CA2027206C

CA2027206C - Sulphonylaminocarbonyltriazolinones

Info

Publication number: CA2027206C
Application number: CA002027206A
Authority: CA
Inventors: Klaus-Helmut Muller; Peter Babczinski; Hans-Joachim Santel; Robert R. Schmidt
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1989-10-12
Filing date: 1990-10-10
Publication date: 1997-12-23
Anticipated expiration: 2010-10-10
Also published as: HUT55369A; KR910007893A; EP0422469A3; EP0683157A1; CZ281525B6; DK0683157T3; DE3934081A1; EP0683157B1; CA2420329A1; CA2420329C; EP0422469B1; PL165494B1; CA2189698A1; ES2222457T3; BR9005095A; EP0422469A2; CA2027206A1; SK280209B6; HU906419D0; AU6459190A

Abstract

Sulphonylaminocarbonyltriazolinones of the general formula (I) (see fig. I) in which R1 represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents an optionally substituted radical from the series comprising alkyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and dialkylamino, and R3 represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula (I) and novel intermediates of the formula (IIa).

(see fig. IIa)

Description

3 iJ

The invention relates to new sulphonylamino-carbonyltriazolinones, to several processes for their preparation, and to their use as herbicide~.
It is known that certain substituted amino-carbonylimidazolinones, such as, fox example, 1-isobutyl~
aminocarbonyl-2-imidazolidinone (isocarbamide), have herbicidal properties (cf. R~ Wegler, Chemie der Pflan~enschutz-undSchadlingsbekampfungsmittel[Chemistry of Plant Protection Agents and Pesticides], Vol~ 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New York, 1977). However, the action of this compound is not satisfactory in all respects. The new sulphonylamino-carbonyl-t~iazolinones of the general formula (I) R3-So2-NH-Co-N ~ N-R1 (I) N=~R 2 in which~5 R1 repres~nts hydrogen, hydroxyl or amino, or repre-sents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cyclo-alk~l, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino,~0 R2 represents hydrogen, hydro~yl, mercapto or amino, or represents an optionally substituted radical from the series comprising alkyl, cycloalkyl, Le A 27 154 - 1 -cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and dialXylamino, and R3 represents an optionally substituted radi~al from the series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula ~I), have now been found.
The new sulphonylaminocarbonyltriazolinones of the general formula (I) are obtained when a) triazolinones of the general formula (II) Hl ~ N-R1 (II) N~R2 in which R1 and R2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the qeneral formula (III) R3-So2-N=C=o (III) in which R3 has the abovementioned ~n; ~g, if appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) Le A 27 154 - 2 -3 ~
o Z-CO-N ~ N-R1 (IV) ~R2 in which Rl and R2 have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphon~mides of ~he general S formula (V) R3-So2-NH2 (V) in which R3 has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or when c~ triazolinones of the general formula (II) o HN ~ N-R
~R2 in which R1 and R2 have the abovementioned meanings Le A 27 154 _ 3 _ ~ ~3 2 ~

are reacted with sulphonamide derivatives of the general formula (VI) R3-So2-NH-Co-Z ~VI) in which R3 has the abo~. ?ntioned -~n i ng and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the pre~ence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, salt~ are formed by customary methods from the compounds of the formula (I) prepared by process ~a), tb) or (c).
The new sulphonylaminocarbonyltriazolinones of the general formula (I) and their salts are distinguished by a powerful herbicidal activity. Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than the known herbicide l-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), which has a similar structure.
The invention preferably relates tG compounds of the formula (I) in which R1 represents hydxogen, hydroxyl or amino, or repre-sents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, C1-C4-alkylcarbonyl or Cl-C4-alkoxy-carbonyl, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine, chlor-ine and~or bromine, or represents C3-C6-cycloalkyl which i~ optionally substituted by fluorine, Le A 27 154 - 4 -chlorine, bl~- inQ and/or C1-C4-alkyl, or represents phenyl-Cl-C3-alkyl which is optionally substituted by fluorine, chlorine, bl~ ; ne~ cyano, nitro, C1-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy and~or Cl-C4-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bL~ in~ cyano, nitro, Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy, fluorine- and/or chlorine-substituted Cl-C3-alkoxy, Cl-C4-alkylthio, fluorine and/or chlorine-substituted Cl-C3-alkylthio, Cl-C4-alkylsul-phinyl~ Cl-C4-alkylsulphonyl and/or Cl-C4-alkoxy-carbonyl, or represents C1-C~-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, phenyl, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl, or rep.resents C3-C4-alkenyloxy, or represents Cl-C4-alkylamino which is optionally substituted by fluorine, cyano, Cl-C4-alkoxy or Cl-C4-alkoxy-car~
bonyl, or represents di-(Cl-C4-alkyl)-amino, R~ represents hydrogen, hydroxyl, mercapto or amino, ox represents Cl-C6-alkyl which is optionally ~ubstitut-ed by fluorine, chlorine, bromine, cyano, C3-C6-cycloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl, or xepresents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C4-alkyl, or represents cyclohexenyl, or repre-sents phenyl-Cl-C3-alkyl which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, nitro, Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or C1-C4-alkoxy carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, Le A 27 154 - 5 -2 ~ ~

bromine, cyano, nitro, Cl-C4-alkyl, trifluoromethyll Cl-C4-alkoxy, fluorine- and/or chlorine-substituted Cl-C3~alkoxy, Cl-C4-alkylthio, fluorine- and/or chlorine-substituted Cl-C3-alkylthio, Cl-C4-alkyl-sulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-alko~y-carbonyl, or represents Cl-C8-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, Cl-C4-alkoxy or Cl-C4-alkoxy-carbonyl, or represents Cl-C4-alkylamino or di-(Cl-C4-alkyl)-amino, and R3 represents the group ~ R5 , where ~4 and R5 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, Cl-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, Cl-C4-alkoxycarbonyl, Cl-C4-alkylamino~carbonyl, di-(Cl-C4-alkyl)amino-carbonyl, hydroxyl, Cl-C4-alkoxy, formyloxy, Cl-C4-alkyl-carbonyloxy, Cl-C4-alkoxy-carbonyloxy, Cl-C4-alkylamino-carbonyloxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, di-(Cl-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl), or represent C2-C6-alkenyl (which is option-ally substituted by fluorine, chlorine, bromine, cyano, Cl-C4 alkoxy-carbonyl, carboxyl or phenyl), or represent C2 C6-alkinyl ~which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent Le A 27 154 - 6 -~ ~q ~ i J ~J ~3 C1-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bl~- ine~ cyano, carboxyl, Cl-C~-alkoxy-carbonyl, Cl-C4-alkoxy, C1-C4-alkylthio, Cl-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), or represent C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, b~l ine, cyano, carboxyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl), or represent C3-C6~alkenyl-oxy (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, b~l- ine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the radical -S(O)p-R6 where p represents the numbers 1 or 2 and R6 represents Cl-C4-alkyl (which is optionally substituted by ~luorine, chlorine, bl~- ine, cyano or Cl-C4-alkoxy-carbonyl)~ C3-C6-alkenyl, C3-C6-alkinyl, Cl-C4~alkoxy, Cl-C4-alkoxy-Cl-C4-alkyl-amino, Cl-C4-alkylamino, di-(Cl-C4-alkyl)-amino or phenyl~ or represents the radical -NHoR7 where R7 represents C1-C12-alkyl (which is optionally substituted by fluorine, chlorine, cyano, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsul-phinyl, Cl-C4-alkylsulphonyl, Cl-C4 alkyl-carbonyl, C1-C4-alkoxycarbonyl, C1-C4-alkyl-amino-carbonyl or di-(Cl-C4 alkyl)-amino-carbonyl), or represents C3-C6-alkenyl (which is option lly substituted by fluorine, Le A 27 154 - 7 -2~

chlorine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Cl-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substi-tuked by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkoxy car-bonyl), or represents benzohydryl, or repre-sents phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C1~C4-alkyl, trifluoromethyl, Cl-C4-alkoxy, Cl-C2-fluoroalkoxy, Cl-C4-alkylthio, trifluol~.. eLhyl-thio or Cl-C4-alkoxycarbonyl), R4 and/or R5 furt.he. -re represent phenyl or phenoxy, or represent Cl-C4-alkylcarbonylamino, Cl-C4-alkoxycarbonylamino, Cl-C4-alkylamino-carbonyl-amino, di-(Cl-C4-alkyl)amino-caxbonylamino, or repre~ent the radical -CO-R8, where R~ represents Cl-C6-alkyl, C1-C6 alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, Cl-C4 alkylthio, Cl-C4-alkylamino, Cl-C4-alkoxyamino, Cl-C4-alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl~-amino (each of which is optionally substituted by fluorine and/or chlorine), R4 and/or Rs furthe ~re represent trimethylsilyl, thiazolinyl, Cl-C4-alkylsulphonyloxy, di-(Cl-C4-alkyl)-aminosulphonylamino, or represent the radical -CH=N-R9, where R9 represents Cl-C6-alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, Cl-C4-alkoxy, C1-C4-alkylthio~ C1-C4 alkylsulphinyl or Cl-C4-alkylsulphonyl, or Le A 27 154 - 8 -~ ~ 2 7 J ~3 ç~

