CA2010647A1

CA2010647A1 - Herbicidal sulphonylimino-azinylheteroazoles and intermediates therefor

Info

Publication number: CA2010647A1
Application number: CA002010647A
Authority: CA
Inventors: Hilmar Wolf; Heinz-Jurgen Wroblowsky; Peter Babczinski; Klaus Lurssen; Hans-Joachim Santel; Robert R. Schmidt
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1989-02-24
Filing date: 1990-02-22
Publication date: 1990-08-24
Also published as: ZA901389B; DE3905714A1; EP0384244A1; JPH02264774A; AU4988290A; BR9000863A

Abstract

ABSTRACT

Herbicidal sulphonylimino-azinlyheteroazoles of the formula

Description

The invention relates to new sulphonylimino-azinylheteroazoles, a process and new intermediates for their preparation and their uce as herbicides.
It is known that 3-amino-1,2,4-triazole (amitrol) can be used as a herbicide (compare Science 145 (1964), 97). However, the action of this compound is not satis-factory in all matters.
The new sulphonylimino-azinylheteroazoles of the general formula (I) z~y ~ 2 :~

R1-502-N ~ (I) E D
in which A represents nitrogen or the grouping C-A1, in which : :
: Al represents hydrogen, halogen, cyano, nitro or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul- : :
phonyl, alkylamino, dialkylamino or phenyl, ~ -~ D represents nitrogen or the grouping C-D1, in which ; Dl represents hydrogen, halogen, cyano, nitro or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul- :-phonyl, alkylamino, dialkylamino or phenyl, (with the proviso that A and D do not both simultaneously repre~ent nitrogen), Le A 26 727 - 1 -E representS oxygen or sulphur, Z0~0647 ~ R1 represents in each case optionally substituted alkyl, aralkyl, aryl or heteroaryl, ~2 represents hydrogen, halogen, hydroxyl, amino or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkyl-amino or dialkylamino, repres~nts nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, halogen, cyano, alXyl, formyl, alkylcarbonyl or alkoxycarbonyl, and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, halogen, hydroxyl, amino or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino or dialkylamino, have now been found.
The new sulphonylimino-azinylheteroazoles of the general formula (I) are Pbtained when sulphonylamino-: 20 heteroazoles of the general formula (II) R1-5O2-NH (II) ..
~ A :
in which E - D
~, D, E and Rl have the abovementioned meanings, are reacted with azines of the general formula (III) N = Z~ (III) ~X~R2 ~e A 26 727 - 2 -in which R2, x, Y and Z have the abovementioned meanings and Q represents halogen or alkylsulphonyl, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.
The new sulphonylimino-azinylheteroazoles of *he general formula (I) are characterized by strong her-bicidal activity. These compounds represent a chemically novel class of herbicides.
Surprisingly, the new compounds of the formula (I) show considerably better herbicidal action than the structurally similar known herbicide aminotriazole (amitrol).
The invention preferably relates to compounds of the formula (I), in which A represents nitrogen or the grouping C-A1, in which A1 represents hydroqen, fluorine, chlorine, bromine, iodine, cyano or nitro, or represents 1 4 Y 1 C4 alkoxy, C1 C4-alkylthio, Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, C1-C4-alkylamino or di-(Cl-C4)-alkyl-amino in each case optionally substituted by fluorine and/or chlorine or Cl-C4-alkoxy, or represents phenyl optionally substituted by fluorine, chlorine, bromine, Cl-C4-alkyl, Cl-C2-fluoro- and/or chloro-alkyl, C1-C4-alkoxy and/or C1-C2-fluoro-and/or -chloro-alkoxy, D represents nitrogen or the grouping C-D1, in which D1 represents hydrogen, fluorine, chlorine, ~ bromine, iodine, cyano or nitro, or represents Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-.~.

Le A 26 727 - 3 -C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkylamino or di-(Cl-C4)-alkyl-amino in each case optionally substituted by fluorine and/or chlorine or C1-C4-alkoxy, or represents phenyl optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, Cl-C2-fluoro- and/or chloro-alkyl, Cl-C4-alkoxy and/or Cl-C2-fluoro-and/or -chloro-alkoxy, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, Rl represents the radical ~ , in which :
R ~ : :
R5 and R6 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, Cl-C6-alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4- :
:~ alkoxycarbonyl, C1-C~-alkylamino-carbonyl, :
di-(C1-C4-alkyl)aminocarbonyl, hydroxyl, 2Q Cl-C4-alkoxy, formyloxy, Cl-C4-alkyl-car-bonyloxy, Cl-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkylthio, Cl-C4-alkylsulphinyl,Cl-C4-alkylsulphonyl, di-(C1-C~-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl~, C2-C6-alkenyl [which i8 optiqnally substituted by fluorine, Le A 26 727 - 4 -.

20~0647 chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxy or phenyl], C2-CB-alkinyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl], C1-C4-alkoxy [which is optionally ~ub-stituted by fluorine, chlorine, bromine, cyano, carboxyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl~, C1-C4-alkylthio [which i~ optionally sub-ctituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4- -alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl], C3-C6-alkenyloxy [which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-cyano or C1-C4-alkoxy-carbonyl], Cz-C6-alkenylthio [which i8 optionally substituted by ~: 20 fluorine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl], C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(o)p-R7, where p reprefient~ the numbers 1 or 2 and R7 represents C1-C~-alkyl twhich is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl], C3-C6-alkenyl, C3-C6-alkinyl,Cl-C~-alkoxy,Cl-C4-alkoxy-30 ~ C1-C4-alkylamino, Cl-C4-alkylamino, di-,~

; Le A 26 727 - 5 -' ..:

-20106~7 - tCl-C4-alkyl)-amino or for the radical -NHOR8, where Ra represents C1-C~-alkyl [which i~
optionally substituted by fluorine, chlorine, cyano, Cl-C~-alkoxy, Cl-C4-alkylthio, C~-C4-alkylsulphinyl, C1-C4-alkylsul- -phonyl, C1-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl, alkylamino-carbonyl or di-(Cl-C4-! alkyl) amino-carbonyl], C3-C6-alkenyl [which i~ optionally substituted by fluorine, chlor-ine or bromine], C3-C~-alkinyl, C3-C6-cycloalkyl, C3-C6-CyC10-alkyl-Cl-C2-alkyl~ phenyl-Cl-C2-.~ alkyl [which i8 optionally substituted by fluorine, chlor-ine, nitro, cyano, Cl-C4-alkyl, Cl-C~-alkoxy or Cl-C~-alkoxy-carbonyl], benzhydryl or phenyl ~: ~ [which i8 optionally ~ubstituted by fluorine, chlorine, nitro, cyano, C~-C~-alkyl, trifluoro-~- ~ 25 methyl, C1-C4-alkoxy, Cl-C2-fluoroalkoxy, C~-C4-alkylthio, ~ trifluoromethylthio or C1-C4-; alkoxy-carbonyl]~
R~ and Rs furthermore represent phenyl or phenoxy, ClC4-alkylcarbony}amino, Cl C~-alkoxycar-,~- .
::

,. ,, ~ . -.

,~ :
Le A 26 727 - 6 - ~.

~ .

