CA2060858A1 - Substituted arylsulphonylaminoguanidinotriazines - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Herbicidally active substituted arylsulphonylamino guanidinotriazines of the general formula (I) (I) in which R1 represents in each case optionally substituted aryl, aralkyl or heteroaryl, R2 represents hydroxyl, amino or in each case optionally substituted alkoxy or alkylamino, R3 represents halogen, alkyl, halogenoalkyl, alkoxyalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylamino or dialkylamino and R4 represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, alkylamino or dialkylamino, excepting the compounds N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-bromophenylsulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-Le A 28 200 phenylsulphonylamino ) -N ' ' ' - ( 2-phenyl-phenylsulphonyl ) -guanidine, N '-(4-methoxy-6-methyl-s-triazin-2-yl ) -N ' ' - ( 2-methoxycarbonyl-phenylsulphonylamino ) -N ' ' ' - ( 2 -phenyl-phenylsulphonyl)-guanidine, N ' - (4,6-dimethoxy-s-triazin-2-yl)-N''- (2-methoxycarbonyl-phenyl-sulphonylamino)-N'''-(2-methylthiophenyl sulphonyl)-guanidine and N-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-isopropoxycarbonyl-phenylsulphonyl)-guanidine, their preparation, and their use as herbicides.

Le A 28 200

Description

2~ ~ 0 ~ 3 ~

The invention relates to new substituted arylsulphonyl-aminoguanidinotriazinas, thei.r preparation, and their use as herbicides.

It has already been di~closed that certain sulphonyl-aminoguanidinoazines such asl for example, N'-(4,6-dimethyl-pyrimidin-2-yl)-N''-(4-methyl-phenylsulphonyl-amino)-N'''-(2-chloro-phenyl-sulphonyl)-guanidineandN'-(4,6-dimethyl-pyrimidin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-methoxycarbonyl-phenyl-sulphonyl)-guanidine, have herbicidal properties (cf.
EP-A 121,082 and EP-A 302,378). However, the herbicidal action of these known compounds is not -~atisfactory in all respects.

Other ~ubstituted arylsulphonylaminoguanidinoazine~ are the sub~ect of an earlier, but not prior-published patent application (cf. DE-P (German Patent Specification) 3,927,770 of 23.08.1989).

Novel sub~tituted arylsulphonylaminoguanidinotriazines of the general formula (I) Le A 28 200 - 1 -2 0 ~

H N==~
C N- ~ 3 ¦ R 2 (I) NH~==~_CO~
`NH-5O
in which Rl represent~ in each case optionally substituted aryl, aralkyl or heteroaryl, S R2 repre~ents hydroxyl, amino or in each ca~e option-ally substituted alkoxy or alkylamino, R3 represents halogen, alkyl, halogenoal~yl, alkoxy-alkyl, alkoxy, halogenoalkoxy, alkylthio, halo-genoalkylthio, alkylamino or dialkylamino and 0 R4 represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, alkylamino or dialkylamino, have now baen found, N~-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-bromophenylsulphonyl)-guanidine, N'-(4,6-dLmethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenyl~ulphonyl-amino)-N'''-(2-phenyl-phenylsulphonyl)-guanidine, N'-(4-methoxy-6-methyl-3-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-phenyl-phenylsulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-Le A 28 20Q - ~ -2 ~ } c~ ~

methoxycarbonyl-phenylsulphonyl.~mino)-N'''-(2-methylthio-phenylsulphonyl)-guanidine and N-(4,6-dimethoxy-3-tri-azin-2-yl)-N~'-(2-methoxycarborlyl-phenylsulphonylamino)-N'''-(2-isopropoxycarbonyl-phenylsulphonyl)-guanidine being excepted (cf. DE-P (Genman Patent Specification) 3,927,770 or EP Application No. 90115373.4/EP-A-0,414,067).

The general formula (I) represents the individual possible tautomers of the formulae (IA), (IB) and (IC) Rl-5O2-N~ ,NH ~ N
C N ~ 3 (I) NH ~ oR2 ~NH-5O2 ~

N ~ (IB) Rl-5O2-NH~ ~N ~ ~ N

NH ~ oR2 `NH-SO

Le A 28 200 - 3 -2a~

R -502-NH~ ,NH--~, ~N
ll R3 ( IC ) N~ ~=~C oR2 NH- 52~_~>

and mixtures of these tautomers.

The new substituted arylsulphonylaminoguanidinotriazines of the general formula (I) are obtained when (a) sulphonyl compounds of the general formula (II) H N==~
R1-SO2-N~-,N ~ ~ N (II) in which R' R3 and R4 have the abovementioned meanings and Rs represents one of the leaving groups mentioned below R6-So2-N-oR7 or -Q-Re, where Le A 28 200 - 4 -2 ~ 8 R~ has the meaning mentioned above for Rl, but need not be identical to Rl in each individual case, R7 represents alkyl, alkenyl or aralkyl, R~ represents alkyl, aralkyl or aryl and Q represents oxygen or sulphur, are reacted with sulphonylhydrazides of the qeneral formula (III) ~ oR2 (III) H2N-NH- S02~
in which R2 has the abovementioned meaning, if appropriate in the presence of a diluent, or when (b) aminoguanidinotriazines of the general formula (IV) 1 ~H, Nc=~
R -5O2-N~ ;N ~\ /N
I R3 (IV) NH
~NH 2 in which Le A 28 200 - 5 -R1 R3 and R4 have the abovementioned meanings, are reacted with sulphonyl halides of the general formula (v) oR2 X-502~ (V) in which R2 has the abovementioned meaning and X represents halogen, or with sulphobenzoic anhydride of the formula (VI) CO ' S2 ~ (VI) if appropriate in the presence of a diluent and if appropriate ln the presence of an acid acceptor, or when (c) substituted arylsulphonylaminoguanidinotriazines of ~he general formula tI), in which R2 represents Le A 28 200 - 6 -2 ~ o ~ ~

optionally substituted alkoxy and Rl, R3 and Ri have the abovementioned meanings, are reacted with aqueous alkali metal hydroxide solutions or with ammonia or with optionally sub-S stituted alkylamines, if appropriate in the presence of a diluent.