represents ben~yl which is optionally substi-tuted by fluorine or chlorine, or xepresents C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlox-ine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, Cl-C4-alkyl, Cl-C4-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents Cl-C6-alkoxy, C3-C6-alkenoxy, C3-C6-Alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, C~-C4-alkyl-amino, di-(Cl-C4-alkyl)-amino, phenylamino, Cl-C"-alkyl-carbonyl-amino, C,-C4-alkoxy-car-bonylamino or C,-C4-alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally substituted by fluorin~, chlorine, bromine or methyl, furthe -re R3 represents the radical -I ~ , where Rl~ represents hydrogen or Cl-C4-al~yl, R'1 and R12 are identical or different and represent hydro~en, fluorine, chlorine, bromine, nitro, cyano, C,-C4-alkyl (which is optionally ~ubstitut-ed by ftuorine and/or chlorine), Cl~C4-alko~y (which is optionally substituted by fluorine and~orchlorine), carboxyl, C1-C4-alkoxy-carbonyl, 1e A 27 154 ~ 9 -~ ~ ~;J ~ fJ 13 .3 dimethylaminocarbonyl,Cl-C4-alkylsulphonyl or di-( C1-C4-a1kY1 )-aminosulphonyl;
furthermore R3 represents the radical R13 ~ R14, where Rl3 and Rl4 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substitut-ed by fluorine and/or chlorine) or C~-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine);
furthermore R3 represents the radical ~ , where Rl5 and Rl~ are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl C4-alkyl (which is optionally substitut~
ed by fluorine and/or chlorine~/ C~-C4-alkoxy (which is optionally substitu~ed hy fluorine and/or chlorine), or represent Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl teach of which is optionally subs~ituted by fluorine and/or chlorine), or r~present di-(Cl-C4-alkyl)-aminosulphonyl or Cl-C4-alko~y-carbonyl or ~i-methyl~minocarbonyl;

Le A 27 154 - 10 -~ 33 2 ~ ~ J li furthermore R3 represents the radical R17 ~ R1~ , where R17 and R18 are identical or different and represent hydrogen, fluorine, chlorine, bL~ ine, Cl-C4-alkyl (which is op~ionally substituted by fluorine and/or bromine), Cl-C4-alkoxy ~which is optionally substi~
tuted by fluorine and/or chlorine), or repre~ent Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl C~-alkyl-sulphonyl (each of which is optionally substituted lQ by fluorine and/or rhlorine), or represent di-(Cl-C4-alkyl)-aminosulphonyl;
furthermore R3 represents the radical ~ R20 ' where A

Rl9 and R20 ar~ identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, Cl-C4-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), Cl-C4-alko~y (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkylthio, C1-C4-alkylsul-phinyl or C~-C4-alkylsulphonyl (which is optional-ly substituted by fluorine and/or chlorine), di-(Cl-C4-alkyl)-~mino-sulphonyl, C1-C4-aIkoxy-car-bonyl or dimethylaminocarbonyl, and A repr~sents oxygen, sulphur or the group N-2~, Le A 27 154 '3 ~

where Z1 represents hydrogen, C1-C4-alkyl (which is optionally s~bstituted by fluorine, chlorine, bLr ine or cyano), C3-C~-cycloalkyl, ben~yl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C1-C4-alkylcarbonyl, Cl-C4-alko~y-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl;
furthermore R3 represents the radical ~ R22 ' where R21 and R22 are identical or different and represent hydrogen, Cl-C4-alkyl, halogen, Cl-C4-alkoxy-carbonyl, Cl-C4-alkoxy or Cl-C4-halogenoalkoxy, Y~ represents sulphur or the group N-R23, where R23 represents hydrogen or Cl-C4-alkyl;
furtherrore R3 represents the radical ~ , where N' ¦ R2 5 R24 represents hydrogen, C1-C4-alkyl, benzyl, quinolinyl or phenyl, R25 represents hydrogen, halogen, cyano, nitro, Cl-C4-al~yl (which is optionally substituted by Le A 27 154 - 12 -~ ~r~ r, fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxol~nyl or Cl-C4-alkoxy-carbonyl, and R26 represents hydrogen, halogen or C1-C4-alkyl;
furthermore R3 represents one of th~ groups listed below, H3CO~ H3C~
S'N- C4H9 ; N~S~OCH2CF3 ~2 ~0 The invencion furthermore preferably relates to the sodium, potassium, magnesium, calcium, ammonium, Cl-C4-alkylammonium, di-tC1-C4-alkyl)-~mmonium, tri-(Cl-C4-al~yl~-ammonium, Cs~ or C6-cycloalkyl-ammonium and di-(Cl-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I~ in which R1, R2 and R3 have the meanings mentioned above as being preferred.
In particular, the invention relates to compounds of the formula (I) in which Rl represents hydrogen, or represents Cl-C~-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, methoxy or e~hoxy, or represents allyl, or represents C3-C6-cycloalkyl, or repre-~e A 27 154 - 13 -sents phenyl, or represents benzyl, or represents Cl-C3-alkoxy, or represents Cl-C3-alkylamino, or represents di-(Cl-C2-alkyl)-amino.
R2 represents hydrogen, or represents Cl-C4-alkyl which is optionally substituted by fluorine and/or chlor-ine or by methoxy or ethoxy, or represents C3-C6-cycloalkyl, or represents phenyl, or represents Cl-C3-alkoxy, or represents Cl-C3-alkylamino, or represents di-(Cl-C2-alkyl)-amino, and R3 represents the group ~ R5 ' where R4 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, Cl-C3-alkylthio, Cl-C3-alkylsulphinyl, Cl-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylamino-sulphonyl, phenyl, phenoxy or C~-C3-alkoxy-car-bonyl, and R5 represents hydrogen, fluorine, chlorine or bromine;
furthermore Rl 1 R3 represents the radical -cH ~ R12 ' where R10 repre~ents hydrogen, Le A 27 154 - 14 3 ;3 -represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and R12 represents hydrogen;
furthermore R3 represents the radical F~O- C S
o where R represents Cl-C4-alkyl, or represents the radical RO
-C~
N~M

where R represents C,-C4-alkyl.
Examples of the compounds according to the invention are listed in Table 1 below - cf. also the Preparation Examples.

Le A 27 154 - 15 -~ '~ 2 ~ 2 ~) , R3-So2-NH-CO-NJ~N-Rl I~R2 ( I ) Table 1: Examples of the colr.pounds oî the formula ~ I ) H

~\ H <~

OC~3 CH2-CH=CH2 C2H5 <~H2 OCH ~ C3H7 ~Hz-~\ ~
O-C~2-CH=CH2 S OOCH3 C2H5 C4Hg-n ~

I,e A 27 154 ~ 16 Table 1 - continuation So2NwocH3 ~H3 C3H7 ~

p C3H7 ~ ZN(CH3~2 CH3 C2H5 Cl Br C2H5 C3H7 ~

OC2H5 e~
OC3H7 CH3 ~ COOCH3 CH3 C3H7 ~COOCH3 COOCH
N(CH3~2 CH2 <~CH23 Le A ~7 154 - 17 -i) 2 r~ ~

Table 1 - continuation NH-CH3 ~ H2_ ~zCHO

OCH3 ~

C~L OCzH5 CH2~> CH2~

~ OCF3 C3H7 ~ N ~

CH3 C H5 CH30 ~ S~N-C4~s Le A 27 154 - 18 -~, ~,.

Table 1 - continuation R 1 R2 E~3 ~CON(CH3)2 CH3 C4H9 ~

~CON(CH3)2 C3~7 CH3 C3H7 ~3 C2~5 C2H5 C3H7 5~2~
OCH;2 ~ CH2 - C 1 C2}15 C2H5 ~

~<
CH3 C3H7~n <~

C3H7~

Le A 27 154 - 19 -~27~1J 3)~

Table 1 - continuation CH3 (~
oc~3 CH3 C4Hg ~CH2-CH3 ~ ~2-C2H5 ~ ~2 C3H7 C3H7 ~ Hz-CN
CH3 CH(CH3)2 ~ H2_ ~COOC2H5 ~\ N'N--Nl~

Le A 27 lS4 - 20 -2 ~3 ,C~

Table 1 - continuation ~COOC2H5 N'7 OCH3 C2H5 G~N

COOCH ( CH3 ) 2 ~C2~5 C2H5 Cl ~CF3 CH3 CH3 I~NJ~
l~r CH3 C2H5 N~N~

/\ /~ ~ ,N~H3 Cl ~CON(CH3)2 CH3 CH(CH~)2 ~ H2 Le A 27 154 - 21 -Table l - continuation Rl R2 R3 Br OCH2-CH=CH2 C2H5 CH3~