ZOiO647 - bonylamino, C,-C4-alkylamino-carbonylaminor di-(C,-C4-alkyl)-amino-carbonylamino, or the radical -CO-R~, where R9 represents C,-C6-alkyl, Cl-C6-alkoxy, C3-CB-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkylthio, amino, Cl-C4-alkyl-amino, Cl-C4-alkoxyamino, Cl-C4-alkoxy-Cl-C4-alkyl-amino or di-(Cl-C4-alkyl)-amino [which are optionally substitu-ted by fluorine and/or chlorine], R5 and R6 furthermore represent Cl-C~-alkylsulphonyl-oxy, di-~Cl-C~-alkyl)-aminosulphonylamino or the radical -CH=N-Rl, where Rl represent~ Cl-C6-alkyl optionally ~ubstituted by fluorine, chlorine, : cyano, carboxyl, Cl-Cj-alkoxy, Cl-C4-alkylthio, Cl C4-alkyl~ulphinyl or Cl-C~-alkylsulphonyl, benzyl option-ally sub~tituted by fluorine or chlorine, C3-CB-alkenyl or C3-C6-: alkinyl optionally substituted by fluorin~ or chlorine, phenyl option-ally sub~tituted by fluorine, chlor-ine, bromine, C~-C4-alkyl, Cl-C4-alkoxy, trifluoromethyl, trifluoro--~ metXoxy or trifluoromethylthio, Cl-C~-alkoxy, C3-CB-alkenoxy, C3-C6-~ alkinoxy or benzyloxy optionally ;~ sub~tituted by fluorine and/or ~ chlorine, amino, Cl-C~-~lkylamino, di-:~, ~e ~_~6 727 : :: ~ -20106~7 (Cl-C4-alkyl)-amino~ phenylamino, Cl-C4-alkyl-carbonyl-amino, Cl-C4-alkoxy-carbonyl-amino, Cl-C4-alkyl-sulphonylamino or phenyl~ulphonyl-amino optionally substituted by fluorine, chlorine, bromine or methyl, in which in addition ~ ,R13 R1 represents the xadical -IH ~ , in which R11 represents hydrogen or C~-C4-alkyl, R12 and Rl3are identical or different and represent hydrogen, fluorine, chlorine, bromine, : nitro, cyano, C1-C4-alkyl [which i8 option-ally substituted by fluorine and/or chlorine]~ C1-C4-alkoxy [which is option-ally ~ub~tituted by fluorine and/or chlorine]~ carboxyl, C1-C~-alkoxy-carbonyl, Cl-C~-alkylsulphonyl or di-( C~-C4-alkyl ) -aminosulphonyl; in which in addition R1 represent~ the radical R14 ~ R15 ~ in which , . ~ .
Rl4 and R15are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl twhich is option-ally ~ub~tltutod by fluorLno and/or . ~: ` ' .

- Le A 26 727 - 8 - -' :

: 2010647 :I chlorine] or C1-C4-alkoxy [which is option-ally substituted by fluorine and/or ~i chlorine]; in which in addition I R1 represents the radical ~ , in which S Rl6 and R17 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl [which is option-ally substituted by fluoxine and/or chlorine], C2-C4-alkenyl [which is option-ally substituted by fluorine and/or chlorine], C1-C4-alkoxy [which is option-ally substituted by fluorine and/or chlorine], C1 C4-alkylthio, Cl-C4-alkylsul-phinyl or C1-C4-alkylsulphonyl [which are : 15 optionally substituted by fluorine and/or chlorine], and di-(C1-C4-alkyl)-amino~ul-~-~ phonyl, C1-C4-alkoxy-carbonyl, dimethyl~
-~ aminocarbonyl or dioxolanyl; in which in addition ~}~
: 20 Rl represents the radical R19 ~ R18 in which ;~ :
R1a and Rl~are identical or different and represent . hydrogen, fluorine, chlorine, bromine, :~ . C1-Cj-alkyl twhich is optionally substitu- :

,~
'`f :
,.
.`.
Le A 26 727 - 9 -1~ i ted by fluorine and/or bromine], C1-C4-alkoxy [which i~ optionally ~ub~tituted by fluorine and/or chlorine], Cl-C4-alkyl-thio,C1-C4-alkylsulphinyl or C1-C4-alkylsul-phonyl [which i8 optionally substituted by fluorine and/or chlorine], or di-(C1-C4- ~: :
alkyl)-aminosulphonyl; in which in addi-tion ~20 R1 repre~ents the radical ~ ~ , in which O ..
R20 and R21are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl [which i8 option-ally substituted by fluorine, chlorine, ~: C1-C4-alkoxy and/or C1-C4-halogenoalkoxyl, ; 15 C~-C4-alkoxy [which is optionally sub-. stituted by fluorine and/or chlorine], .~ C1-C~-alkylthio, C1-C~-alkylsulphinyl or .~ C1-C~-alkylsulphonyl twhich is optionally substituted by fluorine and/or chlorine], di-(C1-C~-alkyl)-amino-sulphonyl or C~-C4-.. ~ alkoxy-carbonyl, and : Q1 represents oxygen, sulphur or the grouping N-. ~ Q2 where ` ~ Q2 represents hydrogen, C1-C4-alkyl [which is optionally substituted by fluorine, chlor-ine, bromine or cyanol, C3-C~-cycloalkyl, : bénzyl, phenyi [which is optionally sub-, .
~ , .
.,- ~ :
. ~ .

- ~e A 26 727 - 10 - ~ ;

:

Z0~06~'~
stituted by fluorine, chlorine, bromine or nitro], Cl-C4-alkylcarbonyl, Cl-C4-alkoxy-carbonyl or di-(Cl-C4-alkyl)-aminocarbonyl;
in which in addition Rl representæ the radical ~ R23 ~ in which R22 and R23are identical or different and represent hydrogen, Cl-C4-alkyl, halogen, C1-C4-alkoxycarbonyl, Cl-C4-alkoxy or C~-C4- ~ :
halogenoalkoxy, lOQ3 represents sulphur or the grouping N-R24, where R24 represents hydrogen or Cl-C4-alkyl; in which in addition ; R27 ~' represents the radical ~ , in which R 6 -~
--.
R25 represents hydrogen, C1-C~-alkyl, phenyl or ~ -15(iso)quinolinyl, -; R26 represents hydrogen, halogen, cyano, nitro, Cl-C4-alkyl twhich is optionally substituted by : fluorine and/or chlorine], Cl-C4-alkoxy twhich ~:~ is optionally substituted by fluorine and/or : : 20chlorine], dioxolanyl or Cl-C~-alkoxy-carbonyl and R27 repre~ents hydrogen, halogen or C1-C~-alkyl;`in . ~ :
, ~

`: ~
. ~e A 26 727 - 11 -Z0~0647 which in addition R1 represents the radical ~ ~ R28 , in which N`S
R28 represents hydrogen, halogen, Cl-C4-alkyl or C1-C4-alkoxy-carbonyl; in which in addition R1 represents the radical ~ -52 in which R~9 represents C1-C4-alkyl and R30 represents C1-C4-alkyl, in which in addition R1 represents the radical ~ , in which )~ . ' ' <~0)= ':"
R~1 :
R31 representq hydrogen or methyl, : . . . -represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, Cl-C4-alkyl, Cl-C4-halogenoalkyl, Cl-C2-alkoxy-Cl-C2-alkyl, bis-(C~-C2-alkoxy)-Cl-C2-alkyl, : ' Cl-C4-alkoxy, Cl-C4-halogenoalkoxy, Cl-C4-alkylthio, . . .
~: 15 C~-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, Cl-C4-alkylamino, dimethylamino or diethylamino, ~- X represents nitrogen or a CH grouping, ~: Y represent~ nitrogen or the grouping C-R3, in which R3 represents hydrogen, fluorine, chlorine, 2~ bromine, cyano, methyl, formyl, acetyl, meth-oxycarbonyl or ethoxycarbonyl, and Le A 26 727 - 12 -.. : . , , , :::.:, - , ., ,,,. ,,,.. ~ ~.. . . . . .

Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorina, bromine, hydroxyl, amino, Cl-C4-alk~l, Cl~C4-halogenoalkyl, Cl-C2-alkoxy-Cl-C2-alkyl, bis-(C~-C2-alkoxy)-C1-C2-alkyl, C~-C4-alkoxy, C~-C4-halogenoalkoxy, C~-C4-alkylthio, C~-C4-alkylsulphinyl, C~-C4-alkylsulphonyl, Cl-C4-alkylamino, dimethylamino or diethylamino.
The invention in particular relates to compounds of the formula (I), in which 10 A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl, trifluoromethyl, di-chloromethyl, trichloromethyl, chlorodifluoro- `
methyl, fluorodichloromethyl, methylthio, ethylthio, propylthio, butylthio or phenyl, D represents nitrogen or the grouping C-Dl in which Dl represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl, trifluoromethyl, di-chloromethyl, trichloromethyl, chlorodifluoro-~ methyl, fluorodichloromethyl, methylthio, : ethylthio, propylthio, butylthio or phenyl, (with the proviso that A and D do not both simultaneously represent nitro~en), ~: E represents oxygen or sulphur, represents the radical ~ , in which Le A 26 727 - 13 -~,~

20~06~7 - R5 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, Cl-C3-alkylthio, Cl-C3-alkyl-sulphinyl, C~-C3-alkylsulphonyl, dimethylamino-sulphonyl, N-methoxy-N-methylamino ulphonyl, phenyl, phenoxy or C,-C3-alkoxy-carbonyl and R6 represents hydrogen, fluorine or chlorine; in which in addition 1 R1 represents the radical -fH ~ R13 in which ~l Rll R~l represents hydrogen, ~ :
R12 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, ~; methylsulphonyl or dimethylaminosulphonyl and R13 repre~ents hydrogen, fluorine or chlorine; in which in addition represents the radical RO-C ~ , in which ,..~
~ O

-: R represents C~-C4-alkyl, or ~; R~ represents the radical ~e A 26 727 - 14 -: ~ ' ' ', Z0~647 11 :
RO-C~T~
~ , in which N'N
C~13 R represent~ Cl-C4-alkyl, or : :
Rl represents the radical ~l ~ , in which N`S ~,.. .
R2~ represents hydrogenl chlorine, methyl, ethyl, methoxycarbonyl or ethoxycarbonyl;
in which in addition R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X repre~ents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, fluorine, chlorine or methyl and z represents nitrogen or the grouping C-R4, in which ~.
R4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, ~ methoxy, ethoxy, propoxy, i~opropoxy, difluoro-: 20 methoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
If, for example, 2 (2-fluoro-phenylsulphonyl-amino)-osazole and 4,6-dimethyl-2-methylsulphonylpyrimi-: ~;

Le A 26 727 - 15 -.
.~ .

- Z0~0647 dine are used as starting substances, then the course of the reaction in the proces~ according to the invention can be outlined by the following equation:

F ~ CH3 ~5 0 2 - NH~ H 3 C - S 0 2~ _~C

3 :
H3C ~CH3 -CH3 502H ~ N
N
~ so2-N ~ ~

Formula (II) provides a general definition of the sulphonylaminoheteroazole~ to be used as starting sub-stances for the preparation of compounds of the formula (I) in the process according to the invention.
In formula (II), ~, D, E and R~ preferably or in particular have those meanings which have already been indicated above as particularly preferred for A, D, E and R~ in connection with the de~cription of the compounds of the formula (I) according to the invention.
Examples of the starting substances of the ~ ~ :
formula (II) are shown in the following Table 1.

: ", ~ -- :' ,'~ ..
.
Le A 26 727 - 16 -,:
~ ~ , 1 '` Z0~0647 Table ls Examples of the starting substances of the formula (II) 'Y`A tIt) E - D

. . . _ .
COOCH~
'~ N CH O ~

~;~ N CH S ~
:~

CH N O ~

~ ~ COOCH3 c.~ CH N S
,~

CH CH O COOCH~

~ ~, , COOCH3 :
CH CH S ~ ; :~
. ~,, ,~ , , ' Le A 26 727 - 17 -Table 1 - Continuation 201064 7 .

N C-CH3 O ~

N C-CH3 S ~

~ COOCH3 COOCH3 :
N C-CF3 S ~

-~ ~ OOCH3 N C-C2H5 5 ~

COOC~3 N C-C~H5 S

N C-SCH3 5 ~

' ',: ' ~ ` :
Z01064~ ~
Table 1 - Continuation a C-C2H5 CH S ~

N C-CHC12 S ~

C-Cl C-C1 S ~

COOC ~H5 ; N CH O ~
1 ~

N CH S ~
COOC2H5 ~:
CH N S

<COO 2 5 C-CH3 N S <~ : ~:
COOC 2H5 ~. ` ' CH CH ~ S

~; Le A, ~6 7,27 - 19 -Table 1 - Continuation . . _ . _ . . _ _ N C - CH3 o ~

COOC2H5 -, N ~-CH3 S ~ :

COOC2Hs N C-SCH3 S ~

~:~ C l :
N CH S

CH N S

.~ .

C-CH3 N S ~ - ~ :

CH CH S

~; N C - CH ~ O
.~

LQ A 26 727 - 20 - ~ -' "'-' -TablQ 1 - Continuation A D E Rl Cl Cl Cl ~: C l N C-C6H5 S ~ ~ ~:

N C-CH ~ CH~ ) 2 5 ~

. .- .

N c-Sc4H9 5 . ~
C l . C-Cl C-Cl S <~ ~;

N CH S ~

"~ :

, Le A 26 727 - 21 ` ` 2010647 Table 1 - Continuation F : -CH N S

C-CH? N S

F
CH CH S

;~ ~F
N C-CH3 S <~

F
. ~ N C-SCH3 s ~ ~ ~

.3~ N CH S ~ ~;

i ~ 8r ` ~ C~l N S

B r I~e A 26 727 -22 ` ~

Table 1 - Continuation A D E R

Br CH CH S

8r N CH S

CH~ ~
CH N S ~ ;
,~

C - CH 3 N ~3 ; ~ N C - CH 3 5 <~3 ~ ;

CH CH S ~

' ;` ~ :
Le A 2 6 7 2 7 - 2 3 zo~0647 Table 1 - Continuation .`
,.

i N CH S

CH N S ~

¦ CF3 C-CH~ N S ~

N C-CH3 5 ~

. ~ N CH S ~

CH N S ~ H3 OCH3 :
. ~=< " ' ~: .' - "
C-CH3 N S ~ ! ;~

OCH~

' . ~ :
Le A 2 6 7 2 7 - 2 4 20~06~
?able 1 - Continuation :., A D E Rl l :
,~1 OCH? ~ -~, CH CH S <~
, OCH3 N C-SCH3 S ~

3 N C - C 6 H 5 S ~

N CH S ~ : :

~ ~ Cll N S
i, ~: :
. ~
. "~ ~ OCHF2 C-CH3 N S ~

~ ~_< 2 i ~ N C-CH3 5 <~

~; C~l CH S

Le A 26 727 - 25 -Table 1 - Continuation N C-SCH3 S ~

: 2 OCHF
C-C1 C-Cl S ~

N CH S ~

:~ CH N S ~ ~ :

C-CH3 . N S ~
k,- ~

N C-CH~ S

CH CH S OCF3 . .

