AU623037B2

AU623037B2 - Sulphonylaminocarbonyltriazolinones having substituents which are bonded via sulphur

Info

Publication number: AU623037B2
Application number: AU63601/90A
Authority: AU
Inventors: Peter Babczinski; Klaus-Helmut Muller; Hans-Joachim Santel; Robert R. Schmidt
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1989-11-03
Filing date: 1990-09-27
Publication date: 1992-04-30
Anticipated expiration: 2010-09-27
Also published as: CA2029132C; KR910009676A; DK0431291T3; EP0431291B1; BR9005572A; CA2029132A1; ES2118711T3; JPH03153675A; DE3936623A1; DE59010840D1; ZA908798B; EP0431291A2; AU6360190A; EP0431291A3

Description

Our Ref: 341386 I 63 0 3F7,o

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: S Related Art: Applicant(s): Bayer Aktiengesellschaft D-5090 Leverkusen Bayerwerk FEDERAL REPUBLIC OF GERMANY ARTHUR S. CAVE CO.

Patent Trade Mark Attorneys Level 10 Barrack Street SYDNEY NSW 2000 Address for Service: Complete specification for the invention entitled "Sulphonylaminocarbonyltriazolinones having substituents which are bonded via sulphur".

The following statement is a full description of this invention, including the best method of performing it known to me:- 1 5020 0 The invention relates to new sulphonylaminocarbonyltriazolinones having substituents which are bonded via sulphur, to a variety of processes for their preparation, and to their use as herbicides.

It is known that certain substituted aminocarbonylimidazolinones, such as, for example, 1-isobutylaminocarbonyl-2-imidazolidinone (isocarbamid), have herbicidal properties (cf. R. Wegler, Chemie der Pflanzenschutz-und und Schadlingsbekimpfungsmittel [Chemistry of Plant Protection Agents and Pesticides], Volume 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New S' York, 1977). However, the action of this compound is not satisfactory in all respects.

The new sulphonylaminocarbonyl-triazolinones 15 having substituents which are bonded via sulphur, of the formula (I) I0 R3 -02-NH-CO-N.N-R1

(I

S(0) -R in which n represents the numbers 0, 1 or 2, R represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical from the S' series comprising alkyl, alkenyl, alkinyl, cyclo- Salkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkyl- Le A 27 156 la amino, cycloalkylamino and dialkylamino,

R

2 represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aralkyl and aryl, and

R

3 represents an optionally substituted radical from Sthe series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula have now been found.

The new sulphonylaminocarbonyltriazolinones having substituents which are bonded via sulphur, of the general formula are obtained when a) triazolinones of the general formula (II) 0

HNI

t N-R1 N S(0)n-R2 in which n, R 1 and R 2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the general formula (III) i I R3-SO 2-N=C= 0

(II)

in which

R

3 has the abovementioned meaning, Sif appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) Le A 27 156 2 7 0 Z-CO- N)N-R1 S(O) 0)2

(IV)

in which n, R 1 and R 2 have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphonamides of the general formula (V)

R

3 -S0 2

-NH

2 t 10 in which

R

3 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) 0 HNiN-R1 nR2

(II)

in which n, R 1 and R 2 have the abovementioned meanings, are reacted with sulphonamide derivatives of the Le A 27 156 3 1 rllL IIII~ P~L~CCI-~ general formula (VI)

R

3

-SO

2 -NH-CO-Z (VI) o in which

R

3 has the abovementioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if desired, salts are formed by customary methods from the compounds of the formula (I) prepared by process or The new sulphonylaminocarbonyltriazolinones having substituents which are bonded via sulphur, of the general formula and their salts are distinguished by a powerful herbicidal activity.

Surprisingly, the new compounds of the formula have a considerably better herbicidal action than the herbicide l-isobutylaminocarbonyl-2-imidazolidinone (isocarbamid), which is known and has a similar structure.

the n

R

1 The invention preferably relates to compounds of formula in which represents the numbers 0, 1 or 2, represents hydrogen, hydroxyl or amino, or represents C 1

-C

6 -alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C 1

-C

4 -alkoxy, Ci-C 4 -alkylcarbonyl or C-C 4 -alkoxy-carbonyl, or represents C 3 -C6-alkenyl or C 3 -C-alkinyl, each of which is optionally substituted by fluorine, chlor- Le A 27 156 4 i7 ine and/or bromine, or represents C 3

-C

6 -cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C 4 -alkyl, or represents phenyl-Cl-C 3 -alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C 1

-C

4 alkyl, trifluoromethyl, Cl-C 4 -alkoxy and/or C 1

-C

4 alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Cl-C 4 -alkyl, trifluoromethyl, Cl-C 4 -alkoxy, fluorine- and/or chlorine-substituted Cl-C 3 -alkoxy, Cl-C 4 -alkylthio, fluorine- and/or phinyl, Cl-C 4 -alkylsulphonyl and/or C-C 4 -alkoxycarbonyl, or represents Cl-C6-alkoxy which is optionally substituted by fluorine, chlorine, cyano, phenyl, Cl-C-alkoxy or Cl-C 4 -alkoxy-carbonyl, or represents C 3

-C

4 -alkenyloxy, or represents Cl-C 4 alkylamino which is optionally substituted by fluorine, cyano, Cl-C 4 -alkoxy or Cl-C 4 -alkoxycarbonyl, or represents C 3 -C-cycloalkylamino or di- (Cl-C 4 -alkyl)-amino, R2 represents Cl-Cr-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C 3

-C

6 cycloalkyl, Cl-C 4 -alkoxy or Cl-C 4 -alkoxycarbonyl, or represents C 3

-C

6 -alkenyl or C 3

-C

6 -alkinyl, each of which is optionally substituted by fluorine, chlor- Sine and/or bromine, or represents C 3

-C

6 ,-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C 4 -alkyl, or represents cyclohexenyl, or represents phenyl-Cl-C 3 -alkyl which Le A 27 156 5 is optionally iubstituted by fluorine, chlorine, bromine, cyano, nitro, Cl-C 4 -alkyl, trif luoromethyl, Cl-C 4 -alkoxy and/or Cl-C 4 -alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C,-C 4 alkyl, trifluoromethyl, Cl-C 4 -alkoxy, fluorineand/or chlorine-substituted Cl-C 3 -alkoxy, C 1

-C

4 alkylthio, fluorine- and/or chlorine-substituted

C,-C

3 -alkylthio, Cl-C 4 -alkyl-sulphinyl, Cl-C 4 -alkylsulphonyl and/or Cl-Cj;.-alkoxy-carbonyl, and R 3 represents the group where R 4 and R 5 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, nitro, Cl-C.-alkyl (which is optionally substituted 6.'15 by fluorine, chlorine, bromine, cyano, carboxyl,

C-C

4 -alkoxycarbonyl, Cl-C 4 -alkylaxino-carbonyl, di- (Cl-C 4 -alkyl )amino-carbonyl, hydroxyl, Cl-C-alkoxy, formyloxy, Cl-C 4 -alkyl-carbonyloxy, Cl-C 4 -alkoxycarbonyloxy, Cl-C 4 -alkylamino-carbonyloxy, C 1

-C

4 alkylthio, Cl-C 4 -alkylsulphinyl, Cl-C 4 -alkylsulphonyl, di- (Cl-C 4 -alkyl) -aininosulphonyl, C 3 -C-CYCloalkyl or phenyl) or represent C 2 -C-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C 4 -alkoxy-carboniyl, carboxyl or phenyl) or J'4 25represent C 2