The novel substituted arylsulphonylaminoguanidinotri-azines of the general formula (I) are distinguished by powerful herbicidal activity.

The invention preferably relates to compounds of the formula (I) in which R1 repre3ents the radical ~ where R9 and R10 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6-alkyl (which is optionally ~ubstituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxycarbonyl, Cl-C4-alkylamino-carbonyl, di-(C1-C4-alkyl)-amino-carbonyl, hydroxyl, Cl-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxycarbonyl-oxy, Cl-C4-alkylaminocarbonyloxy, Cl-C4-alkyl-thio, C1-C4-alkylsulphinyl, Cl-C4-alkyl-~ulphonyl, di-(C1-C~-alkyl)aminosulphonyl, Le A 2~ 200 - 7 -2 ~

C3-C6-cycloalkyl or phenyl), or represent C2-C6-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C~-C4-alkoxycarbonyl, carboxyl or phenyl), or S represent C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C~-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent C~-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C~-C4-alkoxy-carbonyl, C~-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or C~-C4-alkylsulphonyl), or represent C~-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C~-C4-alkoxy-carbonyl, Cl-C4-alkylthio, C,-C4-alkylsulphinyl or C~-C4-alkylsulphonyl), or represent C3-C6-alkenyloxy (which i3 optionally substituted by fluorine, chlorine, bromine, cyano or C~-C4-alkoxy-carbonyl), or repre~ent C2-C6-alkenylthio (which is optionally ~ubstituted by fluorine, chlorine, bromine, cyano, nitro, C~-C3-alkylthio or C,-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(O)p-Rl1 where p represents the numbers l or 2 and Rll represents Cl-C~-alkyl (which is optionally ~ubatituted by fluorine, chlorine, Le A ?8 200 - 8 -bromine, cyano or Cl-C4-alkoxy-carbonyl), C3-C6-alkenyl, C3-C6-alkinyl, Cl-C4-alkoxy, Cl-C4-alkoxy-Cl-C4-alkylamino, C~ C4-alkyl-amino, di-(Cl-C4-alkyl)-amino or the S radical -NHORl2 where Rl2 represents C1-C12-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkyl-carbonyl, Cl-C4-alko~ycarbonyl, Cl-C4-alkylamino-carbonyl or di-(Cl-C4-alkyl)-amino-carbonyl), or repre-sents C3-C6-alkenyl (which is 1~ optionally substituted by fluorine, chlorine or bromine), or represents C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Cl-C2-alkyl,phenyl-Cl-C2-alkyl (which is optionally ~ubstituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl), or represents benzylhydryl, or repre-sents phenyl (which is optionally substituted by fluorine chlorine, nitro,cyano, C1-C4-alkyl, trifluoro-methyl, Cl-C4-alkoxy, Cl-C2-fluoro-alkoxy, Cl-C4-alkylthio, trifluoro-methylthio or C1-C4-alkoxy-carbonyl), Le A 28 200 - 9 -2 ~ v ~

Ra and R10 furthermore represent phenyl or phenoxy, or represent amino, C,-C4-alkylcarbonylamino, Cl-C4-alkoxy-carbonylamino, Cl-C4-alkylamino-carbonyl-amino, di-~C1-C4-alkyl)-amino-carbon-ylamino, or represent the radical -Co-R13 where Rl3 represents Cl-C6-alkyl, Cl-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkyl-thio, C1-C4-alkylamino, C1-C~-alkoxyamino, C1-C4-alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino (which are optionally sub-stituted by fluorine and/or chlorine), R9 and R10furthermore repre4ent C1-C4-alkylsulphonyl-oxy, di-(C1-C4-alkyl)-~minosulphonylamino, thiazolyloxy, or represent the radical -CHzN-~14 where R14 represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsul-phonyl, or represents benzyl which is optionally substituted by fluorine or chlorine, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlorine, or represents phenyl which is optionally ~ub-stituted by fluorine, chlorine, bromine, Cl-C~-alkyl, Cl-C~-alkoxy, trifluoromethyl, Le A 28 200 - 10 -2 ~

trifluoromethoxy or trifluoromethylthio, or represents C~-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine S and/or chlorine, or represents amino, Cl-C4-alkylaminoI di-(Cl-C4-alkyl)-amino, phenylamino, Cl-C4- alkyl-carbonyl-amino, Cl-C4-alkoxy-carbonylamino, Cl-C4-alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl, furthermore R1 represents the radical -CH ~ where Rl5 represents hydrogen or C1-C4-alkyl, R15 and R17 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which i8 optionally sub-stituted by fluorine andtor chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, Cl~C4-alkoxy-carbonyl, C1-C~-alkylqulphonyl or di-tCl-C~-alkyl)-aminosulphonyl; furthermore Le A 28 200 - 11 -2~ o'~