,CH3 S~2 ~ N~
OCH3 C2H5 ~ OCH3 Br CH3 CH ( CH3 ) 2 ~

CH3 CH2-CH=CH2 <~

CH3 CH2-O-CH3 ~
SCHtCH3)2 CH3 CH2-O-c2H5 ~

C2H5 C2H4-0-CH3 ~

~ CON~CH3)2 CH~ - CH = CH2 H ~J~

Le A 27 154 - 22 -f~ I

~able 1 - continuation Rl R2 R3 CH2-CH=CH2 CH~ ~

~ r CH2-CH=CH2 C2H5 N~N~
c~3 ~ [~
~2H5 S~A~COOCH3 CH3 C3H? ~

NH-CH3 C2~5 Cl NH-CH3 ~ H2_ Si(CH3~3 CH3 C3H7 ~

ON(CH3)2 C2H5 Cl Le A 27 154 - 23 ~3~ ~f~,~J~

q~able 1 - continuation E~ 1 RZ E~

~CON ( CH 3 ) 2 CH3~
CH3 C3H7 N'S~OCH2-CF3 ~\ ~0 C 2H s N~7~

CH3 ~ N S3 ~3 C2H5 ~

OCH3 CH ( CH3 ) 2 ~CH2-~C2HS C2H5 ~
~CF3 ~J ~ J ~ ~

Table 1 - continuation CH3 C2H5 e~

O SOzCH3 OCH3 ~ ~

SO~CH3 OCH3 H ~

c~3 C2H5 ~~
Br CH2-CH=CH2 CH2-0-CH3 ~e A 27 154 - 25 -Table 1 - continuation Rl R2 R3 N(C113)2 N(CH3)2 ~

If, for example, 2,6-difluorophenyl isocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (a) according to the invention can be outlined by the following equation:

o ~S ~2 - N = C = O t H~NJ~U~CH 3 >

O
~S02 - NH - CO~NJ~N'OCH3 F U=~C2~5 If, for example, 2-methylthio-benzenesulphonamide and 2-chlorocarbonyl-4-dimethylamino-2,4-dihydro 3H-1,2,4-triazol-3-one are used as starting subst2nces, the course lQ of the reaction in process tb) according to the invention Le A 27 154 - 26 -7 ,.' ~ ~

can be outlined by the following equation:

SCH o 2 NH2 Cl -CO~NIJ~N~N ~ CH3 ) 2 -HCl H

SCH3 ~
~502-NH-co~NlJ~N~N ( CH3 12 N==L--H

If, for example, N-methoxycarbonyl-2-methoxy-benzenesul-phonamide and 5-diethylamino-4-difluoromethyl-2,4-di-hydro-3H-1,2,4-triazol-3-one are used as starting sub- .
stances, the course of the reaction in process (c) according to the invention can be outlined by the -follow-ing ~quation:

OCH3 Ll l~=< H~N~N~CHF2 ~S02-NH-COOCH3 ~ l l N~N(C2H5 )2 OCH3 ~
-HOCH3 e~S02-NH-CO~NJ~N'CHF2 N(C2H5 ~2 Formula (II) provides a general definition of the triazo-Le A 27 154 - 27 -linones to be used as starting substances in processes (a) and (c) according to the invention for the prepara-tion of compounds of the formula (I).
In formula (II), Rl and R2 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 preferred, or particularly preferred, for R1 and R2 .
Examples of the starting substances of the formula (II) are listed in Table 2 belowO

HN ~ NfRl (II) N=I~R2 Table 2: Examples of the starting substances of the formula (II) Rl R2 H H

C3~7 H

Le A 27 154 - 28 -~ ~ 7 i3 n Table 2 - continuation Rl R2 CH(CH3)2 H

CqHg H
CH2CH(CH3)2 H
C(CH3)3 H

H CH~CH3)2 H CH2CH(CH3)2 H CtCH3)3 C~F2 H

CH2C~20CH3 c~3 CH3 Le A 27 154 - 29 ~

7i~jlSi Table 2 - continuation CH3 CH~CH3~2 CH3 c4~9 CH3 CH2CH(C~3)2 CH3 C(CH3~3 CH(CH3)2 CH~

CH2CH(CH3)2 CH3 C2H5 C2~5, ~3 C~3 C2H5 CF~
C~2CHF2 c~3 ~e A 27 1~4 - 30 -2 ~ J

Table 2 - continuation Rl R2 C2H5 CqH9 ~CH2 ~CH2 ~CH2 CH~3 - CH
~CH2 CH3 N(CH3)2 C2H5 N ~ CH3 ) 2 OCH ~

C3}17 -Le A 27 154 - 31 -f'~ ~3 f~ 3 r~

Table 2 - continuation Rl R2 ~ C3H7 NHCH3 C2~5 N(CH3)2 CH3 N(CH3)2 Cz~g5 NtC~3)2 C3~7 Le A 27 154 - ~2 -. ~ .

: ' Table 2 - continuation Rl R2 ~C2H5 CH3 ~C2H5 C2H5 /\
CHz-O-C2H5 /~
N ( CH3 ) 2 {~
o - CH2 - cH= CHz CH3 O-CH2-CH=CH2 C2H5 O-CH2-CH=CH~ C3H7 ~~C112~CH-CH2-Br c3~7 Br Le A 27 154 - 33 -~ ~ 2 ~ ~ , Table 2 ~ continuation OCH3 ~

OCH3 ~>

OCH3 N ( CH3 ) 2 N~CH3)2 N(CH3)2 ~1 N(CH3)z {~

Le A 27 154 _ 3d, w ~J ~ ;) S~ ,~3 ~3J, ~

Table 2 - continuation Rl R2 ~\ ~3 ~ C2H5 NH-CH3 ~H2-0-CH ~
/ \ CH2-0-CH~

Le A ~7 154 - 35 -~J '~!ç~ 4 The starting substances of the formula (II~ are known and/or can be prepared by processes known per se (cf.
Chem. ser. 90 (1957), 909-921; loc.cit. 98 (1965), 3025-3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra-5 hedron 32 (1976), 2347-2352; Helv. Chim. Acta 63 51980), 841-859; J. Chem. Soc. C 1967, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301,946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11 1988, DE-P 3,916,207/LeA 26,849 dated 18.05.1989;
~E-P 3,916,208/Le~ 26,850 dated 18.05.1989; J. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated 24.05.1989).
For example, the triazolinones of the formula (II) are obt~ine~ when ~) oxadiazolinones of the general formula (VII) H~NJ~O ( Y I I ) N=~R2 in which R2 has the abovementioned meaning are reacted with amino compounds of the general formula (VIII) H2N-R1 (VIII) in which R1 has the abovemen~ioned meaning, Le A 27 154 - 36 -at temperatures between 20~C and 120~C and, if appropriate, in the presence of a diluent, such as, for example, water, and the hydrazine derivatives formed ~y this process, of the general formula (IX) H~ ,,C O - NH - R 1 ,N~ ( I X ) in which R1 and R2 have the abov.- -ntioned meanings, are isolated by customary methods (cf. the Preparation Examples) and - or if appropriate even without inte~ ate isolation - the compounds of the formula (IX) are condensed at temperatures between 20~C and 120~C and, if appropriateg in the presence of a basic condensation auxiliary, such as, for example, sodium hydroxide, and, if appropriate, in the presence of a diluent, such as, for example, water, to give the compounds of the formula (II) (cf. EP-A 301,946, DE-OS (German Published Specification~ 3,743,493/LeA 25,759 and the Preparation Examples), or when ~) amino compounds of the general fo~mula (VIII) ~2N-R1 (VIII~

Le A 27 154 - 37 -in which Rl has the abo~ementioned meaning, are reacted with carbonic acid derivatives, such as, for example, diphenyl carbonate, then with hydrazine or hydrazine hydrate and eventually with a car-boxylic acid derivative or carbonic acid derivative of the general formula (X) (RO)3C-R2 (X) in wh.ich R2 has the abo~ -ntioned meaning and R represents lower alkyl, at temperatures between 0~C and 150~C and, if appropriate, in the presence of a diluent, such as, for example, ethylene chloride (cf.
DE-P 3,920,270/LeA 26l937 dated 21.06.1989, DE-P 3,928,662/LeA 27,137 dated 30.08.1989, and the Preparation Examples).
The triazolinones of the general formula (IIa) HNJ~N~A 1 ( I I a ) I~A 2 in which A represents in each case optionally substituted alkyl, alkenyl~ cycloalkyl, alkoxy or dialkyl-amino and A represents hydrogen, or represents in each case optionally substituted alkyl, cycloalkyl, aralkyl, aryl or alkoxy, Le A 27 154 - 38 -~2 ~f'J~J

provided that both Al and A2 do not simultaneously re-present alkyl, are new and a subject of the present invention.
The new triazolinones of the formula (IIa) are obtained either when oxadiazolinones of the general formula (VIIa) H''NJ~ (VIla) ~A2 in which A2 has the abovementioned meaning, are reacted with amino compounds of the general formula (VIIIa) H2N-A1 (VIlIa) in which Al has the abovementioned meaning, analogously to the process described above under (~), or when amino compounds of the ~eneral formula (VIIIa) H2N-A1 (VIII3~