-C

6 -alkinyl (which is optionally substi- 6~ tuted by fluorine, chlorine, bromine, cyano, C 1

-C

4 alkoxy-carbonyl, carboxyl or phenyl), or represent Le A 27 156-6 6 Cl-C 4 -alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1

-C

4 alkoxy-carbonyl, Cl-C-alkoxy, Cl-C 4 -alkylthio, C 1

C

4 alkylsulphinyl or Cl-C 4 -alkylsulphonyl), or represent Cl-C 4 -alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C 1

-C

4 alkoxy-carbonyl, Cl-C 4 -alkylthio, Cl-C 4 -alkylsulphinyl or Cl-C 4 -alkylsulphonyl), or represent C 3 -C,,-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C 4 -alkoxy-carbonyl) or represent C 2 -C,-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, Cl-C 3 -alkylthio or Cl-C 4 -alkoxycarbonyl)

C

3

-C

6 -alkinyloxy or C 3

-C

6 -alkinylthio, or represent the radical -S(O)P-R 6 where p represents the numbers 1 or 2 and represents CI-C 4 -alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C 4 -alkoxy-carbonyl), C 3 -C-alkenyl,

C

3

-C

6 -alkiflyl, Cl-C 4 -alkoxy, C 1

-C

4 -alkoxy-Cl-C 4 alkylamino, CI-C 4 -alkyl amino, di- (C,-C-alkyl) amino or phenyl, or represents the radical -NHOR 7 where R 7 represents Cl-Cl.-alkyl (which is optionally substituted by fluorine, chlorine, cyano,

C,-C

4 -alkoxy, Cl-C 4 -alkylthio, Cl-C 4 -alkylsulphinyl, Cl-C 4 -alkylsulphonyl, Cl-C 4 -alkylcarbonyl, Cl-C 4 -alkoxycarbonyl, Cl-C 4 -alkylamino-carbonyl or di-- (Cl-C 4 -alkyl -aminocarbonyl) or represents C 3

-C

6 -alkenyl (which 220 3.O 30 Le A 27 156-7 7

I

200 is optionally substituted by fluorine, chlorine or bromine) C.-C-alkinyl, C 3

-C

6 cyc loalkyl, C.-C-cycloalkyl-Cl-C 2 -alkyl, phenyl-Cl-C 2 -alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C-C 4 -alkyl, Cl-C 4 -alkoxy or C 1

-C

4 alkoxy-carbonyl), or represents benzhydryl, or represents phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, Cl-C 4 -alkyl, trifluoromethyl, C 1

-C

4 alkoxy, C 1

-C

2 -fluoroalkoxy, Cl-C 4 -alkylthio, trif luoromethylthio or Cl-C 4 -alkoxycarbonyl) R 4 and/or R 5 furthermore represent phenyl or phenoxy, or represent C 1

-C

4 -alkylc arbonyl amino, C 1

-C

4 alkoxycarbonylamino, Cl-C 4 -alkylamino-carbonylamino or di- (C 1

-C

4 -al kyl) -amino -c arbonylamino, or represent the radical -CO-R 8 where R represents C-C 6 -alkyl, Cl-C-alkoxy, C 3

-C

6 cycloalkoxy, C 3 -C-alkenyloxy, C 1

-C

4 alkylthio, C 1

-C

4 -alkyl amino, Cl-C 4 -alkoxyamino, C 1

-C

4 alkoxy-Cl-C 4 -alkyl -amino or di- (C-C 4 -alkyl) amino (each of which is optionally substituted by fluorine and/or chlorine), R 4 and/or R 5 furthermore represent trimethylsilyl, thiazolinyl, Cl-C 4 -alkylsulphonyloxy or di- (Cl-C 4 alkyl)-aminosulphonylamino, or represent the radical -CH=N-Rg where

R

9 represents Cl-C 6 -alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, Cl-C 4 -alkoxy, Cl-C-alkylthio, C 1

-C

4 Le A 27 156- 8 alkylsulphinyl or C 1

-C

4 -alkylsulphonyl, or represents benzyl which is optionally substituted by fluorine or chlorine, or represents C 3

-C

6 -alkenyl or C 3

-C

6 -alkinyl, each of which is optionally substituted by fluorine or chlorine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C 1

-C

4 -alkyl, Ci-C 4 -alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C 1

-C

6 -alkoxy, C 3 -C.-alkenoxy, C 3 -C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, C 1 alkylamino, di-(C -C 4 -alkyl) -amino, phenylamino, CI-C 4 -alkyl-carbonyl-amino, Ci-C,alkoxy-carbonylamino or C 1

-C

4 -alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally eubstituted by fluorine, S chlorine, bromine or methyl, furthermore

-CH

R

3 represents the radical where

R

10

R

11

R

1 represents hydrogen or C 1

-C

4 -alkyl,

R

1 and R 12 are identical or different and represent S hydrogen, fluorine, chlorine, bromine, nitro, cyano, Ci-C 4 -alkyl (which is optionally substii tuted by fluorine and/or chlorine), Cl-C 4 -alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, C 1

-C

4 -alkoxy-carbonyl, Le A 27 156 9 dimethylaminocarbonyl, Ci-C 4 -alkylsulphonyl or di- (Ci-C 4 -alkyl)-aminosulphonyl; furthermore

R

3 represents the radical R 13 I 14 where

R

13 and R 14 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Ci-C 4 -alkyl (which is optionally substituted by fluorine and/or chlorine) or Ci-C 4 -alkoxy (which is optionally substituted by fluorine and/or chlorine); furthermore R 1

R

3 represents the radical where

R

16 R1 5 and R 16 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C,-C 4 -alkyl (which is optionally substituted by fluorine and/or chlorine), Ci-C,alkoxy (which is optionally substituted by fluorine and/or chlorine), or represents Ci-C,i alkylthio, Ci-C 4 -alkylsulphinyl or Ci-C 4 -alkylsulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represents aminosulphonyl, mono-(Ci-C 4 -alkyl)-aminosulphonyl, or represents di-(Ci-C 4 -alkyl)-aminosulphonyl or Ci-C 4 -alkoxycarbonyl or dimethylaminocarbonyl; furthermore

R

3 represents the radical R 1 7 i18 where Le A 27 156 10

II___L

R

17 and R 18 are identical or different and represent hydrogen, fluorine, chlorine, bromine, Cl-C 4 -alkyl (which is optionally substituted by fluorine and/or bromine), C 1

-C

4 -alkoxy (which is optionally substituted by fluorine and/or chlorine), or represent i Ci-C 4 -alkylthio, Ci-C 4 -alkylsulphinyl or Ci-C 4 -alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), or represent di-(Ci-C 4 alkyl)-aminosulphonyl; furthermore

R

1 9

R

3 represents the radical 20 where

R

19 and R 20 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C 1

-C

4 -alkyl (which is optionally substituted by fluorine and/or chlorine), CI-C 4 -alkoxy (which is optionally substituted by fluorine and/or chlorine), Ci-C 4 -alkylthio, C 1

-C

4 -alkylsulphinyl or Ci-C4-alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C -C 4 -alkyl)-amino-sulphonyl, Ci-C 4 -alkoxy-carbonyl or dimethylaminocarbonyl, and A represents oxygen, sulphur or the group N-Z 1 where

Z

1 represents hydrogen, Ci-C 4 -alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C 3

-C

6 -cycloalkyl, benzyl, phenyl (which is optionally substituted by Le A 27 156 11 -P 1_ I~ fluorine, chlorine, bromine or nitro), C 1