R18~Rlg Rl represents the radical where R1~ and Rl3 are identical or different and represent hydrogen, fluorine, c:hlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally sub-stituted by fluorine and/or chlorine) or C1-C4-alkoxy (which i~ optionally substituted by fluorine and/or chlorine); furthermore Rl represents the radical ~ where R20and R21 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally sub-stituted by fluorine and/or chlorine~, C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), or represent C1-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkyl-sulphonyl (which are optionally sub6tituted by fluorine and/or chlorine), and also represent di-(C1-C~-alkyl)-aminocarbonyl or C1-C4-alkoxy-carbonyl; furthermore R1 represents the radical R22 ~ 23 where Le A 28 200 - 12 -2~o~8 R22 and R23 are identical or different and reprsent hydrogen, fluorine, chlorine, bromine, Cl-C4-alkyl (which is optionally sub~tituted by fluorine and/or bromine), Cl-C4-alkoxy (which is optionally sub~tituted by fluorine and/or chlorine), or represent C1-C"-alkylthi.o, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl ~which are optionally substituted by fluorine and~or chlorine), or represent di-(C1-C4-alkyl)-aminosulphonyl;
furthermore R1 represents the radical ~ 2s where R24 and R25 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl (which is optionally substi-tuted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C~-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which i5 optionally substituted by fluorine and/or chlorine), di-(C,-C4-alkyl)-amino-sulphonyl or C~-C4-alkoxycarbonyl, and Al represents oxygen, sulphur or the group N-Zl, where zl represents hydrogen, Cl-C4-alkyl (which is Le A 28 200 - 13 -optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cyclo-alkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), Cl--C4-al~ylcarbonyl, Cl-C4-alkoxy-carbonyl or di-(Cl-C4-alkyl)-amino-carbonyl; furthermore Rl represents the radical ~ ~_N where R25 represents hydrogen, Cl-Cs-alkyl or halogen, R27 represents hydrogen or Cl-C5-alkyl and yl represents sulphur or the group N-R2a where R2B represents hydrogen or Cl-C5-alkyl, furthermore R31 Rl represents the radical ~ ~ 30 where N

l29 R2~ represent3 hydrogen, Cl-C4-alkyl, phenyl, naphthyl or (iso)quinolinyl, R30 represents hydrogen, halogen, cyano, nitro, Cl-C4-alkyl (which i~ optionally sub3tituted by Le A 28 200 - 14 -fluorine and/or chlo:rine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine) or Cl-C4-alkoxycarbonyl and R31 represents hydrogen, halogen or C1-C4-alkyl furthermore R1 represents the radical ~ 2 where R32 represents Cl-C3-alkyl and R33 represents Cl-C4-alkyl, furthermore ~

R1 represents the radical furthermore R2 represents hydroxyl, amino, or represents Cl-C4-alkoxy or C1-C4-alkylamino, each of which is option-ally substituted by fluorine, chlorine, methoxy or ethoxy, R3 represents fluorine, chlorine, bromine, Cl-C4-alkyl, Cl-C~-halogenoalkyl, Cl-C2-alkoxy-Cl-C2-alkyl, Cl-C4-alkoxy, Cl-C~-halogenoalkoxy, Cl-C4-alkylthio, Le A 28 200 - 15 Cl-C4-halogenoalkylthio, Cl-C4-alkylamino, dimethylamino or diethylamino, and R4 represents f luorine, chlorine, bromine, C,-C4-alkyl, cyclopropyl, Cl-C4-alkoxy" Cl-C4-alkylthio, C1-C4-alkylamino, dimethylamino or diethylamino, N ' - ( 4, 6-dimethoxy-s-triazin-2-yl ) -N ' ' - ( 2-methoxycarbonyl-phenylsulphonylamino ) -N ~ ~ ~ - ( 2 -bromo-phenylsulphonyl ) -guanidine, N ' - ( 4, 6-dimethoxy-s-triazin-2-yl ) -N ' ' - ( 2-methoxycarbonyl-phenyl~ulphonylamino ) -N ' ~ ~ - ( 2 -phenyl-phenylsulphonyl ) -guanidine, N ~ - ( 4-methoxy-6-methyl-s-triazin-2-yl ) -N ' ~ - ( 2-me~hoxycarbonyl-phenylsulphonyl-amino ) -N ~ ~ ' - ( 2-phenyl-phenylsulphonyl ) -guanidine, N ' -( 4, 6-dimethoxy~s-triazin-2-yl ) -N ' ' - ( 2-methoxycarbonyl-phenylsulphonylamino ) -N ~ ' ' - ( 2-methylthio-phenylsulphonyl ) -guanidine and N- ( 4, 6-dimethoxy-s-tri-azin-2 -yl ) -N ' ' ' - ( 2-methoxycarbonyl--phenylsulphonylamino ) -N ' ' ~ - ( 2-isopropoxycarbonyl phenylsulphonyl ) -guanidine being excepted (cf. DE-P (German Patent Specification) 3,927,770) .

In particular, the invention relates to compounds of the formula ( I ) in which R1 o R1 represents the radical ~ where R

R~ represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, Le A_28 200 - 16 -2 ~ t, 8 Cl-C3-alkylthio, Cl-C3-alkylsulphinyl~ Cl-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy, methoxy-S carbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, chloroethoxycarbonyl, methoxyethoxycarbonyl, n-, i- or s-butoxy-carbonyl, n-, i- or s-pentoxycarbonyl, and Rl represents hydrogen, fluorine or chlorine;
furthermore Rl represents the radical ~l ~ where RlS 6 Rl5 represents hydrogen, Rlfi represents fluorine, chlorine, bromine, methyl, methoxy, ethoxy, difluoromethoxy, trifluoro-methoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylamino~ulphonyl, and Rl7 represents hydrogen, fluorine or chlorine;
furthermore R1 repre~ent~ the radical ~~ 1l where R represents methyl or ethyl, or Le A 28 200 - 17 -~ ~ J~ 0 Ro-C ~ ~
R represents the radical N~N where c~3 R represents methyl or ethyl, R2 represents hydroxyl, amino, methoxy, ethoxy, prop-oxy, isopropoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, 2-ethoxy-ethoxy, methylamino, ethylamino, propyl-amino or isopropylamino, R3 represent~ chlorine, methyl, trifluoromethyl, methoxy, ethoxy, methylthio, e~hylthio~ methylamino, ethylamino, dimethylamino or diethylamino, and R4 represents methyl, ethyl, cyclopropyl, methoxy, ethoxy, propoxy, isopropoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethyl-amino, N'-(4,6-dimethoxy-3-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-bromo-phenylsulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N~ (2-phenyl-phenyl ulphonyl)-guanidine, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonyl-amino)-N'''-(2-phenyl-phenylsulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2 yl)-N''-(2-methoxycarbonyl-Le A ?8 200 - 18 -2 ~