are reacted with carbonic acid derivatives, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of Le A 27 154 - 39 -~. ~3 ,~ ~ J~g the general formula (xa) ( RO ) 3C-A2 ( Xa ) in which A2 and R have the abovementioned meanings, analogously to the process described above under (~) (also see the Preparation Examples).
In the general formul~ (IIa), Al preferably represents Cl-C6-alkyl. C3-C5-alkenyl or C3-C6-cycloalkyl, or represents Cl-C6-alkoxy which is optionally substituted by fluorine, chlo-rine, bromine, cyano, Cl-C4-alkoxy or Cl-C4-alk-oxy-carbonyl, in particular methyl, ethyl, allyl, cyclopropyl, methoxy, ethoxy, propoxy or isoprop-oxy, or represents di-(Cl-C4-alkyl)-a~ino, in par-ticular dimethyla~ino or diethylamino, and A2 preferaLbly represents hydrogen, or represents Cl-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy, Cl-C4-alkyl-carbonyl or Cl-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C4-alkyl, or represents phenyl-Cl-C3-alkyl which is optionally substituted by iluorine/ chlorine, bromine, cyano, nitro, Cl-C4-alkyl, trifluoromethyl, C~C4-alkoxy and~or Cl-C4-alXoxycarbonyl, or represents phenyl which i8 optionally substituted by fluorine, chlor-ine, bromine, cyano, nitro, Cl-C4~alkyl, trifluoro-methyl, Cl-C4-alkoxy, fluorin~- and~or chlorine-substituted Cl-C3-alkoxy, Cl-C4-alkylthio, fluorine-and/or chlorine-substituted Cl-C3-alkylthio~ Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-Le A 27 154 _ 40 ~

alkoxy-carbonyl, or represents C1-C4-alkoxy, in particular hydrogen, Cl-C4-alkyl ~hich is option-ally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl, S or represents methoxy ~r ethoxy, provided that both Al and A2 do not simultaneously re~
present Cl-C6-alkyl.
The ~ompounds of the formulae (VII), (VIIa~, (VIII), (VIIIa) and (X) or (Xa) which are to be us~d as starting substances for the preparation of the triazolin-ones of the formulae (II) or (IIa) are known (cf. He~v.
Chim. Acta 55 ~1972), 1174; EP-A 301,946; DE-OS (Ge ~n Published Specification) 3,743,493).
Formula (III) provides a general definition of the sulphonyl isocyanates further to be used as starting substances in process (a) accoxding to the invention for the preparation of compounds of the foxmula (I).
In formula (III), R3 prPferably, or in particular, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being prefer-red, or particularly preferred, for R3.
Examples of the starting substances of the formula (III) which may be mentioned are:
2-flucro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluorometh-oxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-l 2-methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylamino-sulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-meth-oxycarbonyl-, 2-ethoxycarbonyl-, 2-propo~ycarbonyl- and 2-isopropoxycarbonyl-phenylsulphonyl isocyanate, 2-fluoro-, 2-chloro-, 2-difluoromethoxy , 2-trifluorometh~

Le A 27 154 41 -2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl isocy~nate,2-methoxycarbon~1-3-thienyl-sulphonylisocya-nate, 4-metho~ycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of th~ formula (III) are known and/ox can be prepared by processes known per 8e (cf. US-P 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808 44,809, 48,143, 51,466, 64,322, 70,041, 173,31~).
Process (a) according to the invention for the preparation of the new compounds of the formula (I~ is preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents.
These preferably include aliphatic and aromatic, option-ally halogenated hydrocarbons, such as pentane, h~ne, heptane, cycloh~Y~ne, petroleum ether, benzine, ligroin, benzene, toluene, 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 di-methyl 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 ex-ample, acetonitrile and propionitrile, amides, such as, for example, dimethylformamidet dimethylacetamide and N-methyl-pyrrolidone, and also dLmethyl sulphoxide, te$ra-methylene sulphone and hexamethylphosphoric triamide.
In process (a) according to the invention, the reaction temperatures can be varied within a substantial Le A 27 154 - 42 -range. In general, the process is carried out at temper-atures between 0~C and 150~C, preferably at temperatures between 10~C and 80~C.
Process (a) accoxding to the invention is gener-ally carried out under atmospheric pressure.
For carrying out process (a) according to the invention, between 1 and 3 moles, preferably between 1 and 2 moles, of sulphonyl isocyanate of the formula (III) are generally employed per mole of triazolinone of the formula (II).
The reactants can be combined in any desired sequence. The reaction mixture is stirred until the reaction is complete and concentrated, and the crude product which r~m~ i n~ in the residue is crystallized using a suitable solvent, such as, for example, diethyl ether. The product of the formula (I) which has been obt~ine~ in crystalline form is isolated by filtration with suction.
Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting substanc-es in process (b) according to the invention for the preparation of compounds of the formula (I).
In formula (IV), R1 and R2, 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 preferred, or particularly preferred, for R1 and R2, and Z preferably represents chlorine, C1-C4-alkoxy, benzyloxy or phenoxy, in particular methoxy or Le A 27 154 - 43 -J ~ 3 phenoxy.
Examples of the starting substances of the formula (IV) which are possible are the compounds of the formula tIV) to be prepared from the compounds of the formula (II) listed in Table 2 and phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or diphenyl carbonate.
The starting substances of the formula (IV) are known and/or can be prepared by processes known per ~e (cf. EP-A 283,876; EP-A 294,666; EP-A 298,371.
The triazolinone derivatives of the formula (IV) are obtained for example when triazolinon~s of the general formula lII) HNJ~N~Rl ( I I ) ~L~R2 in which R1 and RZ have the abov.~ -~tioned me~nings, are reacted with carbonic acid derivatives of the general formula (XI) z co-z1 (XI~

in which ~ has the abov. -ntioned --n i ~g and L~ A 27 154 - 44 -b~

Z1 represents a leaving group, such as chlorine, methoxy, benzyloxy or phenoxy, at temperatures between -20~C and +100~C, if appropriate in the presence of a diluent, such as, for example r tetrahydrofuran, and, if appropriate, in the presence of an acid acceptor, Ruch as, for example, sodium hydride or potassium tert-butylate (cf. the Preparation Examples).
Formula (V) provides a general definition of the sulpho~ides further to be used as starting ~ubstances in process (b) according to the in~ention for the prepar-ation of compounds of the formula (I).
In formula (V), R3 preferably, or in particular, has the --n;ng which has already been mentioned above in connection with the description of the compounds of th~
formula (I) according to the invention as being pre-ferred, or particularly preferred, for R3.
Examples of the starting substances of the formula (V) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluorometh-oxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylamino-sulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy~N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-meth-oxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-.isopropoxycarbonyl-benzenesulphonamide, 2-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl- and 2-ethoxycarbonyl-phenylmethanesul-phon~m ide, 2-methoxycar~onyl-3-thiophenesulphonamide, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl pyrazol-Le A 27 154 - 45 -5-sulphonamide.
The sulphonamides of the formula (V) axe known and/or can be prepared by processes known pex se (cf.
US-P 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (b) according to the invention for the preparation of the new compounds of the formula ~I) is preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents, for example those which have been indicated above in the case of process (a) according to the invention.
Acid acceptors which can be employed in process (b) according to the invention are all aaid-bind-ing agents which can customarily be used for reactions of this type. The 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 hydroxide, alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate, potassium carbonate, sodium tert-butylate and potassium tert-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylben~ylamine, pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diazabi-cyclo-t2,2,2J-octane (DABCO).
When carrying out process (b) according to the invention, the reaction temperatures can be ~aried within a substantial range. In general, the process i5 carried Le A 27 154 ~ 46 -out at temperatures between 0~C and lOODC, preferably at temperatures between 10~C and 60~C.
In general, process (b) according to the inven-tion is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process (b) according to the invention, the specifically required ~tarting substances are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess. In general, the reactions are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in process (b) according to the invention is carried out in each case by customary methods.
The triazolinones of the formula (II) which are to be used as starting substances in process (c) accord-ing to the invention for the preparation of compounds ofthe formula (I) have already been described as starting substances for process (a) according to the invention.
Formula (VI) provides a general definition of the sulphonamide derivatives further to be u~ed as starting substances in process ~c) according to the invention for the preparation of compounds of the formula (I).
In formula ~VI), R3 and Z 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~ or (IV) according to the Le A 27 154 - 47 ~

~J 3.,~ r.) ~

invention as bein~ preferred, or particularly preferred, for R3 and Z.
Process (c) according to the invention is prefer-ably carried out using diluents. Suitable diluents in this context are the same organic solvents as have been mentioned above in connection with the description of process (a) according to the invention.
If appropriate, process (c) is carried out in the presence of an acid acceptor. Suitable acid-binding agents in this context are the same as have been men-tioned above in connection with the description of process (b) according to the invention.
When carrying out process (c) according to the invention the reaction temperatures can be varied within a substantial range. In general, the process i5 carried out at temperatures between 0~C and 100~CI preferably at temperatures between 10~C and 60~C.
In general, process (c) according to the inYen-tion is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process ~c~ according to the invention, the specifically required starting substances are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess. In general, the reactions are carried out in a 6uitable diluent in the presence of an acid acceptor, and the reaction mixture is st~rred for several hours at ~he ~pecifically required temperature. Working-up in Le A 27 154 - 48 -~,t~ //J~)3 process (c) according to the invention is carried out in each case by customary methods.
To convert the compounds of the formula (I) into salts, they are stirred with suitable salt formers, such as, for example, sodium hydroxide, sodium methylate, sodium ethylate, potassium hydroxide, potassium methylate or potassium ethylate, ammonia, isopropylamine, dibutyl-amine or triethylamine, using suitable diluents, such as, for example, water, methanol or ethanol. The salts can be isolated as crystalline products - then if appropriate after concentrating the mi~ture.
The active compounds according to the invention can be used as defoliants, desiccants, agents for de-stroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadèst sense, there axe to be understood all plants which grow in locations where they are undesired. 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 usedt for example, in connec~ion with the follow-ing plants:
DicotYledon weeds of the qenera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, 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,Centaurea,Tnfolium, 3 0 Ranunculus a n d Taraxacum.
DicotYledon cultures of the qenera Gossypium, Le A 27 154 - 49 -~J s'~ f~

Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cuc~mis and Cucurbita.
Monocotyledon weeds of the qenera: Echinochloa, Setaria, Panicum, Digitaria/ Phleum, Poa, Pestuca, Eleusine, Brachiaria, Lolium, Bromus, A~ena, Cyperus, Sorghum, AyLo~Lon~ Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, An~n~5 ~ 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 concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tre~ plantings. Equal-ly, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decor-ative 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, inlawns,~,meadowsandpas~es, and for the selective combating of weeds in annual cultures.
The compounds of the formula ~I) according to the Le A 27 154 _ 50 invention are suitable for combating monocotyledon and dicotyledon weeds both in the prc i -rgence and the post-emergence method. They are markedly more effective than, for ~xample, isocarh~mi~e.
To a certain extent, the compounds according to the invention also show a fungicidal action, for example against powdery mildews and against apple scab, and also against Pyricularia oryzae on rice.
The active compounds can be converted into the customary formulations, such as ~olutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, ~uspension-emulsion concentrates, 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 a~ents, that is emulsifying agents and/or dispersing agents andtor foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suit-able in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohe~ne or paraffins, for example petrole~m fractions, mineral and vegetable oils, alcohols, such as ~e A 27 154 - 51 -butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohe~Anone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable: for ~xample ammonium 8alts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, ~uch as highly disper~e ~ilica, 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 granules 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 ~uitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis 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 alcohol and polyvinyl acetate, as well as natural phospholipids, ~uch as cephalins and lecithins, and Le A 27 154 - 52 -?~ J J

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 pi~ments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, mangane~e, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per 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 formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known her~icides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dLmethylurea (METABENZ~HIAZURON) 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;
furthP -re also mixtures with 2,4-dichlorophsnoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butric acid ~2,4-DB); 2,4-dichlorophenoxypropionic acid ~2,4-DP); 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid (ACIF~UORFEN); 2-chloro-2',6'-diethyl N-methoxy-methyl-he A 27 154 - 53 -h .~S ~ J ~

acetanilide (AT~Ac~T~QR); 2-chloro-4-ethylamino- 6 iso-propylamino-1,3,5-triazine (ATRAZINE); methyl 2-[[[t[(4,6-dimethoxypyrimidin-2-yl)-amino]carbonyl]-amino]-sulphonyl]-methyl]-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitro-benzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-~butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)-acetamide (~U~CFT~OR); ethyl 2-~[(4--chloro-6-lQ methoxy-2-pyrimidinyl)-aminocarbonyll-aminosulphonyl}-benzoate( CHLORIMURON);2 -chloro-N-{[(4-methoxy-6-m2thyl-1,3,5-txiazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-phenyl)-urea(CHLORTOLURON); 2-chloro~4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine~CYANAZINE);2,6-dichlo-robenzonitrile(DICRT.O~P.~IL);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester ( DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxa~olidin-3-one (DIMETHAZONE); ~-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-on2 (ETHIOZIN); 2-{4-[6-chloro-2-benzoxazolyl)-oxy~-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP);
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); NIN-dimethyl-N'-(3-trifluoromethylphenyl)-urea (FLUOMETURON); l-m~thyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-pyridone (FLURIDONE 3; 5-(2-chloro-4-trifluoromethyl~phenoxy)-N-methylsulphonyl-2-nitrobenzamide (F~M~.SAFEN); N-phos-phonomethyl-glycine ( GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4~ methylethyl)-5-oxo Le A 27 154 - 54 -lH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZA~ETHABENZ);
2-(4,5-dihydro-4-methyl-4-is~propyl-5-oxo-lH-Lmidazol-2-yl)-pyridine-3-carboxylic acid (IMAZAPYR); 2-[5-methyl-5-(1--me~hylethyl)-4-oxo-2-imidazolin-2-yl]-3-~uinolin-carboxylic acid (TM~7~QuIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(lH)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid ~IMA~E~HAPYR); 3,5-diiodo-4-hydroxy-benzonitrile ( IOXYNIL); N,N-dimethyl-N'-(4-iso-propylphenyl)-urea (ISOPROTURON); (2-methyl-4-chloro-phenoxy)-acetic acid (MCPA); (4-chloro-2-methylphenoxy)-propionic acid (MCPP); N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET); 2-chloro-N-(2,6-dimethyl-phenyi)-N-[(lH)-pyrazol-l-yl-methyl]-acetamide (ME~A7.~CR~OR); 2-ethyl-6-methyl-N~(1-methyl-2-metho~
xyethyl)-chloroacetanilide (METOLACXLOR); 2-~[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic aicd or its methyl ester (METSULFURON); 1-(3-trifluoromethyl-phenyl)-4-methyl-amino-5-chloro-6-pyridazone (NORFLURAZON); N-(l-ethyl-propyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thio-carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL); 2-[1-(ethoxamino)-butylidene~-5-(2-ethylthiopropyl)-1,3-cyclohex~ione (SETHOXYDIM); methyl 2-{[(4,6-dimethyl-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate (SULFOMETURON); 4-ethylamino-2-t-butyl~mino-6-methylthio-s-triazine (TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3~5~triazin-2-yl)-amino]-carbonyl3-aminol-sulphonyl]-thiophene-2-carboxyla~e (THIAMETURON); S-Le A 27 154 - 55 -~2,3,3-trichloroallyl~-N~N-diisopropylthiocarbamate t TRI -ALLATE ), 2,6-dinitro-4-trifluoromethyl-N,N-dipro-pylaniline (TRIFLURALIN). Suprisingly ,some mixtures also show a ~ynergistic effect.
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 solutions ~ suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing 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 ~oil before sowing.
The amount of active compound used can vary within a sub~tantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 15 kg of active compound per hectare of soil surface, preferably between 0.05 and 10 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.

~e A 27 154 - 56 -~Jlj2 Preparation Examples:
EXamD1e 1 CC)OCH3 O ~
~S ~2 ~ NH - CO~N N,L_1 (Process (a)) 3.0 g (17.95 mmol) of 4-cyclopentyl-5-methyl-2,4-5dihydro 3H-1,2,4-triazol-3-one are dissolved in 60 ml of acetonitrile, and 6.9 g ~28.6 mmol) of 2-methoxycarbonyl-phenylsulphonyl isocyanate, dissolved in 20 ml of aceto~
nitrile, are added to this ~olution with s~irxing. The reaction mixture is stirred for 6 hours at 20~C and then 10concentrated. The residue which ~ i n~ is stirred with diethyl ether, and the product which has been obtained in cry~t~lline form is isolated by filtration with suction.
. This gives 6.6 g (90 ~ of theory) of 4-cyclo-pentyl-5-methyl~2-(2-methoxycarbonyl-phenylsulphonyl-15aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 146 DC .

Le A 27 154 - 57 -~"/,i7J 7 ~

Exampl~ 2 Cl O
~2 -NH - CO~NJ~N~CH3 (Process (b) ) 1,8 g (11.8 mmol) of 1,8-diazabicyclo-~5,4,0]-undec-7~ene (DBU) are added to a stirred mixture of 3.0 g (12.1 mmol) of 5-ethyl-4~methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.5 g (12.2 mmol) of 2-chloro-6-methyl-benzenesulphonamide and 60 ml of aceto-nitrile. The reaction mixture is stirred for 2 hours at 20~C, then poured into about twice the volume of ice-water, and a pH of about 2 is established by dropwise addition of concentrated hydrochloric acid. The product which has been obt~ined during this process in crystal-line form is isolated by ~iltration with ~uction.
This gives 3.2 g (73.5 % of theory) of 5-ethyl-4-methyl-2-(2-chloro-6-methyl-phenyl3ulphonyl-amino-carbonyl)-2,4-dihydro-3H-1,2,4-triazol 3-one of melting point 176~C.
For example the compounds of the formula (I) listed in Table 3 below can al80 be prepared analogously to Examples 1 and 2 and ~ollowing the general instruc-tions of the preparation processes according to the invention.

Le A 27 154 _ 5~ _ J ~

R3-So2-NH-Co~NJ~N~Rl ( I ) Table 3: Preparation Examples of the compounds of the formula (l) (m.p. = melting point)-~x. Rl R2 R3 m~p. (~C) No.
COOC~3 3 C6H5 CH~ ~ 1s8 4 CH3 C2H5 ~ 15 9 C~H5 C2Hs ~ 115 6 CH3 C3~7 ~ 1 4 3 Cl 7 C2H5 C2H5 ~$ 139 ~H3 ~e A 27 154 - 59 -Table 3: - continuation Ex. R1 R2 R3 m.p. (~C) No.
Cl 8 CH3 C3H7 ~ 141 ~H3 g OCH3 CH~ ~ 121 So2N(cH3)2 OCH3 CH3 ~ ~ 1 BO

11 OC~3 CH3 CH3 149 12 QCH3 C2H5 ~ 144 ~--( 13 OCH3 C3H7 ~ 128 5O2N(CH3)2 14 CH3 C2H5 ~ 173 Le A 27 154 - 60 -~JJ ~P ~ J~ i,J ~

Table 3: - continuation Ex. R1 R2 R3 m.p. (~C~
No .