-C

4 alkylcarbonyl, Ci-C 4 -alkoxy-:arbonyl or di- (Ci-C 4 -alkyl)-aminocarbonyl; furthermore

R

2 1

-N

R

3 represents the radical 22 where

R

21 and R 22 are identical or different and represent hydrogen, C 1

-C

4 -alkyl, halogen, C 1

-C

4 -alkoxycarbonyl, C 1

-C

4 -alkoxy or C 1

-C

4 -halogenoalkoxy, Y1 represents sulphur or the group N-R 23 where

R

23 represents hydrogen or Cl-C 4 -alkyl; furthermore 26

R

2 6

R

3 represents the radical where

R

2 2424

R

2 represents hydrogen, C 1

-C

4 -alkyl, benzyl, pyridyl, quinolinyl or phenyl,

R

25 represents hydrogen, halogen, cyano, nitro, Ci-C 4 -alkyl (which is optionally substituted by j fluorine and/or chlorine), C 1

-C

4 -alkoxy (which is optionally substituted by fluorine and/or 20 chlorine), dioxolanyl or C 1

-C

4 -alkoxy-carbonyl and

R

26 represents hydrogen, halogen or Ci-C 4 -alkyl; furthermore Le A 27 156 12

R

3 represents one of the groups listed below,

H

3 CO -C

H

3 C -CH2CF S'N-CdHq NSO CH 2

CF

3 1 The invention furthermore preferably relates to sodium salts, potassium salts, magnesium salts, calcium salts, ammonium salts, C 1

-C

4 -alkyl-ammonium salts, di-(C 1

-C

4 -alkyl) -ammonium salts, tri-(Ci-C 4 -alkyl) -ammonium salts, C 5 or C.-cycloalkyl-ammonium salts and di-(C-C 2 alkyl)-benzyl-ammonium salts of compounds of the formula in which n, R 1

R

2 and R 3 have the meanings indicated above as being preferred.

0 In particular, the invention relates to compounds of the formula in which n represents the numbers 0, 1 or 2,

R

1 represents hydrogen or amino, or represents Cl-C 4 alkyl which is optionally substituted by fluorine, 5 cyano, methoxy or ethoxy, or represents allyl, or represents C 3

-C

6 -cycloalkyl, or represents benzyl, or represents phenyl, or represents Ci-C 4 -alkoxy, or represents C 3

-C

4 -alkenyloxy, or represents C1-C 3 alkylamino, C 3

-C

6 -cycloalkylamino, or represents di- 0 (Ci-C 3 -alkyl) -amino, S1 Le A 27 156 13

R

2 represents hydrogen, or represents C 1

-C

4 -alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C 3

-C

4 -alkenyl which is optionally substituted by fluorine and/or chlorine, or represents C 3

-C

6 -cycloalkyl, or represents benzyl which is optionally substituted by fluorine, chlorine and/or methyl, and

R

3 represents the group where

R

4

R

4 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxyethoxy, Ci-C 3 -alkylthio, C-C 3 -alkylsulphinyl, Ci-C 3 -alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, methoxyaminosulphonyl, phenyl, phenoxy or C 1

-C

3 -alkoxy-carbonyl, and

R

5 represents hydrogen, fluorine, chlorine or bromine; furthermore Rl 1 R12

R

3 represents the radical where R1 0 represents hydrogen, R" represents fluorine, chlorine, bromine, methyl, Le A 27 156 14 methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and

R

12 represents hydrogen; furthermore

R

3 represents the radical RO-C S

IO

0 where R represents C 1 -C-alkyl, or represents the radical 0

II

RO- C

N-N

I

a oo o o where R represents Cl-C 4 -alkyl. CH 3 Examples of the compounds according to the invention are listed in Table 1 below cf. also the Preparation Examples.

0 R3-SO2-NH-CO-NJN-R 1 .|0I lN-- S(O0)R2 !i Le A 27 156 15 Table 1: Examples of the compounds of the formula (I) CH3

F

C CH3 CH3 C 1 C CH3 CH3 CH3 OCHF2 C S02N(CH3)2 COOCH3 H2- CH3 CH3 CH3 Le A 27 156 16 Table 1: (Continuation)

PR

1

R

2

R

3 n

CH

3

C

2

H

5 I 0 S OOCH 3 CH- C H 5 0 2

C

2

H

5

C

2

H

5 /0'

CF

3

*C

2

H

5

C

3

H

7 0 S *l

CH

3

H

2 0

OCH

2

CH

2 C 1

KNJC

2

H

5 ~0

CH(CH

3 2 c~ CON(CH 3 2 0 Le A 27 156 -1 17 7 Table 1: (Continuation)

CH

3

CH

3 C2H CH C CH 3 )2

CH

2

-CH=CH

2

CH

3

C

2

H

C

2

H

caI S0 2

NH

2 SCH (CH 3 )2 S0 2

CH

3

F

S i (CH3 3 a a A a a r,

CH

3 'a a

OCF

3

C

3

H

7 H 2

C

2

H

5

CH

3 C 2

H

YI'NaCO(H) a, a Le A 27 156 18 7 Ta-ble 1: (Continuation)

CH

2

CH

3

C

2

H

5 Br

OCH

2

CH

2

-OCH-

3

CH

3

CH

3 01 0 0 0

CH

-KD

CH

3

C

3

H

7 -n

C

2

H

SO

2

N(CCH

3 )2

OCHF

2

H

2

COOCH(CH

3 2 Cl 4 I I Le A 27 156 19 Table 1: (Continuation)

CH

3

CH

3

CH

3

CH

3

C

2

H

COOC

2

H

\H

C

CH

2

-CECH-

N

CH

3 C 2

H

C

2

H

5

CH

3 2CF

COOCH

3 NNN

CH

S. I SI S I S I Le A 27 156 20 Table 1: (Continuation) CH3

CH-

3 2, C 1

CH

3

C

2

H

5

CH-

2

-CH=CH

2

CH

2

-CH=CH

2 C3H7~~ H3C_: CON (CH 3 2

C

2

H

C

2

H

CH-

3 cS- OO 0CH 3

COOCH

3 ClI I, I I, I

OCH

3 0C 2

H

5

CH

3

C

2

H

COOCH

3

SO

2

NCH

3

(OCH

3 I I I III II S I I I Le A 27 156 21 Table 1: (Continuation) Rl R2 R3n

CH

3 0C 3

H

7

CH

2

-CH=CH

2

C:_

OCH

3

CH

3

CH

3 0 Cl

CH

3 Br

C

2

H

5 /0 o CH 3 cl 1 C 2 H C 2

H

5 0 0 2.CH 3

C

2

H

*0 02 Le A27 156 22 Table 1: (Continuation) RI 2R OC HF 2

CH

3

C

3

H

7

H

2 0

OCH

3

CH

3 E7 COCH 3 0

OCH

3 0C 2

H

5

CH

3 0 0CH 2

CH

2 -C 1 0C 2

H

5

C

2

H

5 \0 0.i F 0-CH 2 -CH2CH 2

C

2

H

5 /0'

CH

3

C

2

H

5 0

CH

3

CH

3

CF

3 0 Le A 27 156 23 Table (Continuation) N (CH 3 2

CH-

3 o 0 S0 2

NH

2

CH

3

C

2

H

5 0

CM

3

SO

2

NH

2

CM

3

C

2

H

5 01 NO- CF 2

-CF

2

C

OCH

2

CM

2 -C 1

N(CH

3 2 C 0 Le A.27 156 24 If, for example, 2,6-difluoro-phenyl isocyanate and 5-ethylthio-4-methoxy-2,4-dihydro-3H-l,2 ,4-triazol- 3-one are used as starting substances, the course of the reaction in process according to the invention can be outlined by the following equation:

F

-,S0 2 -N=C~0

F

0 H-N- N-NOCH 3

-SC

2

H

F 0 C\ S0 2 -NH-CO1N'jN)-OCH 3 F 3 C 2

H

if, for example, 2-methylthio-benzenesulphonamide and 2-chlorocarbonyl-4-dimethylamino-5-propylthio-2 ,4dihydro-3H-l,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (b) according to the invention can be outlined by the followirg equation:

I.,

.1

SCH

3 C -S0 2 -NH2 0 C C- C 0 N'i-N (C H1) 2

SC

3

H

7

-HC.