phenylsulphonylamino ) -N ~ 2 -methylthio-phenylsulphonyl)-guanidine and N-(4,6-dimethoxy-s-tri-azin-2-yl)-N''-(2-methoxycarboslyl-phenylsulphonylamino)-N'''-(2-isopropoxycarbonyl-phenylsulphonyl)-guanidine S being excepted (cf. DE P (German Patent Specification) 3,q27,770) .

Very particularly preferxed compounds of the fonnula (I) are those in which thP -COR2 group is in the ortho-position to the SO2 group, and R1, R2, R3 and R4 have the meanings mentioned above as being particularly preferred, the previously mentioned compounds being excepted.

If, for example, N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-methoxy-N'',N'''-bis-(2-fluoro-phenylsulphonyl)-guanidine and 2-methoxycarbonyl-benzenesulphonylhydrazide are used as starting substances, the course of the reaction in process (a) according to the invention can be outlined by the following equation:

Le A 28 200 - 19 -5 ~

6~ N=< H2N-NH-502 <~S02-N-OCH3 ~< N=c<
---- ~ ~502-N~ ,NH--<~ ~N

-Q--502-NHocH3 NH~ OCH3 F NH- S02~) If, for example, N'-(4,6-dimethoxy-s-triazin-2-yl)-N~'-amino-N'''-(2-difluoromethoxy-phenylsulphonyl)-guanidine and 2-ethoxycarbonylbenzenesulphonyl chloride are used as starting substances, the course of the reaction in process (b) according to the invention can be outlined by the following equation:

HF2 ~ CH3 COOC2H5 Le A 28 200 20 -g ~ 8 ~ OCHF
-HCl ~ 5O2-N~ ,NH--~ ~N
¦ OCH~
NH~ r==~

Cot)c2H5 If, for example, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''~(2-methoxycarbonyl-phenylsulphonyl)-guanidine and ammonia are used as starting Rub~tances, the course of the S reaction in proce~s (c) according to the invention can be outlined by the following equation:

Le A 28 200 - 21 -COOC~3 OCH3 r - ~ N ~ ~ NH3 S02 - N~ ,NH ~ ~N >
C N ~ - HOCH3 C~
NH
NH-502 ~ ~

COOCH3 OC~3 N
C N ~
¦ CH3 N~
r--~

Formula ~II) provides a general definition of the sul-phonyl compounds to be used as starting substances in proce~s (a) according to ~he invention. In formula (II), Rl, R3 and R4 preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being pre-ferred, or particularly pref~rred, for Rl, R3 and R4, and R5 preferably represents one of the leaving groups mentioned below R6 -SO -N-oR7 2 1 or -Q-R , where Le A 2~ 200 - 22 -2 ~

R6 has the meaning mentioned above ~s being preferred for Rl, but need not be identical to R1 in each individual case, R7 represents C1-C4-alkyl, C3-C4-alkenyl or benzyl, R8 represents Cl-C4-alky:L, benzyl or phenyl and Q represents oxygen or sulphur.

In particular, R5 repre~ents the group R6 - S02 - N- oR7 ~ where R6 has the meaning given above as being particu-larly preferred for R1, but need not be identi cal to R1 in each individual case, and R7 represents methyl, or R5 represents the group _Q_R8 where R3 rspresents methyl or phenyl and Q represents oxygen or sulphur.

The starting substances of ~he formula (II) are known and/or can be prepared by processes known per se (cf.

Le A 28 200 - 23 -2 ~ ~ ~(3~ ~

EP-A 121,082, EP-A 172,957, EP-A 173,321, EP-A 173,956, EP A 224,078, EP-A 5,986 and E$'-A 24,215).

Formula (III) provides a yeneral definition of the sulphonylhydrazides further to be used as starting substances in the process according to the invention. In formula ~III), R2 preferably, or in particular, has the meaning which has already been mentioned above in connec-tion with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, for R2.

The following may be mention~d as examples of the com~
pounds of the formula (III):
2-methoxycarbonyl-,4-methoxycarbonyl-,2 ethoxycarbonyl-and 4-ethoxycarbonyl-benzenesulphonylhydrazide. ~

The starting substances of the formula (III) are known and/or can be prepared by processes known per se (cf.
Org. Synth. 40 (1960), 93 - 95; EP-A 302,378; Eqypt. J.
Pharm. Sci 22 (1981), 207-221 - cited in Chem. Abstracts 100, 191704y).

Process (a) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Preferred diluents which are suitable for this are water and/or polar organic solvents ~uch as methanol, ethanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran, Le A 28 200 - 24 -2~3~g5~

dioxane, methyl acetate, ethyl acetate, acetonitrile, propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulphoxide and tetramethyl.-ene sulphone.

When carrying out process (a) according to the invention, the reaction temperatures can be varied within a substan-tial range. In general, the process is carried out at temperatures between 0C and 150CI preferably at temper-atures between 10 DC and lOO~C.