5O2N(CH3)2 C~3 C3H7 ~ 133 16 C2H5 ~ 154 17 OCH3 CH(CH3)2 ~ 137 SO2N~CH~2 /\ ~< ' 18 C2H5 ~ 174 19 C3H7 ~ 97 CH3 N(CH3)z ~ 168 21 OCH2C6H5 CH3 ~ 174 Cl 22 C2H5 C3H7 ~ 136 Le A 27 154 - 61 -~ 3 ~ ~ r~J ~i~3 Table 3: - continuation Ex. Rl R2 R3 m.p. ( C) No .

23 N(CH3)2 C2H5 ~ 139 24 N(CH332 H ~ 197 N(CH3)2 CH(CH3)2 ~ 148 26 ~C2HS C2H5 ~ . 153 27 ~C2H5 C3H7 ~ 155 COOCH~
~ ~C
28 CH(CH3)2 ~ 186 Cl 29 C3H7 ~ 146 N(CH332 C3H7 ~ llo Le A 27 154 - 62 -~ ~J 1~ t,3 ~J

Table 3: - continuation Ex. Rl R2 R3 m.p. ( qC) No .

~\ ~<
31 N(CH3)2 <~ 131 COOC~3 32 C2H5 C4H9 ~ 98 COOC~13 33 CH3 C4H9 ~ 113 34 C3H7 C4H9 e~ 88 3s C~Hg ~ 117 36 O~H3 C4H9 ~ 117 37 CH3 ~ 141 38 C2H5 ~ 130 Le A 27 154 - 63 -~J~ J~
.
Table 3: - continuation Ex . Rl R2 R3 m . p . ( C ) No .

39 C3H7 ~ 139 COOCH
~ ~\ ~e~ 3 ~ 151 41 {~ CH3 ~ lSl 42 CH(C113)2 NHCH(CH3)2 ~ 135 43 N~CH3)2 N~C113)2 ~ 171 44 CH3 C3H7 ~ 168 ~5 C2~5 N(CH3)2 ~ 134 4 6 CH3 C2HS ~ 16 7 Le A 27 154 64 -Table 3: - continuation Ex. R1 R2 R3 m.p. (~C) No.

47 NH2 C3H7 ~ 120 48 ~ NH ~ ~ 120 49 H ~ 195 -CH2CH=CHz C2H5 ~ 108 51 -CH2CH=CH2 H ~ 158 52 OCH3 C3H7 ~ 110 - 111 53 CHz ~ H ~ 212 - 214 54 C3H7 H ~ 1~8 - 169 Le A 27 154 - 65 -Table 3: - continuation Ex. Rl ~2 R3 m.p. (~C) No.

C3H7 ~ 103 - 105 56 C2H5 ~ 127 57 OCH3 C2H5 ~ 111 - 113 COOC~3 /\ ~
58 -OCH3 ~ 139 59 -1~HCH3 C3H7~n ~ 196 F
CH3 C3H7 n ~ 178 61 ~ H ~ 177 Le A 27 154 - 66 -~ ~ f. . .~ - 3 ~ ~
;
Table 3: - continuation Ex. Rl R2 R3 m.p. ~C) No.

62 -CH2CH(CH3)2 C2H5 ~ 123 63 -CH2-CH=~H2 C3H7 n ~ (amorphous) 64 CH2 ~ C2H5 ~ 157 ~ C2H5 ~ 117 66 -C~CH3)3 C2H5 ~ 182 67 ~ C2H5 ~ 133 68 ~ C2H5 ~ 162 6~ -CH2-CH-CH2 CH3 ~ 120 L~ A 27 154 _ ~7 -~ ~ ~', ?, ? ~

Table 3: - c~ntinuation Ex. Rl- R R3 m.p. (~C) NoO

~ C2H5 ~ 183 71 C2H5 H ~ 196 COOC~3 72 ~ CH3 ~ 153 73 -OCH3 ~ 138 74 CH(CH3)2 H ~ 191 ~ H ~ 191 76 ~ H ~ lq2 77 -C~CH3)3 H ~ 211 Le A 27 154 - 68 -~,l$j,,~"~

Table 3: - continuation Ex. R1 R2 R3 m.p. ~ DC) No.

COOC~3 78 -CHz-CH-CH2Br CH3 ~ 110 Br 79 CH3 -CH20CH3 ~ 152 CH3 C2H5 ~ 174 81 CH3 -CH20C2H5 ~ F3 123 82 -OCH3 C3H7~n ~ (amorphous) ~\ ,~CON(CH3)2 83 C2H5 ~ 124 84 -CH20CH3 ~ 102 -CH20CH3 ~ 155 Le A 27 154 - 69 -~ ~ ~ r~1 Table 3: - continuation Ex. Rl R2 R3 m.p. (~C) No.

86 -CH20C2H5 ~ OCH3 123 87 -CH20C2H5 ~

88 -N(CH3)2 ~ 189 Cl3 89 -OCH3 C2H5 ~ 15S

C2H5 ~ 133 91 -OCH3 C3H7~n ~ 125 92 C~H5 ~ 138 5 OOCH~

Le A 27 154 ~ 70 -r' Table 3. - continuation Ex . R1 R2 R3 m . p . ( C ) No .

93 -OC2H5 C2H5 ~ 132 94 -0C2Hs C3H7~n ~ 107 -OCH3 CH(CH3)2 ~ 128 g6 OCH3 CH3 ~ 119 97 C3H7 n ~ COOCH3 100 ~ 140 98 ~

99 -N(CH3)2 ~ 163 100 -N(CH3)2 ~ 182 Le A 27 154 - 71 -~ !3 Table 3: - continuation Ex. R1 R2 R3 m.p. t~C) No.

101 CH3 -N(CH3)2 ~ 181 102 CH3 -OCH3 ~ 1 150 103 C2H5 ~ 147 104 -CH2-CH=CH2 CH3 ~ 132 105 -CH2-CH=CH2 C2H5 ~ 109 106 -CH2-CH=CH2 C3H7~n ~ 104 Le A 27 154 72 -Table 3: - continuation EX. Rl RZ R3 m.p. ~ C) No.

107 -OC2H5 C2H5 ~ 147 Cl3 108 -~C2H5 C3H7 n ~ 136 109 -~CH3 CH(CH3)2 ~ H3 126 Cl 110 CH3 CH3 ~ 146 111 CH3 ~ 175 112 CH3 CH(CH3)2 ~ 124 Le A 27 154 _ 73 _ Table 3: - continuation Ex. R~ R2 R3 m.p. (~C) No.

113 CH~ ~ 171 114 CH(CH3)2 ~ 132 115 ~ 167 116 CH3 C~3 ~ 155 117 CH3 CZH5 ~ 147 118 CH3 C3H7 n ~ 16 ~e A 27 154 - 74 -~able 3: - continuation Ex . R1 R2 R3 m . p . ~ C ) No .

119 OCH3 C2H5, ~COOCH3 Cx COOCH3 120 --CH2 C2H5 ~ 132 Le A 27 154 _ 75 _ Startinq substances of the formula (II):
Exa~pl~ (II-1) o H7J~N~OC 2H5 steP 1:

H-N-co-NH-oc2H5 ( IX- 1 ) A mixture of 68.5 g (0.60 mol) of 5-methyl-lr3,4-oxadiazolin-2-one, 45.8 g (0.75 mol) of 0-ethyl-hydroxyl-amine and 400 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and reconcentrated. The residue which is obtained in this process is stirred with diethyl ether, and the product which has been obtained in crys~alline form is isolated by filtration with suction.
This gives 77.5 g (74 % of theory) of 1-ethoxy-aminocarbonyl-2-propionyl-hydrazine of m~lting point 122~C.