. .

~ Le A 2Ç 727 - 26 - . ~ :~

,~ ' ' ,.

`` 20~0647 Table l - Continuation .
A D E Rl :

C-Cl C-Cl S ~

N CH S ~

CH N S

` OCH2CH2C 1 ;;
C-CH~ N S

N C-CH3 S ~

OCH2CH2Cl ~ :
; ~ CH CH S ~ : ~.v;.

~ N C-SCH3 S

; ! oCH2CH2Cl : ~
` N C-CF3 S ~ :~ :

Le A 26 727 - 27 ~

Table 1 - Continuation OCH2cH2c 1 N C-C6H5 S ~

~ N C~l S ~
,, SCH3 A C H N S ~

~: SCH3 ¦ C-CH3 N S

¦ N C-CH3 S SCH3 :

; N C-SCH3 S SCH3 N C-C6H5 S ~ H3 Le A 26 727 - 28 -Z0~0647 :
Table 1 - Continuation , ~< 3 CH CH S <~
f SCH3 C-Cl C-Cl S <~

N CH S ~

~< 2 ~ 2 N CH S

C6H5 ' ' :~
N CH S <~

,` ~ : :.
,'', ',~ ~- .

26 ~27 - 29 ~

~ 20106~7 ; The starting substances of the formula (II) are not yet known from the literature.
The new compounds of the formula (II) are obtained when ~, 5 ~) aminoheteroazoles of the general formula (IV) i N ~ E ( ~ I_I . .
A v in which A, D and E have the abovementioned meanings, are reacted with sulphonyl halides or sulphonic anhydrides of the general formula (V) Rl-So2_Q4 (V) : in which :~: R1 ha~ the abovementioned meaning and Q4 represents chlorine, bromine or the grouping -O-SO2-R1, in which Rl ha~ the abovementioned meaning, if appropriate in the presence of an acid acceptor, such a~, for example, pyridine and if appropriate in the pre~ence of a diluent, such as, for example, pyridine, methylene chloride, acetone, ace~onitrile, ~ --tetrahydrofuran, dioxane or dimethylformamide, at empsratures between -50-C and +50C and, if : appropriate, the reaction product i8 treated with nmmonia, or when :::

. .. ~:
` ~, Le A 26 727 - 30 -:
~ .

;1 20~0647 :. ~) heteroazoles of the general formula (VI) N l E (VI) in which A, D and E have the abovementioned meanings and S Q5 represents halogen or alkylsulphonyl, are reacted with sulphonyl amides of the general formula (VII) Rl-S2-NH2 (VII
in which Rl has the abovementioned meaning, ~ ~
if appropriate in the pre~ence of an acid acceptor, ~ .
such as, for example, potas~ium carbonate, and if appropriate in the presence of a diluent, such a~, :
for:example, acetonitrile, tetrahydrofuran, dioxane or dimethylformamide, at temperatures between 0C
and 150C.
Formula (IV) provides a general definition of the -~
~1 aminoheteroazoles required as intermediates. In formula (IV), A, D and E preferably or in particular have those meaning~ which have already been indicated above in -~ connection with the description of the compounds of the ~-~ . formula (I) according to the invention as preferred or as particularly preferred for A, D and E. :~:
Examples of the compounds of the;formula (IV) : :
-Le A ~ 727 - 31 -.:
~:;

which may be mentioned are:
2-amino-oxazole,2-amino-thiazole,2-amino-1,3,4-thiadia-zole, 5-amino-1,2,4-thiadiazole, 2-amino-1,3,4-oxadia-zole, 2-amino-4-methyl-thiazole, 2-amino-5-methyl-thia-zole, 2-amino-5-methyl-1,3,4-thiadiazole, 2-amino-5-e~hyl-1,3,4-thiadiazole, 2-amino-5-trifluoromethyl-1,3,4-thiadiazole, 2-amino-S-difluoromethyl-1,3,4-thiadiazole, 2-amino-5-dichloromethyl-1,3,4-thiadiazole, 2-amino-5-¦ methylthio-1,3,4-thiadiazole and 2-amino-5-phenyl-1,3,4-I 10 thiadiazole.
~he aminoheteroazoles of the formula (IV) are known and/or can be prepared by methods which are known per se (compare Comprehensive Heterocyclic Chemistry, Vol. 6, Pergamon Press 1984).
lS Formula (V) provide~ a general definition of the sulphonic acid halides or anhydrides further to be used as intermediates. In formula (V), R1 preferably or in particular has th~t meaning which has been indicated above in the context of the description of the compounds of the formula (I) accordinq to the invention as pre-ferred or as particularly preferred and Q4 preferably represents chlorine.
Examples of the compounds of the formula (V) which may be mentioned are:
benzenesulphonyl chloride, 2-chloro-, 3-chloro-, 4-chloro-, 2,5-dichloro-, 2-fluoro-, 4-fluoro-, 2-bromo-, 4-bromo-, 2-cyano-, 2-nitro-, 4-nitro-, 2-methyl-, 4-methyl-, 2-chloromethyl-, 2-trifluoromethyl-, 2-methoxy-4-methoxy-, 2-methylthio-, 2-trifluoromethylthio-, 2-difluoromethylthio-, 2-cyclopropyloxyc~rbonyl-, 2-phen-Le A 2~ 727 - 32 -:.
oxy-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-(2-chloroethoxy~-, 2-methylthiomethyl-, 2-dimethylaminosul-~, phonyl-, 2-phenyl-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-2-dLmethylaminocarbonyl- and 2-diethylaminocarbonyl-benzenesulphonyl chloride as well as (2-chloro-phenyl)-, (2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and (2-~3 trifluoromethoxy-phenyl)-methanesulphonyl chloride, 2-chloro-6-methyl-benzenesulphonyl chloride and 2,6-di-chloro-benzenesulphonyl chloride.
.~ 10 The sulphonic acid halides or anhydrides of the formula (Y) are known and/or can be prepared by processes which are known per se (compare J. Org. Chem. 33 (1968), 2104; J. Org. Chem. 25 (1960), 1824; DE-AS (German ,1 Published Specification) 2,308,262; EP-OS 23,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; US-PS 2,929,820, 4,282,242; 4,348,220 and 4,372,778 and Angew. Chem. 23 (1981), 151).
Formula (VI) provides a general definition of the heteroazoles further required as intermediates. In formula (VI), A, D and E preferably or in particular have those meanings which have already been indicated above as preferred or as particularly preferred for A, D and E in connection with the de cription of the compounds of the formula (I) according to the invention and Q5 preferably represents fluorine, chlorine, bromine or C1-C4-alkyl-sulphonyl, in particular chlorine or methylsulphonyl.
Examples of the compounds of the formula (VI) which may be mentioned are:
¦ 2-chloro-oxazole, 2-~hloro-thiazole, 2-chloro- and 2-¦ 30 methyl-sulphonyl-1,3,4-thiadiazole, 2-chloro-1,3,4-Le A 26 727 - 33 -.