For carrying out process (a) according to the invention, between 1 and 5 moles, preferably between 1 and 3 moles, of sulphonylhydrazide of the formula (III) are generally employed per mole of sulphonyl compound of the formula ~II).

In general, the reactants are combined at room tempera-ture or with ice-cooling, and the reaction mi~ture is stirred until the reaction i8 complete, if necessary at elevated temperature. After cooling, the products of the formula (I) are generally obtained in crystalline form and can be isolated by filtration with suction.

Formula (IV) provides a general definition of the amino-guanidinotriazines to be used as starting substances in proces~ (b) according to the invention for the prepar-ation of compounds of the formula (I).

In formula (IV), Rl, R3 and R~ preferably, or in Le A 28 200 - 25 -particular, have those meanings which have already been mentioned above in connection w:ith the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, fo~ R1, R3 and R4.

The ~tarting 6ubstances of the formula (IV) are known and/or can be prepared by processes known per se (cf.
EP-A 224,078, US-P (US Patent Specification) 4,725,303, EP-A 343,462).

The aminoguanidinotriazines of the formula (IV) are obtained when sulphonyl compounds of the general formula (II) - above - are reacted with hydrazine or a hydrazine/water adduct ("hydrazine hydrate") analogously to process (a) according to the invention, if appropriate in the presence of a diluent such as, for example, methylene chloride, methanol or ethanol, and if appropriate in the presence of a desiccant such as, for example, sodium sulphate, at temperatures between -20C
and +80C, preferably between 0C and 50C.

Formula (V) provides a general definition of the sul-phonyl halides furthermore to b~ used as starting subs~ances in process (b) according to the invention.

In formula (V), R2 preferably, or in particular, has the meaning which has already been mentioned above in connec-tion with the description of the compounds of the formula(I) according to the invention as being preferred, or Le A 28 200 - 26 -2~ 3~

particularly preferred, for R2, and X preferably repre-sents fluorine, chlorine or bromine, in particular chlorine.

Examples of the starting substances of the formula (V) which may be mentioned are:
2-methoxycarbonyl- and 2-ethoxycarbonyl- and also 4-methoxycarbonyl- and 4-ethoxycarbonyl-benzenesulphonyl chloride.

The starting substances of the formula (V) - as well as the starting compound of the formula (VI), are known and/or can be prepared by processes known per se (cf.
EP-A 173,320 and EP-A 173,321).

Process (b) according to the invention for the prepar-ation of the new compounds of the formula (I) is prefer-ably carried out using diluents. Suitable diluents forthis purpo e are virtually all inert organic solvents.
These preferably include aliphatic and aromatic, option-ally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, me~hylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chloroben7ene and o-dichlorobenzene, ethers such a~ d~ethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such a~ acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters ~uch as methyl acetate and ethyl acetate, nitriles such as, for example, Le A 28 200 - 27 -2~4~ J~

acetonitrile and propionitrile, amides such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.

Acid acceptors which can be employed in process (b) according to the invention are all acid-binding agents which can customarily be used for reactions of this type.
~he following are preferably suitable: alkali metal hydroxides such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxidel alkali metal carbon-ates and alkali metal alcoholates such as sodium carbon-ate, potassium carbonate, sodium tert-butylate and potassium tert-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diaza-bicyclo-[2,2,2]-octane (DA~CO).

When carrying out process (b) according to the invention, the reaction temperature~ can be varied within a substan-tial range. In general, the process is carried out at temperatures between -100C and +100C, preferably at temperatures between -70~C and +70C.

Process (b) according to the invention i~ generally carried out under atmospheric pressure. However, the Le A 28 200 - 28 -~ iL7' ~

process can also be carried out under increased or reduced pressure.

For carrying out process (b) according to the invention, the starting substances required in each case are gener-ally employed in approximately equimolar amounts. How-ever, it is also possible to use one of the two components employed in each case in a larger excess. The reactions are generally carried out in a suitable dilu-ent, if appropriate in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the particular temperature required. Work-up in process (b) according to the invention i8 carried out in each case by customary methods.

With the proviso that, in formula (I), R2 represents optionally substituted alkoxy, this formula provides a general definition of the substituted arylsulphonylamino-guanidinotriazines to be used as starting substances in process (c) according to the invention. In this case, Rl, R3 and R4 preferably, or in particular, have those mean-ings which have already been mentioned above in connec-tion with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, for R~, R3 and R4, and R2 prefer-ably represents C1-C4-alkoxy which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, and in particular represents methoxy, ethoxy, propoxy, i~opropoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy or 2-ethoxy-ethoxy.

Le A ?8 200 - 29 -2 ~

Tha compounds of the formula (I) to be employed as starting substances in process (c) according to the invention are new compounds according to the invention;
they can be prepared by processes ~a) or (b) according to the invention.

Aqueous alkali metal hydroxide solutions which can be employed in process (c) according to the invention are solutions of alkali metal hydroxides, such as, for example, of lithium hydroxide, sodium hydroxide or pota~sium hydroxide, in water. It i~ preferred to employ aqueou~ ~odium hydroxide solution in process (c) accord-ing to the invention.

In process (c) according to the invention, ammonia can be employed as a gas or in solution, preferably as an lS aqueous solution.

Optionally substituted alkylamines which can be employed in process (c) according to the invention are preferably alkylamines which have 1 to 4 carbon atoms and which are optionally substituted by fluorine, chlorine, methoxy or ethoxy, in particular methylamine, ethylamine, propyl-amine and isopropylamine.

If appropriate, process (c) according to the invention is carried out u~ing diluents. ~esides water and alcohols such as, for example, methanol, ethanol and isopropanol, suitable diluents are virtually all inert organic Le A 28 2~0 - 30 -2 ~

solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, hep~ane, cyclohexane, petroleum ether, benzine, ligroin, benzene, to:Luene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as, for example, acetonitrile and propionitrile, amides such as, for example, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide,tetramethylene sulphone and hexamethylpho~phoric tri-amide.

