32 are identical or different and represent hydrogen, methyl, or methoxy;
and wherein, furthermore, Az represents a radical from the series comprising pyrazole, imidazole and triazole, which is optionally substit-uted by chlorine, bromine, iodine, nitro, C1-C4-alkyl [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is optionally substituted by fluorine and/or chlorine], C1-C4-alkylthio [which is optionally substituted by fluorine and/or chlorine] and/or phenyl [which is optionally substituted by fluorine, chlorine, bromine, iodine, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C4-alkylthio, trifluoromethylthio, cyano, nitro or C1-C4-alkoxy-carbonyl]
or a metal salt or strong acid adduct thereof.

2. A compound, salt or adduct according to claim 1, in which R1 is R2 is or R4 is fluorine, chlorine, bromine, methyl, chloromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluor-omethoxy, methylthio, methylsulphinyl, methylsulphonyl, C1-C2-alkylaminosulphonyl, phenyl, C1-C3-alkoxycarbonyl, C3-C6-cycloalkyloxycarbonyl, difluoromethylthio, trifluoromethylthio or isopropylthio, R26 is hydrogen, methyl, hydroxyl, fluorine, chlorine, bromine, methoxy or difluoromethoxy, R27 is hydrogen, chlorine, bromine or methyl and R28 is C1-C3-alkyl, hydroxyl, fluorine, chlorine, bromine, or C1-C3-alkoxy;
R29 is fluorine, chlorine, bromine, hydroxyl, methyl, cyclopropyl, methoxy, ethoxy, methylthio or ethylthio, and R30 is fluorine, chlorine, bromine, hydroxyl, methyl, cyclopropyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino or diethylamino, and Az is a pyrazole or imidazole radical which is optionally substituted by methyl.

3. A compound, salt or adduct according to claim 1, in which R1 is wherein R4 is methoxycarbonyl, chlorine, bromine, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, propoxycarbonyl, or diethylaminosulphonyl, R2 is wherein R26 is methyl or methoxy, R27 is hydrogen, R28 is methyl or methoxy, and Az is 3,5-dimethylpyrazol-1-yl, 1-imidazolyl, or 1-pyrazolyl.

4. A metal salt of the compound according to claim 1, 2 or 3 wherein the metal is sodium, potassium or calcium.

5. An adduct of the compound according to claim 1, 2 or 3 with a strong acid, wherein the strong acid is a hydrogen halide acid, sulphuric acid, an alkanesulphonic acid which has 1 to 4 carbon atoms and is optionally substituted by fluorine or chlorine, or benzene- or naphthalenesulphonic acid which is optionally substituted by fluorine, chlorine, bromine or methyl.

6. 3,5-Dimethyl-1-[(4,6-dimethylpyrimidin-2-yl)amino-(2-methoxy-carbonylbenzenesulphonyl)iminomethyl]pyrazole of the formula or a metal salt or strong acid adduct thereof.

7. 3,5-Dimethyl-1[(4,6-dimethylpyrimidin-2-yl)amino-(2-chloro-4-methylthiobenzenesulphonyl)iminomethyl]pyrazole of the formula or a metal salt or strong acid adduct thereof.

8. 3,5-Dimethyl-1-[(4-methoxy-6-methylpyrimidin-2-yl) amino-(2-bromobenzenesulphonyl)iminomethyl]pyrazole of the formula or a metal salt or strong acid adduct thereof.

9. 1-[2-Bromobenzenesulphonylimino-(4,6-dimethylpyrim-idin-2-yl)aminomethyl]imidazole of the formula or a metal salt or strong acid adduct thereof.

10. A process for the preparation of an amidinoazole of the general formula (I) as defined in claim 1, which process comprises reacting a sulphonylguanidine derivative of the formula (II) (II) in which R1 and R2 have the meanings as defined in claim 1 and R3 represents an optionally substituted hydrocarbon radical, with a compound of the formula (III) M-Az (III) in which Az has the meaning as defined in claim 1 and M represents hydrogen or one equivalent of a metal, if appropriate in the presence of a base and in the presence of a diluent, at temperatures between 0°C and 100°C, and, where necessary, treating the product of the formula (I) thereby obtained with a metal derivative or with an acid.

11. A method of combating weeds which comprises applying to the weeds or to their habitat a herbicidally effective amount of a compound according to claim 1.

12. A method according to claim 11 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable carrier or diluent.

13. A method according to claim 12 wherein the active ingredient concentration in said composition is between 0.1 and 95% by weight.

14. A method according to claim 12 wherein the active ingredient concentration in said composition is between 0.5 and 90% by weight.

15. A method according to claim 11, 12 or 13 wherein the compound is applied as a pre-emergence herbicide.

16. A method according to claim 11, 12 or 13 wherein the compound is applied as a post-emergence herbicide.

17. A method according to claim 11, 12 or 13 wherein the compound is applied to an area of cultivation at a rate of between 0.001 and 10 kg/ha.

18. A method according to claim 11, 12 or 13 wherein the compound is applied to an area of cultivation at a rate of between 0.05 and 5 kg/ha.

19. A method according to claim 11, 12 or 13 wherein such compound is 3,5-dimethyl-1-[(4,6-dimethylpyrimidin-2-yl)amino-(2-methoxycarbonyl-benzenesulphonyl)iminomethyl]pyrazole.

20. A method according to claim 11, 12 or 13 wherein such compound is 3,5-dimethyl-1-[(4,6-dimethylpyrimidin-2-yl)amino-(2-chloro-4-methylthio-benzenesulphonyl)iminomethyl]pyrazole.

21. A method according to claim 11, 12 or 13 wherein such compound is 3,5-dimethyl-1-[(4-methoxy-6-methylpyrimidin-2-yl) amino-(2-bromobenzenesulphonyl)iminomethyl]pyrazole.

22. A method according to claim 11, 12 or 13 wherein such compound is 1-[2-bromobenzenesulphonylimino-(4,6-dimethylpyrim-idin-2-yl)amino-methyl]imidazole.