::

oxadiazole, 5-chloro-1,2,4-thiadiazole, 2-chloro-4-methyl-thiazole, 2,4,5-trichloro-thiazole, 2-chloro-5-methyl-thiazole, 2-chloro- and 2-methylsulphonyl-5-methyl-1,3,4-thiadiazole, 2-chloro- and 2-methylsul-phonyl-5-ethyl-1,3,4-thiadiazole, 2-chloro- and 2-methyl-sulphonyl-5-trifluoromethyl-1,3,4-thiadiazole, 2-chloro-and 2-methylsulphonyl-5-difluoromethyl-1,3,4-thiadiazole, 2-chloro- and 2-methylsulphonyl~S-dichloromethyl-1,3,4-thiadiazole, 2-chloro- and 2-methylsulphonyl-5-methyl-thio-1,3,4-thiadiazole and 2-chloro-5-phenyl-1,3,4-thiadiazole.
The heteroazoles of the formula (VI) are known and/or can be prepared by methods which are known per s~
(compare Comprehensive Heterocyclic Chemistry, Vol 6, Pergamon Press 1984).
Formula (VII) provides a general definition of the sulphonyl amides further to be used as intermediates.
In formula (VII), Rl preferably or in particular ha~ that meaning which has been indicated above as preferred or as particularly preferred in the context of the de~cription of the compounds of the formula (I) according to the invention.
Startin~ substance~ of the formula (VII) which may be mentioned, for example, are:
benzenesulphonyl a~ide, 2-chloro-, 3-chloro-, 4-chloro-, 2,5-dichloro-, 2-fluoro-, 4-fluoro-, 2-bromo-, 4-bromo-, 2-cyano-, 2-nitro-, 4-nitro- 2-methyl-, 4-methyl-, 2-chloromethyl-, 2-trifluoromethyl-, 2-methoxy-, 4-methoxy-2-methylthio-, 2-trifluoromethylthio-, 2-difluoromethyl-thio-, 2-cyclopropyloxycarbonyl-, 2-phenoxy-, 2-difluoro-Le A 26 727 - 34 -methoxy-, 2-trifluoromethoxy-, 2-(2-chloroethoxy)-, 2-methyl~hiomethyl-, 2-dimethylaminosulphonyl-, 2-phenyl-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-dimethylamino-carbonyl- and 2-diethylaminocarbonyl-benzenesulphonyl amide and (2-chloro-phenyl)-, (2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)-and(2-~rifluoromethoxy-phenyl)-methanesulphonyl amide, 2-chloro-6-methyl-benzene-,~ sulphonyl chloride and 2,6-dichloro-benzenesulphonyl amide.
1 10 The sulphonic acid amides of the formula (VII) are known and/or can be prepared by methods which are Xnown per se (compare J. Org. Chem. 33 (1968), 2104; J.
¦ Org. Chem. 25 (1960), 1824; DE-AS (German Published ! Specification) 2,308,262; EP-OS 23,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; US-PS 2,929,820, 4,282,242; 4,348,220 and 4,372,778 and Angew. Chem. 93 (1981), 151).
I Formula (III) provide~ a general definition of the azines further to be used as starting substance~ in the process for the preparation of the new compounds of ~ the formula (I) according to the invention. In formula l (III), R2, X, Y and Z preferably or in particular have those meanings which have already been indicated above as preferred or as particularly preferred for R2, X, Y and Z
~1 25 in connection with the description of the compounds of the formula (I) according to the invention, and Q prefer-ably represents fluorine, chlorine, bromine or Cl-C4-alkylsulphonyl, in particular chlorine or methyl-sulphonyl.
Examplesi of the compound~ of the formula (ITI) Le A 26 727 - 35 -20iO647 which may be mentioned are:
2-chloro- and 2-methylsulphonyl-4,6-dimethyl-pyrimidine, -4-methyl-6-methoxy-pyrimidine, -4,6-dimethoxy-pyrimi-dine,-4-methyl-6-ethoxy-pyrimidine,-4-chloro-6-methoxy-pyrimidine, -4-methyl-pyrimidine, -4-chloro-6-methyl-pyrimidine, 4-trifluoromethyl-6-methoxy-pyrimidine, -4-methoxy-6-difluoromethoxy-pyrimidine, -4-methyl-6-di-fluoromethoxy-pyrimidine, -4,6-bis-difluoromethoxy-pyrimidine,-4-chloro-6-ethoxy-pyrimidine,-4,6-diethoxy-pyrimidine,-4,5-dichloro-6-methyl-pyrimidine,-4-methyl-5-chloro-6-methoxy-pyrimidine, -4,6-dichloro-pyrimidine, -4-ethyl-6-methoxy-pyrimidine, -5-chloro-4,6-dimethoxy-pyrimidine and -4,6-bis-trifluoromethyl-pyrLmidine, in addition 2-chloro-4,6-dimethyl-s-triazine, 2-chloro-4-methyl-6-methoxy-s-triazine, 2-chloro-4,6-dimethoxy-s-triazine, 2,4-dichloro-6-methoxy-s-triazine, 2-chloro-4-ethyl-6-methoxy-s-triazine and 2-chloro-4-methyl-6-ethoxy-s-triazine.
The azines of the formula (III) are known and/or can be prepared by methods which are known per ~e (com-pare J. Chem. Soc. 1957, 1830, 1833; J. Org. Chem. 26 (1961), 792; US-P 3,308,119 and US-P 4,711,959).
The process for the preparation of the new compound-~ of the formula (I) according to the invention is preferably carried out using diluents. Suitable diluents here are virtually all inert organic solvents.
These preferably include aliphatic and aromatic, option-ally halogenated hydrocarbons such a~ pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, b-nzun-, tolu-n , xyl-n-, m-thyl-ne chlorid-, ethylene Le A 26 727 - 36 -,i , .
chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ~; ether, glycol dimethyl ether and diglycol dimethyl ether, , tetrahydrofuran and dioxane, ketones such as acetone, 3~ 5 methyl ethyl ketone, methyl isopropyl ketone and methyl t, isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as, for example, acetonitrile and propionitrile, amides such as, for example, dimethyl-formamide, dLmethylacetamide and N-methyl-pyrrolidone and dimethyl sulphoxide, tetramethylene sulphone and hexa-methylphosphoramide.
Acid acceptors which can be employed in the process according to the invention are all acid binding agents customarily utilizable for reactions of this type.
Suitable alkali metal hydroxides are preferably those ~uch as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxide, alkali metal carbonates and alkoxide~ such as sodium carbonate and potassium car-bonate, sodium tert-butoxide and potassium tert-butoxide, and further aliphatic, aromatic or heterocyclic amine~, for example triethylamine, trimethylamine, dimethylani-line, dimethylbenzylamine, pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene ~ DBN ), 1,8-diazabicyclo-[5,4,0]-undec-7-ene ( DBU ) and 1,4-diazabicyclo-~2,2,2]-octane ( DABCO ) .
The reaction temperatures in the process accord-ing to the invention can be varied within a relatively large range. In general, the reaction is carried out at temperatures between 0C and 150C, preferably at tem-peratures between 20C and lOO~C.