When carrying out process (c) according to the invention, the reaction temperatures can be varied within a substan-tial range. In general, the process is carried out attemperatures between 0C and 120C, preferably at tempe-ratures between 20C and 100C.

Process (c) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.

To carry out process (c) according to the invention, Le A 28 200 - 31 -2 ~ 8 between 1 and 10 moles, preferably between 1 and 5 moles, of al~ali metal hydroxide, ammonia or amine are generally employed per mole of starting compound of the formula (I).

In general, the starting compo~lnd of the formula (I) is introduced first, at room temperature, if appropriate in a diluent, and the aqueous alkali metal hydroxide solu-tion, the ammonia or the amine is then metered in, if appropriate at increased temperature. The reac~ion mixture is stirred until the reaction is complete and worked up by customary methods (cf. the Preparation Examples).

The active compounds according to the invention can be used as defolian~s, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are unde-sired. Whether the substances according to the invention 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 following plants:

Dicotyledon weeds o~ the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, PoEtulaca, Le A 28 200 - 32 -Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lind~rn:ia, Lamium, V~eronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

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

~onocotyledon weeds of the qenera: Echinochloa, Setaria~
Panicum, ~igitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

~onocotyledon cultures of_ the genera: Ory~a, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Anana~, A~paragus and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the ~ame manner to other plants.

The compounds are suitable, depending on the concentra-tion, 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 Le A 28 200 - 33 -2 ~

compounds can be employed for combating weeds in peren-nial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea S plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture land, and for the selective combating of weeds in annual cultures.

The compounds of the formula (I) according to the inven-tion are particularly suitable for selectively combating dicotyledon weeds in monocotyledon cultures, both by the pre-emerg~nce and the post-emergence method.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concen-trates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsify-ing agents and/or dispersing agent~ and/or foam-forming agents.

In the case of the use of water as an extender, organic Le A 28 200 - 34 -2 ~

solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are ~uitable in the main: aroma~ics, such as xyl.ene, ~oluene, or alkyl-naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such a~ cyclohexane or paraffins, for example petroleum fractions~ mineral and vegetable oils, alcohols, such as butanol or glycol as well 2S their ethers and esters, ketones, ~uch as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol-vents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammon-ium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, ~uch as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granule~ of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene iatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as Le A 28 200 - 35 -2 ~ S 8 well as albumen hydrolysis products; as dispersing agents the following 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 latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, 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 inorganic pig-ments, 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,manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 p~r cent by weight of active compound, preferably between 0.5 and 90~.

For combating weeds, the active compounds according to the invention, as such or in the form of their formula-tions, can also be used as mixtures with known herbi-cides, finished formulations or tank mixes being pos-8 ible.

Suitable herbicides for the mixtures are known Le A 28 200 - 36 -2 ~

herbicides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethyl-urea (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet, and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soya beans;
furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D);

4-(2,4-dichlorophenoxy)-bu~yric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BENTAZONE);
methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate(BIFENOX);
3,5-dibromo~4-hydroxy-benzonitrile (BROMOXYNIL); 2-chloro-N{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}bsnzenesulphonamide (CHLORSULFURON); N,N-di-methyl-N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON);
2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl eqter or its ethyl ester (FENOXAPROP);
[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its l-methylheptyl e~ter (FLUROXYPYR); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-lH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ);
3,5-diiodo-4-hydroxyben20nitrile (IOXYNIL); N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON);
(2-methyl-4-chlorophenoxy)-acetic acid (MCPA);
(4-chloro-2-methylphenoxy)-propionic acid (MCPP);

Le ~ 28 200 - 37 -20~a~8 N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFEN-ACET); 2-{[~((4-methoxy-6-methyl1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic acid or its methyl ester (METSULFURON); N-(1-ethylpropyl)-3,4-di-S methyl-2,6-dinitroaniline (PENDIMETHALIN); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE);
methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl~-amino]-sulphonyl]-thiophene-2-carboxylate (THIAMETURON); 5-2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate. Surpri~ingly, some mixturesalso show synergistic action.

A mixture with other known active compounds, such as fungicides, insecticide~, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is 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 solutions, suspensions, emulsions, powders, pastes and granules.
They are used in the customary manner, for example by watering, spraying, atomizing or ~cattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.

They can al~o be incorporated into the soil before sowing.

Le A 28 200 - 38 -2 ~ 8 The amount of active compound used can vary within a substantial range. It depends lessentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, preferably between 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.

Preparation ExamPles:

Example 1 COOC2H5 CH~
SO2-NH~ ~N-~ ~ N
¦ OCH3 NH

(Process (b)) A mixture of 7.5 g (18.3 mmol) of N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N''-amino-N'''-(2-ethoxycarbonylphenyl-sulphonyl~-guanidine, 2.28 g (20.3 mmol) of diazabicyclo-[2,2,2]-oct~ne (DABCO) and 100 ml of methylene chloride i cooled to -70C, and a solution of 4.53 g (18.3 mmol) of 2-ethoxycarbonyl-benzenesulphonyl chloride in 20 ml of methylene chloride is added dropwise with stirring to Le A 28 200 - 39 -this mixture. Afker the cooling bath has been removed, the reaction mixture is stirred for a further lS hours (at the end at 20C). It is then diluted with 100 ml of methylene chloride and washed twice with approx. 200 ml of water each time. The organic phasP i5 dried with magnesium sulphate and filterecl. The solvent is removed from the filtrate by distillation under a waterpump vacuum, the residue is brought to crystallisation with ethyl acetate, and the crystalline product is isolated by filtration with suction.