Le A 27 154 - 76 -Ste~ 2:

H7 ~ N~OC2H5 (II-l) NC~C 2 H 5 A mixture of 75c5 g (0.43 mol) of l-ethoxyamino-carbonyl-2-propionyl-hydrazine, 17.5 g (0.44 mol) of sodium hydroxide and 300 ml of water is refluxed for 12 hours. When the mixture is cold, a ph of between 3 and 4 is established by adding concentrated hydrochloric acid, and the mixture is concentrated. The residue is stirred with ethyl acetate, and the sodium chloride which has r~;ned undissolved is separated off by filtration with suction. The filtrate is concentrated, the residue i5 stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtra-tion with suction.
This gives 37 g (55 % of theory) of 4~ethoxy-5-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 93~C.
Example (II-2) H7J~N~CH3 ( I 1-2 ) N=l~C 3H 7 mixture of 40 g (0.31 mol) of 5-propyl-1,3,4-~e A 27 154 - 77 -oxadiazolin-2-one, 109 g of aqueous methylamine solution (32 % strength, 1.125 mol of CH3NH2) and 500 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and reconcentrated. The residue obtained in this process is stirred with diethyl ether, and the product which has been obtained in crys-talline form is isolated by filtration with suction.
This gives 31.7 g (72 % of theory) of 4-methyl-5-propyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 86~C.
Example (II-3) O
HN ~ N~N(CH3)2 856 g (4.0 mol) of diphenyl carbonate are dis-solved in 588 g of ethylene chloride. 245 g (4.0 mol) of dimethylhydrazine (98 % pure) are added dropwise with lS water-cooling, and the mixture is heated slowly and, for 4 hours, stirred at 60~C.
After the mixture has cooled to 20~C, 200 g (4.0 mol) of hydrazine hydrate are added dropwise, and the mixture is then stirxed for 12 hours. It is warmed to 70-80~C and, for about 1 hour, stirring is continued.
When cold, the solution is dis~illed in vacuo, during which pro ess ethylene chloride and water are removed (final bottom t~mrPrature 100~C~. The abo~e phenolic Le A 27 154 - 78 ~ -dimethyl carbodihydrazide solution is added dropwise in the course of 90 minutes at reflux temperature (about 102~C) to 424 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has formed is removed by distil-lation, phenol is distilled off in vacuo, after which282 g of product mixture are obtained at a head temper-ature of 85-105CC. This mixture is boiled with ~00 ml of acetone, and filtered at boiling point, and the filtrate is then cooled. The product which has been obtained in this process in crystalline form is isolated by filtra-tion with suction.
This gives 71 g (14 % of theory) of 4-dimethyl-amino-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 127~C
For example the compounds of the formulae (II) and (IIa) listed in Table 4 below can also be prepared analogously to Examples (II-l) to (II-3).

HNJ~N--Rl ( I I ) N R

Le A 27 154 - 79 ,3 f i ~able 4: Preparation examples of the compounds of the formula (II) ~x. R1 R2 m.p. (~C) No.

II-S CH(CH3)2 CH3 118 II-9 CH(CH3)2 C2H5 102 II-10 C~H5 C3H7 97 I1-11 C3H7 C3H7 (amorphous) II-12 CH(CH3)2 C3H7 91 II-13 CH3 CH~CH3)2 9Z
II 14 C2H5 CH(CH3)2(amorphous) II-15 c3~7 CH(CH3)2(amorphous) II-16 CH(CH3)2 CH(CH3)2 168 /\

I1-19 OCH3 c~3 178 II-21 OCH3 c3~7 127 Le A 27 154 - 80 -,7 !iJ ~ I Ir~

Table 4 - continuation ~x. ~1 R2 m.p. (~C) No.
II-22 OCH3 CH(CH3)2 130 Il-23 ~CH2c6H5 CH3 106 ~\

11-26 ~C2H5 C3H7 72 ~\
II-27 CHtCH3)2 12~

II-29 C2H5 C4H~ 76 Il-30 C3H7 C4H9(amorphous) .~

Le A 27 154 - 81 -3 ~

Table 4 - continuation Ex. R1 R2 m.p. (~C) No.

II-37 N(CH3)2 CH3 153 II-38 N~CH3)2 C2H5 114 II-3s N(CH3)2 C3H7 108 Il-40 N(CH3)2 CH(CH3)2 100 II-41 CH3 N(CH3)2 80 ~\
II-42 N~CH3)2 134 II-4~ CHtCH3)2 NHCH(CH3)z205 II-44 N~CH3)2 NtCH3)2 93 II-45 C2H5 N(CH3)2 50 II-46 n CH3 145 II-47 ~ CH3 163 II-49 ~CH3 136 - 137 II-51 NH2 H 19?
II-52 NH~ CH3 230 I I-5:3 NH2 C~3 163 Le A 27 154 - 82 -~ f;,~?~lJ~

Tabl~ 4 continuation EX. Rl ~2m.p. ( ~C) No.

II-54 NHCH~ CH(CH3~2 105 /~

II-56 ~H2 C2H5 170 II-61 NHCH3 N~CH3)2 129 II-63 NH2 ~ 1 248 C~3 II-66 NH2 ~ 210 II-6R NH~ N(C2H5)2 196 Le A 27 l54 - 83 - I

~ 3~.J

Table 4 - continuation Ex~ Rl R2 m.p. ~ C) No.

II-70 NH2 CHtCH3~2 172 II-71 N~2 C(CH3~3 261 II-72 NH2 CH2CH2~CH3 98 II-73 NH2 C(CH3)2C2H5213 II-75 NH2 OCH3 (amorphous) lI-76 NH2 CH20CH3 134 II-78 NtCH3)2 CH3 153 II-79 CH2 ~ ~ C1 C2H5 103 II-80 -CH2CHtCH3)2 C2~5 105 II-82 N(CH3)2 CHtCH3~2(amorphous) II-85 NH2 N(CH3~2 207 Le A 27 154 - 84 -Table 4 - continuation Ex. R1 R2m.p. ( ~C) No .

II-87 NH2 ~ 223 II-88 NH2 NHcH(cH3)2152 II-89 NHCH3 NHCH(C~3~2120 11-90 ~ NH ~ 254 II-91 N(CH3~2 II-93 C3H? H 48 Il-94 C6H5 C2H5 124 Il-95 C(CH3~3 C2H5 158 II-97 ~ C2~5 108 Il-99 -CH2CH=CH2 CH3 108 II-100 C6H5 CiY3 150 II-101 ~ CH~ 116 II-102 ~ C~H5 146 II-104 CH(CH3)2 H 105 Le A 27 154 - 85 -~::

Table 4 - continuation Ex. R1 R2 m.p. ( C) No.

II-105 ~ H 79 II-106 ~ H 162 II-107C(CH3)3 H 194 II-108-CH2-CH-CH2Br CH3 111 Br II-109CH3 -C~20CH3 104 II-110CH3 -CH20C~H5 102 II-lI1 ~ -CH20CH3 102 II-112 ~ -CH20C2H5 119 II-113 ~ -N(CH3)2 130 ~CH3 'C2H5 ,CH3 II-115NHz -N 165 C3H7 n ~C2H5 ~C3H7-n 'I-117NH2 -N 0 267 Le A 27 154 - 86 -The compound of Example (II-118) disclosed in Table 4 (above) can be prepared as follows:
o HN ~ N~CH~ 118) C~

50.2 g (0.33 mol) of hydrazino-formic acid phenyl es~er (= l-phenoxycarbonyl-hydrazine) and 36.~ g (0.33 mol;
90 % purity) of 0,0,~-trimethyl-iminocarbonate are mixed at 40 ~C with 100 ml of 1,2-dichlorobenzene, and this mixture is then stirred for two hours at 60 ~C. There-after the mixture is heated further up to 120 ~C, while methanol (formed during the reaction) is being distilled off. Then the reaction mixture is cooled and heated again in vacuo (0.01 mbar) to a temperature of 120 ~C in order to remove any remaining volatile com-pounds (me~hanol, phenol and 1,2-dichlorobenzene) from the reaction mixture. At a temperature above 120 ~C the reaction product is distilled roughly and then crystal lized from toluene.
This gives 7.5 g (18 % of theory) of 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-one as colorless crystals of melting point 144 ~C.

Le A 27 154 - 87 -i ~ .

~ J~

Examples of hydrazine derivatives of the formula (IX) which can be obtained analogously to Ex-~ ample (II-1), ~tep 1, are li~ted in Table 5 below.
H-N-CO-NH-Rl I (IX) Table 5: Examples of the hydrazine derivatives of the formula (IX) Ex, R1 R2 m.p. (~C) No.

IX-2 OCH3 CzH5 120 ~X-3 OCH3 C3H7 125 IX-4 OCH3 CH~CH3)2 127 IX-5 ~CH2c6H5 CH3 lOO
~\
IX-6 C2~5 174 ~\

IX-8 ~C2H5 C3H7 119 ~\
IX-9 CH(CH3)2 ISO

Le A 27 154 - 88 -Table 5 - continuation Ex. R1 R~ m.p. ( ~C) No .

~ /\

/\

IX-14 CH2-CH=CH2 C~H7 134 /\
IX-15 -CH20C2H5 9?

Le A 27 154 - 89 -f;~ ~J~ ~

Startin~ sub6tances of the formula ~IV):
Example (IV-l) ~ J~
~ -CO'N N~CH3 N=L~C 2H 5 6.4 g (0.05 mol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2l4-triazol-3-one are dissolved in 80 ml of tetra-5 hydrofur~n, and 1.8 g ~0.06 mol) of sodi~m hydride (8~ %
of substance) are added under nitrogen. After the mixture has been stirred for one hour at 20~C, 7.9 g (0~05 mol) of phenyl chloroformate are added dropwise, and the reaction mixture is stirred at 20~C for a further 20 hours. After the mixture has been concentrated, the residue is taken up in methylene chloride, and the mixture is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated, the residue is triturated with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 4.5 g (36 % of theory) of 5-ethyl-4-methyl~2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 141~C.
For example the compounds of the formula (IY) listed in Table 6 beIow can also be prepared analogously to Example (IV-1).

~e A 27 154 _ go -.

h ~ ~J

Z - CO'N~N'Rl t I V ) ~=L~R2 Table 6: Examples of the compounds of the formula ( IV) Ex. ~ 2 z m.p. ( ~C) No .

lV-2 C3H7 C3H7 C6~5 88 IV-3 OCH3 C3~7 C6H5 82 ~\ .