Le A 26 727 - 37 -20~0647 The process according to the invention i8 in general carried out under normal pressure. However, it is also possible to work at elevated or reduced pressure.
In order to carry out the process according to the invention, the starting substances required in each case are in general employed in approximately equLmolar amounts. However, it is also possible to use one of the two components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. The work-up in the process according to the invention is in each case carried out according to customary methods.
The active compounds according to the invention can be used as defoliants, desiccants, agents for des-troying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides -depends es~entially on the amount used.
The active compounds according to the invention can be used, for example, in connection with ~he follow-ing plants:
DLcotyledon weed~ of the genera: Sinapis,Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, A~brosia, Cirsium, Carduus, Sonchus, Solanum, Le A 26 727 - 38 -", .. .
20~0647 '~i`!
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, ~, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, ~, 5Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras-sic~, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the ~enera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, lOSorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the aenera: Oryza, 15Zea, Triticum, ~ordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds accord-ing to the invention is in no way res~ricted to these genera, but also extends in the same manner to other 20plant~.
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.
25Equally, the compounds can be employed for combating weeds in perennial cultures, for ex2mple afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee planta-tion~, tea plantations, rubber plantations, oil palm 30plantations, cocoa plantations, soft fruit plantings and Le A 26 72? 39 hopfields, and for the selective combating of weeds in -~ annual cultures.
The compounds of the formula (I) according to the invention are suitable for selectively combating mono-cotyledon and dicotyledon weeds in monocotyledon anddicotyledon cultures both in the pre-emergence and in the post-emergence method.
The active compound~ can be converted into the cus~omary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials Lmpregnated 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 extender~, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that i5 emulsifying agents and/or dispersing agents and/or 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 cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, Le A 26 727 - 40 -,:

20~0647 ,.
ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol-vents, ~uch as dimethylformamide and dimethyl sulphoxide, as well as water.
. 5 As solid carriers there are suitable: for example ~:., ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, mont-.~ morillonite or diatomaceous earth, and ground synthetic .~ minerals, such as highly disperse silica, alumina and :j3 10 silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural minerals 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, corn cobs and tobacco stalks;
as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, ~1 s~ch as polyoxyethylene fatty acid esters, polyoxyethyl-ene fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkylsulphonates, alkyl sulphates, aryl-3 sulphonates as well as albumin hydrolysis products; as dispersing agents there are suitable: for example lignin-:~ sulphite waste liquors and methylcellulose.
Adhasives 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 phos-pholipids, such as cephalins and lecithins, and synthetic phospholipids, can be uced in the formulations. Further additives can be mineral and vegetable oils.

Le A 26 727 - 41 -_, ~ . . . . . . . . . .

~.j!

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-~ 5 stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling 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 component-Q for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3-(~,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N~N~-dimethyl-urea ¦ (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (META-MI~RON) for combating weeds in sugar beets and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soy beans; further-more also 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butyric acid (2,4-D3); 2,4-dichlorophen-oxypropionic acid (2,4-DP); 5-(2-chloro-4-trifluoro-methyl-phenoxy)-2-nitro-benzoic acid (ACIFLUORFEN); N-(methoxymethyl) -2,6-diethyl-chloroacetanilide (ALACHLOR);
methyl -6,6-dimethyl-2,4-dioxo-3-~1-(2-propenyloxyamino)-bu~ylidene]-cyclohexanecarboxylic acid (ALLOXYDIM); 2-Le A 26 727 - 42 -a ~$ 2010647 chloro-4-ethylamino-6-i~opropylamino-1,3,5-triazine (ATRAZINE); 3-iqopropyl-2,1,3-benzothiadiazin-4-one 2,2-'~'J dioxide (BENTAZONE); met~yl 5-(2,4-dichlorophenoxy)-2-~ nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzo-::~ 5 nitrile (BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-. diethylphenyl)-acetamide(~UTACHLOR);N,N-dimethyl-N'-(3-.j chloro-4-methylphenyl)-urea(cHloRToLuRoN);exo-l-methyl-.: 4-(1-methylethyl)-2-(2-methylphenyl-methoxy)-7-oxabi-;~, cyclo-(2,2,1)-heptane (CINMETHYLIN); 3,6-dichloro-2-'3j 10 pyridinecarboxylic acid (CLOPYRALID); 2-chloro-4-ethyl-;~ amino-6-(3-cyanopropylamino)-1,3,5-triazine (CYANAZINE);
'' 2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its ,J methyl ester or its ethyl ester (DICLOFOP); S-ethyl N,N-di-n-propyl-thiocarbamate (EPTAME); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); 2-~4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its l-methyl-heptyl ester ~FL~ROXYPYR); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN);
2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]-phenoxy}-propanoic acid or its ethyl ester (HALOXYFOP);
3,5-diiodo-4-hydroxybenzonitrile(IOXYNIL);N,N-dimethyl-: N'-(4-isopropylphenyl)-urea (ISOPROTURON), (2-ethoxy-1-methyl-2-oxo-ethyl)-5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrobenzoate (LAC~OFEN); (2-methyl-4-chloro-phenoxy)-acetic acid (MCPA); (4-chloro-2-methylphenoxy3-propionic acid ~(MCPP) t N-methyl-2-(1,3-benzothia~ol-2-Le A 26 727 - 43 -~ ` Z01064~ :
.
yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-dimethyl-henyl)-N~ H)-pyrazol-l-yl-methyl]-acetamide (METAZA-CHLOR); 2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-~ chloroacetanilide (METOLACHLOR); S-ethyl N,N-hexamethyl-c 5 ene-thiolcarbamate (MOLINATE) 4-(di-n-propylamino)-3,5-dinitrobenzenesulphonamide (ORYZALIN); 2 chloro-4-tri-fluoromethylphenyl 3-ethoxy-4-nitro-phenyl ether (OXY-f FLUORFEN); N-(l-ethylpropyl)-3,4-dimethyl-2,6-dinitroani-i line (PENDIMETHALIN); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE); 2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); 2-chloro-4,6-bis-(ethylamino)-1,3,5-tri-azine (SIMAZINE); 2,4-bis-[N-ethylamino]-6-methylthio-1,3,5-triazine (SIMETRYNE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); S-t(4-chloro-phenyl)-methyl]-N,N-diethyl-thiocarbamate (THIOBENCARB);
S-(2,3,3-trichloroallyl)-N,N-diisopropyl-thiolcarbamate (TRIALLATE); 2,6-dinitro-4-trifluoromethyl-N,N-dipropyl-aniline (TRIFLURALIN) and ethyl 2-[4-(6-chloro-quinoxa-lin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOPETHYL~.
Surprisingly, some mixtures also show a synergistic action.
Mixtures with other known active compounds, such : as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil ~tructure, are also possible.
The active compounds can be used as auch, 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 Le A 26 727 - 44 -201064~

granules. They are used in the cuctomary 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 0.005 and 5 kg of active compound per hectare of soil surface, preferably between 0.01 and 3 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.