SCH

3 0 S2N-O-N N-(H42

-SC

3

H

7

I

C,

Le A 27 156 25 If, for example, N-methoxycarbonyl-2-methoxybenzenesulphonamide and 5-methylsulphonyl-4-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process according to the invention can be outlined by the fo lowing equation:

OCH

3 j 'S0 2

-NH-COOCH

3

SO

2

CH

3

OCH

3 0 CH -S0 2

-NH-CO-N"N-CHF

2 -HOCH3

S

2

CH

3 Formula (II) provides a general definition of the triazolinones to be used as starting substances in processes and according to the invention for the preparation of compounds of the formula In Formula n, R 1 and R 2 preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the I Le A 27 156 26 compounds of the formula according to the inve 7 ~ntion as being preferred, or particularly preferred, for n, R and R 2 Examples of the starting substances of the formula (II) are listed in Table 2 below.

0 HN)'N-R1 S n-R

(II)

Table 2: Examples of the formula (II) starting substances of the

I

.tIj C H 3

C

2

H

5

C

3

H

7

CH

3

CH

3

CH

3

CH

3

CH

3

CH

3 A 04

CH(CH

3 2

C

4

H

9 Le A 27 156 27 Table 2: (Continuation Rl

CHK

CH

3

CH

3

CH

3

CH

3 I, gj

~,II

*I

I

III

I'

CH

3

C

2

H

5 C3H

CH

2

CH=CH

2

CH

2 -CHBr-CH- 2 Br

CH

3

C

2

H

C

3

H

7 CH C CH 3 2

CH

2

CH

2 C CH

C

2

H

C

2

H

C

2

H

C

2

H

C2H C 3

H

7

CH

2

CH=CH

2 I I I I I I

I

II I~ II I I

I

Le A27 156 28 Table 2:-(Continuation

C

2 1H 5

C

3

H

7

CH

2

-CH=CH

2

C

2

H

5

C

3

H

7

OCH

3

OCX

3 CHC (C 3 2

CH(CCH

3 )2 CH C CH 3 2

C

3

H

7

C

3

H

7

-CH

2

-C--CX

C

3

H

7

CX

3

C

2

H

0 a 0 0 00 Le A 27 156 29 The starting substances of the formula (III) are known and/or can be prepared by processes known per se (cf. J. Heterocycl. Chem. 15 (1978), pp. 377-384; DE-OS (German Published Specification) 2,250,572; DE-OS (German Published Specification) 2,527,676; DE-OS (German Published Specification) 3,709,574; US Patent 4,098,896; US Patent 4,110 332; JP-A-52-125 168).

Formula (III) provides a general definition of the sulphonyl isocyanates also to be used as starting substances in process according to the invention for the preparation of compounds of the formula In formula (III), R 3 preferably, or in particular, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula according to the invention as being preferred, or particularly preferred, for R 3 Examples of the starting substances of the formula (III) which may be mentioned are: 2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2- 20 trifluoromethyl-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-Nmethyl)-aminosulphony.-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-isopropoxycarbonyl-phenylsulphonyl isocyanate, 2fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl isocyanate, 2-methoxycarbonyl-3-thienyl-sulphonyl isocyanate, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1- Le A 27 156 30 The sulphonyl isocyanates of the formula (III) are known and/or :an be prepared by processes known per se (cf. US Patent 4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, i 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, j 173,312).

Process according to the invention for the i preparation of the new compounds of the formula is i 10 preferably carried out using diluents. Suitable diluents i for this purpose are virtually all inert organic solvents. These preferably include aliphatic and aromatic, ii optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, 1 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, 20 ketones, such as acetone, methyl ethyl ketone, methyl Sisopropyl 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-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.

In process according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at Le A 27 156 31 11 temperatures between 0°C and 150°C, preferably at temperatures between 10 0 C and 80 0

C.

Process according to the invention is generally carried out under atmospheric pressure.

For carrying out process 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 the product is isolated by filtration with suction. In another work-up variant, the mixture is concentrated, and the crude product which remains in the residue is crystallized with a suitable solvent, such as, for example, diethyl ether. The product of the formula which in this process is obtained in crystalline form, is isolated by filtration with suction.

S' Formula (IV) provides a general definition of the 20 triazolinone derivatives to be used as starting sub- S. stances in process according to the invention for the preparation of compounds of the formula In formula n, R' and R 2 preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula according to the invention as being preferred, or particularly preferred, for n, R 1 and R 2 and Z preferably represents chlorine, Ci-C 4 -alkoxy, benzyloxy or phenoxy, in particular methoxy or phenoxy.

Le A 27 156 32 i Possible examples of the starting substances of formula (IV) are the compounds of the formula (IV) 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) were hitherto unknown.

The new triazolinone derivatives of the formula (IV) are obtained when triazolinones of the general formula (II) 0

-R

2 (0 n

(II)

0 15 i, in which n, R 1 and R 2 have the abovementioned meanings, are reacted with carbonic acid derivatives of the general formula (XI)

Z-CO-Z

1

(XI)

in which Z has the abovementioned meaning and

Z

i represents a leaving group, such as chlorine, methoxy, benzyloxy or phenoxy, if appropriate in the presence of a diluent, such as, for Le A 27 156 33 2 example, tetrahydrofuran, and if appropriate in the presence of an acid acceptor, such as, for example, sodium hydride or potassium tert-butylate, at temperatures between -20"C and +100 0 C (cf. also the Preparation Examples).

Formula provides a general definition of the sulphonamides also to be used as starting substances in process according to the invention for the preparation of compounds of the formula In formula R 3 preferably, or in particular, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula according to the invention as being preferred, or particularly preferred, for R 3 Examples of the starting substances of the formula which may be mentioned are: 2-fluoro-, 2-chloro--, 2-bromo-, 2-methyl-, 2-methoxy-, 2trifluoromethyl-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-Nmethyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2 -isopropoxycarbonyl-benzenesulphonamide, 2-fluoro-, 2chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2methoxycarbonyl- and 2-ethoxycarbonyl-phenylmethanesulphonamide, 2 -methoxycarbonyl-3-thiophenesulphonamide, 4methoxycarbonyl- and 4 -ethoxycarbonyl-l-methyl-pyrazol- 30 The sulphonamides of the formula are known A I I Le A 27 156 34 and/or can be prepared by processes known per se (cf.US Patents 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, 173,312).

In process according to the invention, preparation of the new compounds of the formula is preferably carried out using diluents. Diluents which are suitable for this purpose are virtually all inert organic solvents, for example those which have been indicated above for process according to the invention.

Acid acceptors which can be employed in process according to the invention are all acid-binding 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 j carbonate, potassium carbonate, sodium tert-butylate and '20 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), 1,8diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo[2,2,2]-octane (DABCO).

In process according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100 0 C, preferably at temperatures between 10 0 C and 60 0

C.