IV-8 ~C2H5 C2H5 C6H5 IV-s OCH2CH=CH2 CH3 C6~5 IV- I O ~ C4H9 Cl,H5 IV-ll c~3 C6H5 IV-~2 NHCH3 C?H5 C6H5 Le A 27 154 - 91 -Table 6 - continuation Ex. R1 R2 z m.p. (~C) No.

IV-14 CH3 NHCH(CH3)2 C6H5 IV-15 MtCH3)2 N(CH3)2 C6H5 IV-17 ~C2H5 C6H5 IV-20 CH(CH3)Z CH(CH3)2 C6H5 IV-21 OCH ~ C2H5 C6H5 89 IV-2Z C3H7 n C6H5 104 Le A 27 154 - 92 use Examples:
In the following use examples,the known herbicide isocarbamide, of formula (A) below, is used as comparison substance:

r~
~N~N - CO-NH- CH2CH ( CH3 ~ 2 ( A ) The formulae of ~he compounds according to the invention used in the Vse Examples are listed indi~idual-ly below in conjunction with the number of the Preparation Examples:

~502-NH-CO~N N~CH3 (4 ~S02-NH-CO'NJ~N'C2H5 ~ 5 _< 11 <~so2-NH-co'N~N~cH3 ( 6 ) Cl O
~502-NH-CO'NJ~N~CH3 ( 2 ) CH3 ~C2H5 Le A 27154 - 9~ -~ ~ ,~f J , ~

ClO

2 NH-C0~7 ~ N~C2~5 t7 C~3 ~ C2H5 (~1 0 SO2-NH-CO~N ~ N'CH3 t8) CH3 ~ 3H7 COOC~3 O

5o2-N~-co~ ~ 'OCH3 (12) 5o2-NH-co~ ~ OC~3 (1~) N(CH3)2 o ~ SO2-NH-co~ ~ CH3 (14 ~ 2~15 5o2N(cH3)2 o SO2-NH-CO~N ~ N~CH3 (15) ~ C3~7 SO2-NH-CO ~ ~ (16) 2~5 COO~ O
SO2-NH-CO~ ~ OCH3 (17 }l~cl~l3)2 Le A 27 154 - 94 -J ~ ~3 5o2N~cH3~2 o ~SO2-N~_co~ ~\ ( 18 ~SO2-NH-CO~N--I~h ~\ ~19 ) N=J~C 3H7 COOCH3 ~
~2 -NH- CO~N~N~C~3 ( 2a ) N ( CH3 ) 2 ~SO2-NH-CO~Oc2H5 ( 26 ) zH5 ~SO2-NH-CO~c2H ( 27 ) COOCH3 ~
~S02-NH-CO~N~ ~\ ~ 28 ) CH(C~3 J2 ~S ~ 2 - NH - C O~N~N ~\ ~ 2 9 J
CH 3 N=C~C3H~

~502-NI~-CO~NJ~N~N (CH ) ( 3D ) 3)~7 Le A 27 154 - 95 ~

:

,~

~5~ 3: ~

S02-NH-CO'N ~ N'C2H5 (32) 5~2 NH-C0~7 ~ N~CH3 (33 4Hg S02-NH-CO~N ~ N'C3H7 (34) ~ C4H9 2 NH-C0'7 ~ ~ ~35 N ~ C4H9 S02-NH-CO'N ~ N'CH3 (37) S02 NH CO~7 ~ 1~C3H7 (39) <~502-NH-C0~7~ ~ (401 Le A 27 154 - g6 -~ 3 502-NH-CO~y ~ N~OCH3 (9) h ~H3 S02-NH-CO~N ~ N'N(C 3)2 (~

COOCH3 N ~ N
SO2-NH-CO' ~OCH3 (36) C4Hg Le A 27 154 - 97 -~ ~ f; i I J ~

ExamPle A

Prc ~ -rgence test Solvent: 5 parts by weight of acetone ~mulsifiero 1 part by weight of alkylaryl polyglycol ether To prepare 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.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation o~
active compound. It is expedient here to keep constant the amount of water per unit area. ~he concentration of 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 of the plants is rated in % damage in comparison with the development of the untreated control. The figures denote:

0 % = no action (like untreated control) 100 % = total destruction In this test a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 6, 8, 12J 13, 16, 17, 18, 19, 20, ~5, 27, 28, 29, 34, 37, 39 and 40.

Le A 27 154 - 98 -Example B

Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight o~ alkylaryl polyglycol ether To prepare a suitable preparation o~ 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 having a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way that the specifically desired amounts of active compound per unit area are applied. The concentration of the spray liquor is chosen in such a way that the speci-fically desired amounts of active substance are applied in lO00 1 of water/ha. After three weeks, the degree of damage of the plan~s is rated in ~ damage in comparison with the development of the untreated control. The fi~ures denote:

0 % = no action (like unkreat~d control) lO0 % = total destruction In this test a clearly superior activity com-pared with the prior ~rt i6 shown, for example, by the compounds of Preparation Examples 2, 4, 5, 6, 7, R, 12, 13, l~, 15, ~6, 17, 18, 19, 20, 2~, ~7, ~8, 29, 30, 32, 33, 34, 35, 37, 39 and 40.

Le A 27 154 - 99 _ Example C

Pyricularia test (rice) / protective Solvent: l2,5 parts by weight of acetone ~ 5jf;~r 0,3 parts by weight of alkylarylpolyglyCol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and~the ~oncentrate is ailuted with water and the stated 2mount of emulsifier to the desired concentration.

To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated with an aqueous spore suspension of Pyricularia orycae. The plants are then placed in a greenhouse at 100 % relative atmospheric humidity and 25~C

Evaluation of the disease infestation is carried out 4 days after the inoculation.

In this test, a very good activity is sho~n, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20~ 30, 31, 32, 33, 34, 35, 36, 37.

Le A 27 l54 - 100 -i~ ~ ( r ;~ ~ IJ ~

Example D

Pyricularia Test (rice) / systemic Solvent : 12,5 parts by weight of acetone Emulsifier: 0,3 parts by weight of alkylaryl-poly-glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.

To test for systemic properties, standard soil in which young plants have been grown is watered with 40 ml of the preparation of active compound. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.
Thereafter, the plants remain in a greenhouse at a temperature of 25~ and a relative atmospheric humidity of 100~ until they are evaluated.

Evaluation of the disease infestation is carried out 4 days after the inoculation.

In this test, an excellent activity is shown, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 36, 37.

Le A 27 1~4 - 101 -

Claims

1. A sulphonylaminocarbonyltriazolinone of the general formula (I) (I) in which R1 represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical selected from alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents an optionally substituted radical selected from alkyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and dialkylamino, and R3 represents an optionally substituted radical selected from alkyl, aralkyl, aryl and heteroaryl, or a salt thereof.

2. Process for the preparation of a sulphonylaminocarbonyl-triazolinone of the general formula (I) as defined in Claim 1, which process comprises a) reacting triazolinone of the general formula (II) (II) in which R1 and R2 are as defined in Claim 1, with a sulphonyl isocyanate of the general formula (III) R3-SO2-N=C=O (III) in which R3 is as defined in Claim 1, or b) reacting a triazolinone derivative of the general formula (IV) (IV) in which R1 and R2 are as defined in Claim 1 and Z represents halogen, alkoxy, aralkoxy or aryloxy, with a sulphonamide of the general formula (V) R3-SO2-NH2 (V) in which R3 is as defined in Claim 1, or c) reacting a triazolinone of the general formula (II) (II) in which R1 and R2 are as defined in Claim 1, with a sulphonamide derivative of the general formula (VI) R3-SO2-NH-CO-Z (VI) in which R3 is as defined in Claim 1 and Z represents halogen, alkoxy, aralkoxy or aryloxy, and, where required, forming a salt thereof.

3. A herbicidal composition comprising a herbicidally effective amount of a compound according to Claim 1 in admixture with a suitable carrier or diluent.

4. A herbicidal composition comprising a herbicidally effective amount of a compound according to Claim 1 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.

5. 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 Claim 1.

6. 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 Claim 1 in admixture with a suitable carrier or diluent.

7. 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 Claim 1 in admixture with a suitable carrier or diluent.

8. 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 Claim 1 in admixture with a suitable carrier or diluent.

9. 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 Claim 1 wherein the compound is applied as a pre-emergence herbicide.

10. 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 Claim 1 wherein the compound is applied as a post-emergence herbicide.

11. 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 Claim 1 wherein the compound is applied to an area of cultivation at a rate of between 0.01 and 15 kg/ha.

12. 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 Claim 1 wherein the compound is applied to an area of cultivation at a rate of between 0.05 and 10 kg/ha.

13. A process for preparing a herbicidal composition comprising admixing a compound according to Claim 1 with a suitable carrier or diluent and/or a surface active agent.

14. A triazolinone of the general formula (IIa) (IIa) in which A1 represents in each case optionally substituted alkyl, alkenyl, cycloalkyl, alkoxy or dialkylamino and A2 represents hydrogen, or represents in each case optionally substituted alkyl, cycloalkyl, aralkyl, aryl or alkoxy, provided that both A1 and A2 do not simultaneously represent alkyl.