. ~

k~ A 26 727 _ 45 _ n:~

Z0106~7 ,.
Preparation Exa~ples Example 1 H5C20~N~OC2H5 N~y~N
COOCH~ ¦
N--N
~S 2 - N=~ ~J

2.99 g (0.01 mol) of 2-(2-methoxycarbonyl-phenyl-S sulphonylamino)-1,3,4-thiadiazole are dissolved in 100 ml of tetrahydrofuran and 1.12 g (0.01 mol) of potassium tert-butoxide are added at 25C. After stirring for 30 minutes, 2.24 g (0.011 mol) of 2-chloro-4,6-diethoxy-s-triazine are added and the reaction mixture is ~oiled under reflux for 20 hours. The mixture is then concentra-¦~ ted in a water ~et vacuum, the residue is shaken with methylene chloride/water, and the organic phase is separated off, dried using sodium sulphate and filtered.
~ The solvent is distilled off from the filtrate in a water -`~ 15 ~et vacuum, the residue is stirred with diethyl ether and the product obtained crystalline in this way is isolated by filtering with suction.
1.4 g (30% of theory) of 2-(2-methoxycarbonyl-~ phenylsulphonylimino)-3-(4,6-diethoxy-triazin-2-yl)-2,3--~ 20 dihydro-1,3,4-thiadiazole of melting point 97C are obtained.
- The compounds of the formula (I) shown in Table 2 below can be prepared analogously to Example 1 and in accordance with the general description of the process according to the invention.

Le A 26 727 - 46 201~6~

Z~Y ~ 2 (I) Rl - 5.02 - N N~X
A
~able 2 E D
Examples of the compounds of the formul~ (I) Ex- A D E Rl ~2 X Y z Melting No. point C

COOCH~ .
~< , .
2 N CH S ~ OCH3 N N C-OCH3 103 3 CH CH S ~ OC~3 N 'N C-OCH3 15 ~: C 1 4 N CH S ~ OCH3 N N C-OCH3 157 CH

:;
.:

' ~
' : -;` ~,`''';' :~'' : Le A 26 7,27 _ 47 ~
, .

Table 2 - Continuation Ex- A D E R1 R2 X Y z Meltin~
- ____ , OCF3 N CH S ~ 0CH3 N N C-OCH~ 159 ¦ COOCH3 1 6 N C-CH3 S ~ OCH~ N N C-OCH3118 Cl :~

7 N C-CH3 S ~ OCH3 N N C-OCH3101 N C-CH3 S ~ OC2H5 N N C-OC2H5 120 O F
:~` /~( 9 N C-CH3 S ~ OCH3 N N C-OCH3 76 F
N C^CH3 S ~ OCH~ N N C-OCH3 151 Cl 11 N C-CH3 S ~ OCH3 N N C-OCH3 97 ~ CH3 ;..... ; : .
:' Le A 2 6 7 2 7 - 4 8 ~

: !~ 2 010 6 4 7 ~ Table 2 - Continuation :~ Ex- A D E R1 R2 X Y z Meltin~
, No. point C

J ~C 1 12 N CH S ~ OC2H5 N N C-OC2H5 133 : CH3 . Cl 13 N C-CH3 S ~ OC2H5 N N C-OC2H5 121 14 N C-CH3 S ~ OC~H5 N N C-OC2H5 119 N C-CH3 S ~ OC2H5 N N C-OC2H5 117 COOCH3 ;
16 N CH S ~ CH2- OCH3 N N C-OCH3 :

17 N CH S ~ CH3 N CH C-CH3 .
~: ~ COOCH~
: 18 N CH S ~ CH3 N CH C-OCH3 142 SO2N(CH3)2 19 N CH S ~ OCH3 N N C-OCH3 187 ~ -: .
: ':
~ Le A 26 727 _ 49 _ : :

:`

Z0~10647 Table_2 - Continuation Ex. A D E R1 ~2 X Y z Meltin~
No. point C
, _ N CH S ~ OCH3 N N C-OCH3 162 21 CH CH S ~ CH3 N CH C - OCH3 COQCH?
22 CH CH S ~ OC2Hs N N C-OC2H5 COOCH~
23 N C-CH3 O ~ OC2H5 N N C-OC2H5 COOCH3 ~ :~
: 24 CH CH S ~ CH3 N N C-OCH

; ~ Cl CH CH S ~ CH3 N CH C-CH3 : ~:

Cl -26 CH CH S ~ CH~ N CH C-CH
Cl ,,, ~
~ .

~ Le A 2~ 72? - 50 -.~ :

à 20~L0~i47 ~ Table ? - continuation No E Rl R2 point ~C

27 CH CH S ~ I OCH3 N CH C-OCH3 28 CH CH S ~ OCH3 N CH C-OCH3 Cl 2q CH CH S ~ CH3 N CH C-CH3 Cl 30CH CH S ~ CH3 N CH C-OCH3 Cl 31 CH CH S ~ CH3 N CH C-OCH3 Cl ~: 32 CH CH S ~ OCH3 N CH C-OCH3 ~ . .

33 N CH S ~ CH3 N CH C-OCH3 ~ :

':

` .~
`
: Le A 26 727 - 51 - : ~:

Table 2 - Continuation Ex A D E Rl R2 X Y z Meltin~
.. .

34 CH CH S ~ OCH3 N N C-OCH3 CH CH S ~ OCH~ N N C-OCH3 ~ COOCH3 36 N CH S ~ OCH3 N CH C-OCH~

Cl 37 N CH S ~ OCH3 N CH C-OCH3 :~ OC~
38 N CH S ~ CH3 N CH C-CH~

CH CH S ~ CH3 N CH C-OCH3 OCF3 ;~
41 N CH S ~ CH~ N CH C-OCH~

',` ~ ':

'~.

~ Le A 26 727 - 52 - ~ :~

Table 2 - Continuation Ex A D E R 1 R2 point ~C

42 N CH S ~ OCH3 N CH C-OCH

43 CH CH S ~ OCH3 N CH C-OCH~

44 CH CH S ~ OCH3 N CH C-OCH3 N CH S ~ CH3 N CH C-CH3 F :
~ 4 6 CH CH S ~ CH3 N CH C-CH3 -~ F
. . ~ ~ ,~ .
47 N CH 5 ~ OCH3 N CH C-OCH3 ~ -Cl , ~ 48 N CH S ~ CH3 N CH C-CH3 ' ,i Le A 26_727 - 53 -.: .
' ~', ., ~

Table 2 - Continuation ~, Ex. A D E R1 R2 X Y z Neltin~
No. _ _ _ point C
Cl 49 N CH S ~ CH3 N CH C-OCH3 N C-CH3 5 ~ CH3 N CH C-CH3 51 N C-CH3 S ~ CH3 N CH C-CH

52 N C-CH3 S ~ CH3 N CH C-CH3 ~ -,;~ 53 CH CH S ~ CH3 N CH C-OCH3 CH~

i ~ 54 CH CH S ~ CH? N CH C-OCH~

" ~ COOCH3 -M C-CH3 S ~ OCH3 N CH C-OCH~

' ! .