Le A 27 156

A

X'W

In general, process according to the invention 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 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 components employed in each case 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. In process according to the invention, working-up is carried out in each case by customary methods.

The triazolinones of the formula (II) to be used as starting substances in process according to the invention for the preparation of compounds of the formula have already been described as starting substances for process according to the invention.

Formula (VI) provides a general definition of the sulphonamide derivatives also to be used as starting 0 substances in process according to the invention for the preparation of compounds of the formula In formula R 3 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 or according to the invention as being preferred, or particularly preferred, for R 3 and Z.

Le A 27 16 36 Le A27 1§6 36 Process according to the invention is preferably carried out using diluents. The same organic solvents which have been mentioned above in connection with the description of process according to the invention are suitable for this purpose.

If appropriate, process is carried out in the presence of an acid acceptor. The same acid-binding agents which have been mentioned above in connection with the description of process according to the invention are suitable for this purpose.

In process according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10 0 C and 60 0

C.

In general, process according to the invention is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.

I

For carrying out process 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 suitable diluent in the presence of an acid acceptor, and i the reaction mixture is stirred for several hours at the specifically required temperature. In process according to the ir-,ention, working-up is carried out in each case by custom"y methods.

Le A 27 156 37 For converting 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, dibutylamine or triethylamine, in suitable diluents, such as, for example, water, methanol or ethanol. The salts can be isolated as crystalline products then if appropriate after concentration.

The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers. By weeds, in the broadest sense, there are 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 used, for example, in connection with the following plants: Dicotyledon weeds of the genera: 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, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Le A 27 156 38

I

Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, i Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Pagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus 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 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 tree plantings.

20 Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop-fields, on lawn, turf and pasture-land, and for the selective combating of weeds in annual cultures.

In particular, the compounds of the formula (I) according to the invention are suitable for selectively combating monocotyledon and dicotyledon weeds in mono- Le A 27 156 39 cotyledon crops, either using the pre-emergence or the post-emergence method. They are markedly more effective than, for example, isocarbamid.

To a certain extent, the compounds according to the invention also show fungicidal action, for example against Pyricularia on rice.

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 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 agents, that is emulsifying agents and/or dispersing agents and/or foamforming agents.

In the case of the use of water as an extender, S: organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, j such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, mer.hyl ethyl ketone, methyl Le A 27 156 40 isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such 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 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 suitable: 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 ligninsulphite 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 Le A 27 156 41 _1 I--*dj /i 9 1" i r r i r :i i pigments, 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, manganese, 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 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 herbicides, such as, for example, l-amino-6-ethylthio-3- (2,2-dimethylpropyl)-1,3,5-triazine-2,4-(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethylurea (METABENZTHIAZURON) for combating weeds in cereals; 4amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet, and 4amino-6-(1,1-dimethylethyl)-3-methylthio-l,2,4-triazin- 5(4H)-one (METRIBUZIN) for combating weeds in soya beans; furthermore also 2,4-dichlrophenoxyacetic acid 4-(2,4-dichlorophenoxy)-butyric acid 2,4-dichlorophenoxypropionic acid 3-isopropyl-2,1,3benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl (2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); 2-chloro- N{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-car- 30 bonyl}benzenesulphonamide (CHLORSULFURON); N,N-dimethyl- .4 4' 4 4' I 4' 4I ,Le A 27 156 42 N'-(3-chloro-4-methylphenyl)-urea (CHIORTOLURON); 2-[4- (2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 4-ainino-6-t-butyl- 3-ethylthio-1, 2,4-triazin-5(4H) -one (ETHIOZIN) (6chloro-2--benzoxazolyl)--ox-]-phenoxv}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); [(4-amino- 3,5-dichloro-6-f luoro-2-pyridin-yl) -oxy] -acetic acid or its 1-methyiheptyl ester (FLUROXYPYR) N-phosphonomethylglycin (GLYPHOSATE) methyl 2- [4,5-dihydro-4-methyl-4- (1methylethyl)-5-oxo-lH-iinidazol-2-yl]-4(5)-methylbenzoate (IXAZAI4ETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N,N-dimethyl-N'-(4.-isopropylphenyl)-urea (ISOPROTURON); (2-methyl-4-chlorophenoxy) -acetic acid (MCPA) (4-chloro-2-methylphenoxy) -propionic acid (MCPP) N-methyl-2-(l,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET) [C(4-methoxy-6-methyl-l,3,5-triazin-2yl) amino) -carbonyl ]-amnino] -sulphonyl}-benzoic acid or its 00a methyl ester (METSULFURON); N-(1-ethylpropyl)-3,4-di- O methyl-2,6-dinitroaniline (PENDIMETHALIN); 0-(6-chloro- 3-phenyl-pyridazin-4-yl)-S-octy1 thiocarbainate (PYRIDATE); 4-ethylamino-2-t-butylainino-6-methylthio-striazine (TERBUTRYNE) and methyl 3-[[[[(4-methoxy-6- 0~0~ methyl-I, 3, 5-triazin-2-yl) -amino] -carbonyl]J-amino] sulphonyl]-thiophene-2-carboxylate (THIAI{ETURON). Surprisingly, some mixtures also show synergistic action.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.

II 30 The active compounds can be used as such, in the Le A 27 156 43 r A 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 soil before sowing.

The amount of active compound used can vary within a substantial 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.

Prenaration Examoles

I

1 Example 1

COOCH

3 0

SO

2

-NH-CO-N

1

N-CH

3

N-S-CH

3 (Process g (20.7 mmol) of 4-methyl-5-methylthio-2,4dihydro-3H-1,2,4-triazol-3-one are dissolved in 60 ml of I I I I Le A 27 156 44 acetonitrile, and 7.0 g (29 mmol) of 2-methoxycarbonylphenylsulphonyl-isocyanate, dissolved in 20 ml of acetonitrile, are added to this solution with stirring.

The reaction mixture is stirred at 20 0 C for 6 hours. The product which is obtained in crystalline form is then isolated by filtration with suction.

This gives 6.0 g (75 of theory) of methylthio-2-(2-methoxycarbonyl-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-l,2,4-triazol-3-one of melting point 184 0

C.

Example 2

OCF

3 0

"-SO

2

-NH-CO-N/)-N-NH

2

N--'S-CH

3 (Process 1.7 g (11.2 mmol) of 1,8-diazabicyclo-[5,4,0]undec-7-ene (DBU) and 2.7 g (11.2 mmol) of 2-trifluoromethoxybenzenesulphonamide are added to a solution of g (11.3 mmol) of 4-amino-5-methylthio-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one in 60 ml of methylene chloride. The reaction mixture is stirred for 4 hours at 20"C, then washed twice with 1 strength hydrochloric acid and three times with water, dried with sodium sulphate, and filtered. The filtrate is concentrated, the residue is stirred with diethyl ether, and the product which is obtained in crystalline form is Le A 27 156 45 2 Tlisolated by filtration with suction.

This gives 2.1 g (45 of theory) of 4-amino-5-methylthio-2-(2-trifluoromethoxy-phenylsulphonyl-aminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 136°C.

For example, the compounds of the formula (I) listed in Table 3 below can also be prepared analogously to Examples 1 and 2 and following the general description of the preparation processes according to the invention.

0 R3-SO2-NH-CO*N''N-(R 1 n-R 2 4 *C

C.

Le A 27 156 46

-A

Table 3: Preparation Excamples of the compounds of the formula (I) Ex.