6.3 g of a first fraction of N'-(4-methoxy-6-methyl-s-tria~in-2-yl)-N''-(2-ethoxycarbonyl-phenylsulphonyl-amino)-N'''-(2-ethoxycarbonyl-phenylsulphonyl)-guanidine are obtained. The mother liquor is concentrated, and the residue which remains here is recrystallised using ethanol, during which process a second product fraction is obtained (1.55 g). Total yield: 7.85 g (69 % of theory); melting point: 165C.

Other examples of the compounds which can be prepared analogously to Example 1 and following the general description of the preparation process according to the invention are those of the formula (I) listed in Table 1 below.

C N ~ (I~
NH r~ COR2 ~NH-SO

Le A 28 200 - 40 -~ !
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Startinq compounds of the formula (IV!:

Exam~le (IV-ll N ~
5O2-NH-C=N-~\ ~ N
NH~ CH3 ~H2 A mixture of 6.5 g (15.3 mmol) of N'-(4-methoxy-6-methyl~
s-triazin-2-yl)-N''-(2-ethoxycarbonylphenylsulphonyl)-S-methyl-isothiourea, 0.77 g (15.3 mmol) of hydrazine hydrate and 150 ml of methylene chloride is stirred for 30 minutes at 20C and then stirred with magnesium sulphate and silica gel, and subjected to filtration with suction. The filtrate is concentrated, the residue is stirred with diethyl ether, and the product which is obtained in crystalline form is isolated by filtration with suction.
4.9 g (78 ~ of theory) of N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N''-amino-N'''-(2-ethoxycarbonyl-phenylsulphonyl)-guanidine of melting point 141C are obtained.

Le A 28 200 Use Exam~es:

Example A

Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of active compound. It is expedient here to keep constant the amount of water per unit area. The active compound concentration in the preparation is of no importance, only the amount of active compound applied per unit being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison with the development of the untreated control. The figures denote:

0 % = no action (like untreated control) lO0 % = total destxuction In this test, a powerful action against weeds combined with good tolerance by wheat is shown, for example, by the compounds of the Preparation Examples l, 4, 5, 6 and 7.

Le A 28 200 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 of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a way 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 1,000 l of water/ha.
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:
0% = no action (like untreated control) 100% = total destruction In this test, a powerful action against weeds combined with good tolerance by wheat is shown, for example, by the compounds of the Preparation Examples l, 4, 5, 6 and 7.

Le A 28 200 - 116 -

Claims (21)

1. Substituted arylsulphonylaminoguanidinotriazines of the general formula (I) (I) in which R1 represents in esch case optionally substituted aryl, aralkyl or heteroaryl, R2 represents hydroxyl, amino or in each case optionally substituted alkoxy or alkylamino, R3 represents halogen, alkyl, halogenoalkyl, alkoxyalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylamino or dialkylamino and R4 represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, alkylamino or dialkylamino, Le A 28 200 excepting the compounds N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-bromophenyl-sulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-phenylphenyl-sulphonyl)-guanidine, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-phenylphenyl-sulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-methylthio-phenylsulphonyl)-guanidine and N-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-methoxycarbonyl-phenylsulphonylamino)-N'''-(2-isopropoxy-carbonyl-phenylsulphonyl)-guanidine.

2. A compound according to claim 1 wherein R1 represents the radical where R9 and R10 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6-alkyl (which is optionally substituted by fluorine, chlor-ine, bromine, cyano, carboxyl, C1-C4-alkoxycarbonyl, C1-C4-alkylamino-carbonyl, di-(C1-C4-alkyl)-aminocarbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylaminocarbonyloxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, di-(C1-C4-alkyl) aminosulphonyl, C3-C6-cycloalkyl or phenyl), or represent C2-C6-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxycarbonyl, carboxyl or phenyl), or represent C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, car-boxyl or phenyl), or represent C1-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), or represent C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), or represent C3-C6-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), or represent C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxy-carbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(O)p-R11 where p represents the numbers 1 or 2 and R11 represents C1-C4-alkyl (which is optionally sub-stituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkylamino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino or the radical -NHOR12 where R12 represents C1-C12-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1 C4-alkylsulphonyl, C1-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylamino-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl), or represents C3-C6-alkenyl (which is optionally substituted by fluorine, chlorine or bromine), or represents C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl), or represents benzylhydryl, or represents phenyl (which is optionally sub-stituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, tri-fluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C4-alkylthio, trifluoromethylthio or C1-C4-alkoxy-carbonyl), R9 and R10 furthermore represent phenyl or phenoxy, or represent amino, C1-C4-alkylcarbonylamino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylaminocarbonylamino, di-(C1-C4-alkyl)-amino-carbonylamino, or represent the radical -CO-R13 where R13 represents C1-C 6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, 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), R9 and R10 furthermore represent C1-C4-alkylsulphonyl-oxy, di-(C1-C4-alkyl)-aminosulphonylamino, thiazolyloxy, or represent the radical -CH=N-R14 where R14 represents C1-C6-alkyl which is optionally sub-stituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, or represents benzyl which is optionally substituted by fluorine or chlorine, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlorine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C1-C6-alkoxy, C3-C6 alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is 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-alkoxy-carbonyl-amino, C1-C4-alkylsulphonylamino, or represents phenylsulphonyl-amino which is optionally substituted by fluorine, chlorine, bromine or methyl, furthermore R1 represents the radical where R15 represents hydrogen or C1-C4-alkyl, R16 and R17 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; furthermore R1 represents the radical where R18 and R19 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); furthermore R1 represents the radical where R20 and R21 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), or represent C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), and also represent di-(C1-C4-alkyl)-aminocar-bonyl or C1-C4-alkoxy-carbonyl; furthermore R1 represents the radical where R22 and R 3 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which is optionally substituted by fluorine and/or bromine), 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;
furthermore R1 represents the radical where R24 and R25 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-alkyl-sulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C1-C4-alkyl)-aminosulphonyl or C1-C4-alkoxy-carbonyl, and A1 represents oxygen, sulphur or the group N-Z1, where Z1 represents hydrogen, C1-C4-alkyl (which is optional-ly substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C1-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl; further-more R1 represents the radical where R26 represents hydrogen, C1-C5-alkyl or halogen, R27 represents hydrogen or C1-C5-alkyl and Y1 represents sulphur or the group N-R28 where R28 represents hydrogen or C1-C5-alkyl, furthermore R1 represents the radical where R29 represents hydrogen, C1-C4-alkyl, phenyl, naphthyl or (iso)quinolinyl, R30 represents hydrogen, halogen, 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) or C1-C4-alkoxycarbonyl and R31 represents hydrogen, halogen or C1-C4-alkyl furthermore R1 represents the radical where R32 represents C1-C3-alkyl and R33 represents C1-C4-alkyl, furthermore R1 represents the radical furthermore R2 represents hydroxyl, amino, or represents C1-C4-alkoxy or C1-C4-alkylamino, each of which is optionally sub-stituted by fluorine, chlorine, methoxy or ethoxy, R3 represents fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4-halogenoalkylthio, C1-C4-alkylamino, dimethylamino or diethylamino, and R4 represents fluorine, chlorine, bromine, C1-C4-alkyl, cyclopropyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino, dimethylamino or diethylamino.