No.

n Melting point 0

C)

3

CH

3

C

2

H

4

CR

3

CR

3

CH(CH

3 2

CH

2

CH=CH

2

V

CCOCH

3

COOCH

3 COaCH 3 COaCH 3

CI,

COaCH 3

COOCH

3 140 6 C 2

H

5

C

2

H

5 7 C 2

H

5

CH

3 8 C 2

H

5

CH

2

C

6

H

5 128 167 185 Le A 27 156 47 Table 3: (Continuation) Ex. R'R2 No.

n Melting point OC) 9

CH

3

CH

2

C

6

H

5 C H 2 C 6H 5

CH

3

COOCH

3

COOCH

3

COOCH

3 143 I1I CH (CH 3 2 12

Q

C I

CH

3 1.42

DCH

3

CR

3

COOCH

3 13 CR 3

C

3

H

7

COOCH

3 14 C 2 HS -CH 2

CH=CH

2 205 142 ill Le A 27 156 48 2 Table 3: (Continuation) Ex. R 1 No.

n Melting point 0

C)

C

2 HSi

C

3

H

7 16 C 2

H

5

CH(CH-

3 2 17

CH

3

CH

3

COOCH

3

COOCH

3

OCF

3

COOCH-

3

COOCH

3

COOCH

3

OCF

3 C5\ 150 125 18 C 3 1-1 7

-CH

2

CH=CH

2 19 C 3

H

7

C

3

H

7 137

C

3

H

7

CH(CH

3 2 121 133 21

CH

3 C2H Le A 27 156 -4 49 Tabl -1 (Continuation) Ex.

No.

n Melting point C) 22 -CH 2

CH=CH

2 23 C 3

H

7 24 CH (CH3 32 S I

COOCH

3

CH

COOCH

3

COOCH

3 ,C OCH-

CF

COOCH

3 163

C

3

H

7

CH-

3 26 CIH, C 2

H

5 130C 27< 28<

C

2

H

5

CH.

3 173 4 Os Le A 27 156 50 Table (Continuation) Ex.

RI

No.

n M~elting point 0

C)

29 -CH 2

-CH=CH

2

CH

3

-CH

2

-CH=CH

2

C

2

H

5 31 -c 32<

COOCH

3

COOCH

3

OCF

3

OCF

3

COOCH

3 128

OH

3

C

2

H

5 182 152 33

CH

3

CH

3 34

CH

3

C

2

H

5

I

CH3 138 Le A- 27 156 52- 51 2 Table 3: (Continuation) Ex. R' No.

n Melting point OC)

CH

3

CH

3 1

CH

3

COOCH

3 36 -CH 2

-CH=CH

2

-CH

2

-CH=CH

2 C 5 101 3-~ 38<

OH

3

C

2

H

5 CH3

CH

3

O

3

OCF

3 190 163 163 133 39 -CH 2

-CH=CH

2

OH

3

-CH

2

-CH=CH

2

C

2

H

5 Le A 2 7 156 52 Table 3: (Continuation) Ex. R' No.

n Melting point (COC)

OC]F

3 41

CH

3

C

3

H

7 13 3

OCR

3 42 C 2

H

5

-CH

2

-CH=CH

2 43 20

C

3

H

7

OCF

3

COOCH

3 44 -CH 2

-CH=CH

2

C

3

H

7

COOCH

3

-CH

2

-CH=CH

2

CH(CH

3 2 *4 4 46

OH

3 C I

CH(CH

3 2

CH

3 I St Le A 27 156 53

-U,

Table (Continuation) Ex. Rl R 2 3n M.'elting No. point 0

C)

47 -CH 2

-CH=CH

2 CH3~ 0 1.65

OH

3 48

-CH

2 -CH=CH 2

C

2

H

5 9 Cl

OH

3 49 51

C

2

H

5

I

C H H 3 2-

OH

3

OH

3 c 2

HS

CHl

OH

3 Cl

CH

3 1.40 131 168 1.29 52 C 2

H

5 Le A 27 156 54 Table 3: (Continuation) Ex. R'R2 No.

n M~elting point 0

C)

53

OH

3 0 3

H

7 1

CH

3 146 125 54

OH

3

I

-CH

2 -CH=0H 2

OH

3 C i

-CH

2

-CH=CH

2

OH

3 20 25 56 C 2

H

5 57 C 2

H

5 141 122 C 3

H

7 1

OH

3 I I 1

-CH

2 -C2H=CH 2

OH

3 58 -CH 2 -cx=CH 2

-CH

2

'-OH=CH

2 CH 3 Le A 27 156 55 Table 3: (Continuation) Ex.- R' No.

n M~elting point 0

C)

59 -CH 2

-CH=CH

2

C

3

H

7

I

OH

3 102 c 1

-CH

2

-CH=CH

2

CH(CH

3 2

CH

3 122 61

CH

3 62 CH, 63 64 c H C CH 3 2

-CH

2 -CH=

OH

2

-CH

2 -CH=

OH

2

CH(CCH

3 )2 OCF3 \3

OCF

3 04 Ile A 27 156 56 Table 3: (Continuation) Ex. R' No.

n M~elting point OC)

C

2

N

5

CH

3 66 C 2

H

5 3

C

2

H

5 0CF 3 OCr3

OCF

3 67 -CH 2 -CH= CH 2

C

3

H

7 138 69 a27 117 68 C 2

H

5 03 )H7 69 -CH 2

-CH=CH

2

CH(CH

3 2 I IV

OCF

3 70 -CH 2

-CH=CH

2

-CH

2

-CH=CH

2 Le A 27 156 57 7 Table 3: (Continuation) Ex. R I n Melting point OC) 71 C 2

H

5

CH(CH

3 2

CH

3

SX--'COOCH

3 72

OH

3

CH

3 193- 194 73

CH

3 74 0 2

H

5

OH

3

COOCH

3 I COOCH 3 176-177 1 175- 177

C

2

H

5 Es COOCH 3 153-155 Le A 27 156 58 Table 3: (Continuation) EX. R R No.

n Melting point 0

C)

76 N(CH 3 2 77 N(CH 3 2

OH

3

C

2

H

5

COOCH

3

COOCH

3 178-179 124-136 7 78 CH 3 F1- ICOOC 2

H

5 188- 191

CH

3 79

OH

3

CH

3 Br 176- 179 154-156

OH

3

O

2

H

5 4 6 Le A 27 156 59 Table 3: (Continuation) Ex. R' No.

n M~elting point CC) 81 82

CH

3 S 83 OH:q 3 84<

OH

3

C

2

H

5

OH

3

OH

3

C

2

H

5 Br Br

OH

3

OH

3 192-195 151-154 157 168 132

II

S S S Le A 27 156 -6 60 Table 3: (Continuation) Ex.

RI

No.

n M~elting point 0

C)

86

CH

3

C

2

H

5

COOCH

3 87-CH 2

-CH=CH

2

-CH

2 -CECH 0 88

-K

CH

2

CECH

CH

2 C C H

COOCH

3

CGOCH

3 i228 3 1 89,

CH

3 143-144

CH

3

CH

3

CH(CCH

3 2 1 07-109 Br 91 CH 3

-CH(CH

3 2 103-104 Le A 27 156 61 Table 3: (Continuation) Ex. Rl No.

n Melting point OC) 92

CH

3 CH (CH 3 2

CF

3

CF

3 114-117 25 9-K

CH

3 194-195 94<

CF

3 N 150- 152 ,0 3

CH

3

C

2

H

5 146-148 4 zV1 Le A 27 156 62 Starting substances of the formula L;I Example (II-1) 0 H-Ni -N-CH 3

_S-CH

3 S tep 1

S

11

CH

3 -NH-C-NH-NH-C00C 2

H

A solution of 175 g (2.4 mol) of methyl isothiocyanate in 300 ml of diethyl ether is added to a solution of 250 g (2.4 mol) of ethyl hydrazinoformate, with stirring. The reaction mixture is stirred for 12 hours at and then cooled to about 10 0 C, and the product which is obtained in crystalline form is isolated by filtration 110 with suction. This gives 404 g (95 of theory) of 4-methyl-l-ethoxycarbonylthiosemicarbazide of melting point 130 0

C.

The following are obtained analogously: 4-ethyl-l-methoxycarbonyl--thiosemnicarbazide (melting point: 142 0

C);

4-propyl-l-methoxycarbonyl-thiosemicarbazide (melting point: 117C 4 -cyclopropyl- 1-methoxycarbonyl-thiosemicarbazide (melting point: 148 0

C);

4-allyl-l-methoxycarbonyl-thiosemicarbazide (melting point: 151*C); 4- d ime th 1a m inoa-1- me tho x yca rbo ny 1- th as em ica r baz id e kmelting point: 144 C) Le A 27 156 63 w Stp 0

H-N,"KN-CH

3 _S K A mixture of lO.Og (56.5 minol) of 4-methyl-iethoxycarbonyl-thiosernicarbazide (cf. Step 4.0 g (29 minol) of potassium carbonate and 80 ml of ethanol is refluxed until the evolution of gas has ceased (about 3 hours) When the mixture is cold, it is concentrated, the residue is stirred with 50 ml of methylene chloride, and the product, which has remained undissolved, is isolated by filtration with suction.

This gives 9.2 g (96 of theory) of the potassiumn salt of 5-mercapto-4-methyl-2,4-dihydro-31,2,4triazol-3-one (melting point >230'C).

The potassium salts of 5-rercapto-4-ethyl-2,4-dihydro-3H-l,2,4-triazol-3-one, 15 5-mercapto-4-propyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 5-mercapto-4-cyclopropyl-2,4-dihydro-3H-1,2,4-triazol-3one, and 5-mercapto-4-allyl-2,4-dihydro-3H-l,2,4-triazol- 3-one, and 5-mercapto-4-dinethvJlamino-2 ,4-dihvldro-3-H- 1,2, 4 -triazol-3-one, all of w~hich melt above 230 0

C,

are obtained analogously.

Le A27 156 -64-

I

H-Ni N-CH 3 j N

S-CH

3 A mixture of 4.0 g (23.7 mmol) of the potassium salt of 5-mercapto-4-methyl-2,4-dihydro-3H-l,2,4-triazol- 3-one (cf. Step 4.1 g (28.9 mmol) of methyl iodide and 80 ml of methanol is stirred for 12 hours at 200C.

The mixture is then concentrated, the residue is stirred with methylene chloride, and the potassium iodide, which has remained undissolved, is separated off by filtration.

The filtrate is concentrated, the residue is stirred with 500 ml of diethyl ether/petroleum ether (1:1 by vol.), and the product which has been obtained in crystalline from is isolated by filtration with suction.

This gives 3.4 g (99 of theory) of methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one of melting 15 point 970C.

For example the compounds of the formula (II) listed in Table 4 below can also be prepared analogously to Example (II-l).

0 I, aI(II) H-N N-R 1 I

I

N 5 (0)n-R 2 Le A 27 156 65 i- k~ Table 4 Preparation Examples of the compounds of the formula (II) Ex.

No.

0 11-2 11-3 11-4 11-6 1 1-14 11-12 11-16 11-17 11-18 11-19 11-20

CH

3

CH

3

OH

3

CH

3

CH

3 C 2 5 2

H

5 2 'H 5 2 5 0 3

H

7 OH (OH 3 2 0 2

H

5

O

3

H

7 OH( OH 3 )2 OH 2

OHOH

2

OH

3 CH7 C -H-

-OH

2

OH=CH

2

OH

3 0 2

H

5 n M.P. 0

C)

(Refractive index) 0 97 0 0 9i 0 58 0 O 0 87 O 73 o 42 0 o 78 0 (nio 0 1,5215) 0 56 0 0 (nD 1,5350O) 0 0 160 0 119 I I t Le A 27 156 66 ,Table 4 (Continuation) Ex.

No.

n mn-p. 0

C)

(Refractive index) 11-21 11-22 11-23 11-24 15-2 11-26 11-27 T 1-28 711-29 11-30 I T-3 1 25 11-32 11-33 11-34 11-35

CH

2

C

6

H

5

-CH

2 CH= CH 2

CH

2

CH=CH!-

2

CH-

-CH

2

-CH=CH

2

-]N(CH

3 2

CF

3

CH

2 -CH=

CM

2

C

3

H

7 CH (CH3 32

-CH

2

CH=CH

2

CH

3

CM

3 C 2

JH

5

CM

3

-CH

2 -CH= CM 2 CH (CH. 2

C

2

HMS

C H 2 C cl

-CH

2

-C-=CH

-CH

2

-C-=CH

94 94 105 13 166 (amorphous)*~ 5 7 168a-1i6 9 146 153 153-154 102-103 o

S

I 1 M-NN~R (D 6 -DHS'O, 360 M'l-z 6 3,6 6 (d S-CH 2 3 4,17 (in, lq-CH 2 4,95-5,28 (mn, 2CH 2 5,75-5,99 (mn, 2CH=); 12,0 (NH) ppm.

Le A 27 156 -6 67 Starting substances of the formula (IV): Example (IV-1 0 -O-CO-N N-NH 2

S--CH

3 22.1 g (0.141 mol) of phenyl chloroformate are added to a mixture of 20.Og (0.137 mol) of methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 5.6 g (0.141 mol) of sodium hydroxide, 0.2 g of tetrabutylammonium bromide and 200 ml of methylene chloride/water by vol.), with vigorous stirring. The reaction mixture is stirred for 12 hours at 20 0 C, and the product which is obtained in crystalline form is isolated by filtration with suction. This gives 34.8 g (95 of theory) of 4-amino-5-methylthio-2-phenoxycarbonyl-2,4dihydro-3H-1,2,4-triazol-3-one of melting point 211°C.

For example the compounds of the formula (IV) listed in Table 5 below can also be prepared analogously to Example (IV-1).

0 Z-CO-N~KN R1 (IV) IS(O)n-R 2 Le A 27 156 68 j mwmww- Table 5 Preparation Examples of the compounds of the formula (IV) Ex. R n Z Melting No.

point 0

C)

IV- 2 IV-3 IV-4

CH

3

CH

3

C

2 H5 CH3

CH

3

CH

3

C

2

H

5

C

2

H

C

3

H

7 0 0 0 0 C I 166 112 IV-6 IV-7 'v-8 IV- 9

CH

2

-CH=CH

2

CH

3

C

2

H

5

C

3

H-

7 0 0 0

O

143 Le A 27 156 69 Table 5 (Continuation) Ex.

R

No.

Melting point OC) IV Kill IV-1ii OCH 3 IV-12 0C 2

H

5 IV-13 OCH 2

-CH=CY

IV- 14 <Kc

C

2

H

5

CH

2

-CH=CH

2

CH

3

C

2

H

~2 C 2

H

CH CH 3 2

CH,

C

3

H

7

CH

3

C

2

H

5 0

\O

0 IV-16 IV- 17

C

2

H

5 NH-

CM

3 a, 4 4S 0 0 \0 0 IV-18 NH-CM 3 Le A 27 156 70 Table 5 (Continuation) Ex. R No.