3. A compound according to claim 1, wherein R1 represents the radical where R9 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C1-C3-alkylthio, C1-C3-alkylsulphinyl, C1-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methyl-aminosulphonyl, phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, chloroethoxycarbonyl, methoxyethoxycarbonyl, n-, i- or s-butoxycarbonyl, n-, i- or s-pentoxycarbonyl, and R10 represents hydrogen, fluorine or chlorine;
furthermore R1 represents the radical where R15 represents hydrogen, R16 represents fluorine, chlorine, bromine, methyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxy-carbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosul-phonyl, and R17 represents hydrogen, fluorine or chlorine, furthermore R1 represents the radical where R represents methyl or ethyl, or R1 represents the radical where R represents methyl or ethyl, R2 represents hydroxyl, amino, methoxy, ethoxy, prop-oxy, isopropoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, 2-ethoxy-ethoxy, methylamino, ethylamino, propylamino or isopropylamino, R3 represents chlorine, methyl, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino, and R4 represents methyl, ethyl, cyclopropyl, methoxy, ethoxy, propoxy, isopropoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino.

4. A compound according to claim 3 wherein the -COR2 group is in the ortho-position to the SO2 group.

5. The compound N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N''-(2-ethoxycarbonyl-phenylsulphonylamino)-N'''-(2-ethoxycar-bonyl-phenylsulphonyl)-guanidine of the formula

6. A compound according to claim 1 wherein -COR2 is -(2-)COOCH3, R4 is -OCH3, R1 is and R3 is -CH3.

7. A compound according to claim 1 wherein -COR2 is -(2-)COOCH3, R4 is -OCH3, R1 is and R3 is -OCH3.

8. A compound according to claim 1 wherein -COR2 is -(2-)COOCH3, R4 is -OCH3, R1 is and R3 is -OCH3.

9. A compound according to claim 1 wherein -COR2 is -(2-)COOCH3, R4 is -OCH3, R1 is and R3 is -CH3.

10. A herblcidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.

11. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 9 in admixture with a solid diluent or carrier, a liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.

12. A method of combating weeds which comprises applying to the weeds, or to a hahitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9.

13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.

14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.

15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90% by weight of a compound according to any one of claims 1 to 9 in admixture with a suitable carrier or diluent.

16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied as a pre-emergence herbicide.

17. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied as a post-emergence herbicide.

18. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied to an area of cultivation at a rate of between 0.01 and 10 kg/ha.

19. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 9 wherein the compound is applied to an area of cultivation at a rate of between 0.05 and 5 kg/ha.

20. A process for preparing a substituted arylsulphonyl-aminoguanidinotriazine of the formula (I) as defined in Claim 1, wherein R1, R2, R3 and R4 are as defined in Claim 1, which process comprises (a) reacting a sulphonyl compound of the general formula (II) (II) in which R1, R3 and R4 have the ahovementioned meanings and R5 represents one of the leaving groups mentioned below or -Q-R8, where R6 has the meaning mentioned above for R1, but need not be identical to R1 in each individual case, R7 represents alkyl, alkenyl or aralkyl, R8 represents alkyl, aralkyl or aryl and Q represents oxygen or sulphur, with a sulphonylhydrazide of the general formula (III) (III) in which R2 has the abovementioned meaning, or (b) reacting an aminoguanidinotriazine of the general formula (IV) (IV) in which R1, R3 and R4 have the abovementioned meanings, with a sulphonyl halide of the general formula (V) (V) in which R2 has the abovementioned meaning and X represents halogen, or with sulphobenzoic anhydride of the formula (VI) (VI) or (c) reacting a substituted arylsulphonylaminoguani-dinotriazine of the general formula (I), in which R2 represents optionally substituted alkoxy and R1, R3 and R4 have the above-mentioned meanings, with an aqueous alkali metal hydroxide solution or with ammonia or with an optionally substituted alkylamine.

21. A process for preparing a herbicidal composition which comprises admixing a compound according to any one of claims 1 to 9 with a diluent, carrier or surface active agent.