Melting point

CC)

IV-19

N(CH

3 2

NH-CH

3

C

2

H-

5

C

3

H

7 IV-21 NH-

CH

3 CH (CH 3 2 0 0 0 0 0 0 0/0\ IV-22 NH-CH 3

CH

2

-CH=CH

2 IV-23 CH 2

-CH=CH

2

C

2

H

5 p a a a at 4I a I.

at S a I Le A 27 156 71 [I Use Examples: In the Use Examples which f ollow, the known herbicide isocarbamid, of the formula below, is used as comparison substance: HNNNr(NCO-NH-CH 2

CH(CH

3

(A

0 (disclosed in, for example, DE-1,795,117).

In the text below, the formulae of the compounds according to the invention used for the Use Examples are listed individually, the numbers being those of the Preparation Examples:

COOCH

3 0

S-CH

3 COOCH- 0 0 2 ~N-C0N~KNCH 3 (3) -S-C

H

COOCH

3 0 S0 2 -NH-C0-CH(CH 3 )2 Le A 27 156 72 lvmww

COOCH

3 0 I\ S-CH-CH=

CH

2

COOCH

3 0 S 0 2 M CONll N l'fr2

COOCH,

N S-CH 2

C

6

H

CCOCH

3 0 _S0 2 -NH-CO-'

-CH

COOCH3 0 S0 2 -NH-C'-lqN

IC

2

H

5 \S CI (9) (13) (14) Le A 27 156 73

COOCH

3 0 _s O2NH-CO-N Nl-C 2 H (16) -S-CH

(CH

3 2

OCF

3 0 so -NH-C0'-)q -N--CH 3 (17) 1I S-CH3

COOCH

3 0 S0 2 -IqH-CO'N -qC 3

H

7 rF 1 S-CH(CH 3 2

OCF

3 0 \7 S 2 -N F -H 3 (21) COOCH3 0 so 0 2 N~ 0N (22) 1I S-CH 2

CH=CH,

2

COOCH

3 0 H S0 2 -N -NNNA.lq (23) S C 3

H

7

COOCH

3 0 11 <77/-S0 2 -1H CO'N.N<(24) S -CH (CH 3 2 Le A 27 156 74 C000H 3 0 \C S0 2 -1H -CO-N l-~C 3

H

7 n S CH 3

OCF

3 0 So /S 2 -NH- C0IN"Nl.-c 3

H

7

S-C

2

H

(26)

COOCH

S

2 IH -CN.

"Sc 2 H (27)

OCF

3 0 0\ S0~ H C 0 .NN<

-C

(28) CO CC H -s0 2N H-3

CH

2 (29)

COOCH

3 0

S

2 -N H -C O-N k-CH 2 -C H =C H 2 1

S-C

2

H

OCF

3 0 /S0 2 -)qH-Co,-,Nl.N< I

S-H

(31) Le A27 156 75

OCF

3 0 2 -14H C0'-N 4N-CH 3

CH

3 S -C 2 H 2 SO 2 NCO"-I N-CH 3 Cl-b- 1N S-CH- C 1 0

/SO

2

NHCON-.NN<K

CH

3 I S-CH 3 ca 0

CH

3 N~ 2

HS

(32) (34) (37 (38) OClF3 0 /S0 2 -IqH-CO'-1,jl'l-CH 2

-CH=CH

2 N S-C 2

H

Le A 27 156 76

IA

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, 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 of the active compound. It is expedient to keep the amount of water per unit area constant. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in da1age 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 clearly superior activity compared with the prior art is shown, for example, by the compounds of Preparation Examples: 1, 3, 4, 5, 6, 7, 13, 17, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 37.

Le A 27 156 77 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 I 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 1 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 clearly superior activity compared with the prior art is shown, for example, by the compounds of Preparation Examples: i, 3, 4, 5, 6, 7, 13, 14, 16, 17, 20, 21, 22, 23, 24, 26, 27, 28, 29, 30, 31, 32, 34, 35, 37, 38, Le A 27 156 78

A

I I Example C Pyricularia test (rice) protective Solvent: 12,5 parts by weight of acetone Emulsifier: 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 concentrate is diluted with water and the stated amount 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 Evaluation of the disease infestation is carried out 4 days after the inoculation.

In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 1, 3, 4, 5, 7, 9, Le A 27 156 79 Example D Pyricularia test (rice) systemic Solvent 12,5 parts by weight of acetone Emulsifier: 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 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 rice plants have been grown is .watered with 40 ml of the preparation of active compound. 7 -ays 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 inocualtion.

In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 1, 3, 4, 5, 7, 15, 17, 21, 22, Le A 27 156 80

Claims

1. Sulphonylaminocarbonyltriazolinones having substituents which are bonded via sulphur, of the general formula 0 R 3 -SO2-NH-CO-N N-R I -R2 in which n represents the numbers 0, 1 or 2, R represents hydrogen, hydroxyl or amino, or repre- sents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cyclo- alkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkyl- amino, cycloalkylamino and dialkylamino, R represents an optionally substituted radical from o the series comprising alkyl, alkenyl, alkinyl, *15 cycloalkyl, cycloalkenyl, aralkyl and aryl, and R represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula

2. Process for the preparation of sulphonylaminotri- azolinones of the general formula according to Claim 1, characterized in that a) triazolinones of the general formula (II) Le A 27 156 81 I" 0 HNIN-R 1 (II) S S(0)n-R2 in which n, R 1 and R 2 have the meanings indicated in Claim 1, are reacted with sulphonyl isocyanates of the general formula (III) R 3 -S02-N=C=0 in which R 3 has the meaning indicated in Claim if appropriate in the presence of a diluent, or in that b) triazolinone derivatives of the general formula (IV) 0 Z-CO-N -N-R1 (IV) i--s -R 2 in which n, R 1 and R 2 have the meanings indicated in Claim 1 and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphonamides of the general Le A 27 156 82 formula (V) 2 -NH 2 (V) in which R 3 has the meaning indicated in Claim 1, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or in that c) triazolinones of the general formula (II) 0 HNZ \N-R1 (11) N -S(O)-R2 0 0 in which n, R 1 and R 2 have the meanings indicated in Claim 1, are reacted with sulphonamide derivatives of the o. general formula (VI) R3-S02-NH-CO-Z (VI) in which R 3 has the meaning indicated in Claim 1 and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if desired, salts are formed by customary Le A 27 156 83 -L 0300p:mmb 84 methods from the compounds for the formula prepared by process or

3. A herbicidal agent in containing as active ingredients at least one sulphonylaminocarbonyltriazolinone of the formula I accordinging to claim 1 together with a herbicidally acceptable carrier or adjunct.

4. Method of combating weeds, characterized in that sulphonylaminocarbonyltriazolinones of the general formula according to Claim 1 are allowed to act on the weeds or their environment.

Process for the preparation of herbicidal agents, characterized in that sulphonylaminocarbonyltriazolinones of the general formula according to Claim 1 are mixed with extenders and/or surface-active agents.

6. Triazolinone derivatives of the general formula (IV) S'0 Z-CO-NJ.N-R 1 (IV) N S(0)n_R2 in which n represents the numbers 0, 1 or 2, R represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino, cycloalkylamino and dialkylamino, R 2 represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aralkyl and aryl, and Z represents halogen, alkoxy, aralkoxy or aryloxy. DATED this 7th day of February, 1992. SBAYER AKTIENGESELLSCHAFT ^y By Its Patent Attorneys DAVIES COLLISON CAVE