Le ~_26 727 - 54 -' 2010~i47 Table 2 - Continuation Ex A D E R1 R2 X Y z Meltin~

Cl 56 N C-CH3 S ~ CH3 N CH C-OCH3 57 N C-CH3 S ~ I CH3 N CH C-OCH3 58 N C-CH3 5 ~ r CH3 N CH C-OCH3 59 N CH S ~ CH3 N CH C-OCH3 r .
N CH S ~ OCH3 N CH C-OCH3 61 N C C2H5 S ~ CH3 N CH C-OCH3 `:
62 N C-C2H5 S ~ CH3 N CH C-OCH3 63 N CH S ~ OOCH~ CH? N CH C-CH3 Le A 26 727 _ 55 _ - 20~0647 Table 2 - Continuation Ex A ~ E R1 R2 X y z Oelttin~c 64 N CH S ~ COOCH3 CH3 N CH C-OCH3 N CH S ~ OOCH3 OCH3 N CH C-OCH3 OCHF2 , 66 N CH S ~ CH3 N CH C-OCH3 67 N CH S ~ CH3 N CH C-OCH

68 N CH S ~ OCH3 N CH C-OCH3 69 N C-SCH3 S ~ CH3 N CH C-CH

Cl N CH S ~ CH3 N CH C-OCH3 F
--( 71 N CH S ~ CH3 N CH C-OCH3 , Le A 26 727 - 56 ~ Table 2 - ContLnuation 20~647 :~ Ex A n E R1 R2 X Y Z Meltin~
point C
:t Br : 72 N CH S ~ CH3 N CH C-CH3 , CH3 73 N CH S ~ CH3 N CH C-OCH3 74 N CH S ~ CH3 N CH C-CH3 N CH S ~ ~H3 N CH C-CH3 COOCH
76 N CH S ~ CH2- OCH3 N CH C-OCH~ -:~

, ~ 77 N CH S ~ CH3 N N C-OCH3 8 N CH S ~ OCH3 N N C-OCH~

:~ COOCH~
79 N CH S ~ CH3 N N C-OCH3 ;

:

:

Le A 26 7~7 - 57 -l ~ , I , 201(~647 : ::
~able 2 - Continuation Ex. A D E R1 R2 X Y z Meltin~
point C

N CH S ~ OCH3 N N C-OCH3 81 N CH S ~ OOCH3 CH3 N N C-OCH3 82 N CH S ~ COOCH3 OCH3 N N C-OCH3 N C-SCH3 S ~ OCH3 N N C-OCH3 SCH?
84 CH CH S ~ OCH3 N CH C-OCH3 N CH S ~ OCH3 N N C-OCH3 ~ 5O2N(CH ) '~ : 86 N CH S ~ OCH3 N CH C-OCH3 `: OCH3 87 N CH S ~ CH~ N CH C-CH3 ' ' `; ~ ' Le A 26 727 - 58 -~: ;
' :: .

i 201064~
. Table 2 - Continuation Ex- A D E R1 R2 X Y z Meltin~
No. point C

8 8 N CH S ~ OCH3 N CH C-Cl 89 N CH S ~ OCHF2 N CH C-OCHF2 90 N CH S ~ CHz- OCH3 N CH C-OCH3 91 N CH S ~ CH2- OCH3 N N C-OCH3 ~ 92 N CH S ¦ ~ OOCH3 OCH3 N CH C-OCH

,~ 93 N CH N ~ COOC2H5 OCH? N CH C-OCH3 CH~

94 N CH S ¦ ~ OOCH3 OCH~ N N C-OCH3 :

Le A 26 727 - 59 _ ~ Table 2 - Continuation 2010647 dEx A D E R1 R2 X Y z Meltin~

.' N==~
95 N CH N ~ C2H5 OCH3 N N C-OCH3 . CH3 COOCH(CH3)2 96 N CH S ~ OCHJ N N C-OCH3 ~' Cl . COOC2H5 97 N CH S ~ OCH3 N CH C-OCH3 CF3 ::~
98 N CH S ~ OCH3 N CH C-OCH3 .
CON(CH3)2 99 N CH S ~ OCH3 N CH C-OCH3 :

C~H5 100 N CH S ~ OCH3 N CH C-OCH3 3 ~
COOC~3 101 CH CH S ~ CH3 N CH C-CH3 ` ` OCF
102 N CH S ~ C2H5 N N C-OC2H5 103N CH S ~ C2H5 N N C-0~2H5 132 : ~:
.

~ .

Table 2 - Continuation Z0106A7 Ex. A D E R1 R2 X Y z Meltin~
No. point C
.~ ,, 104 N CH S ~ OCH3 N N C-OCH3 128 105 N CH S ~ OCH3 N N C-OCH3 165 106 N CH S ~ OC2H5 N N C-OCH3 9 107 N CH S ~ OC2H5 N N C-OCH3 ~ 108 N CH S ~ OC2H5 N N C-OCH3 137 `:~ CH3 109 N CH S ~ OCH3 N N C-OCH3 , :; ~ 3 3 111 N CH S ~ OC2H5 N N C-OCH3 112 N CH S ~ OC2H5 N N C-OC2H5 I` , I` ~ A 26 727 - 61 -~ 20106~7 Table 2 - Continuation ~ Ex. A D E R1 R2 X Y z Meltin~
-1 No. point C
.~l CF3 i 113 N CH S ~ OC2H5 N N C-OCH3 114 N CH S ~3 OC2115 N N C-OC~H5 Cl 115 N CH S ~ CH3 N N C-CH3 CH3 ~:

116 N CH S Cl ~ OCH3 N N C-OCH3 : CH3 117 CH CH S ~ OCH3 N N C-OCH3 ~` Cl ` ~ 118 N CH S H3C ~ OCH3 N N C-OCH3 ., Cl ~ 119 CH CH S ~ OCH3 N N C-OCH3 ";~ CH3 :~
Cl '. :.
; 120 CH C~ S . ~ ! OCH3 N N C-OCH3 .

~ Cl ;~: 121 CH CH S ~ C~3 N CH C-OCH3 , .
~, ~ Le A 26 727 - 62 -< : ~

Z0~0647 Table 2 - Continuation Ex. A DE R1 R2 X Y z Neltin~
No. point C

122 CH CHS ~ CH3 N CH C-OCH3 123 CH CHS ~ ~H3 N CH C-OCH3 124 CH CHS ~ CH~ N CH C-OCH~

125 CH CH S ~H2- oc2H5 N N C-9C2H5 ; COOCH3 126 CH CH S ~ ~2 Oc2~s N N C-OCH3 127 CH CHS ~ CH3 N CH C-OCH

~`~ Cl -~ 128 CH CHS ~ OC2H5 N N C-OCH3 . COOC2H5 129 CH CH S ~ OCH3 N N C-OCH3 1~0 CH CH S ~ OC2H5 N N C-OCH3 ;

-.
:' Le A 26 727 - 63 ~

: ~

20~06A7 Table 2 - Continuation Ex . A D E R 1 R2 X r z Meltin~
No. point C

131 CH CH S ~ OCH3 N N C-OCH3 132 CH CH S ~ OC2H5 N N C-OCH3 133 CH CH S ~ OC2H5 N N C-OCH3 134 CH CH S ~ OCH~ N N C-OCH3 ~`: OCF3 : 135 CH CH S ~ CH3 N CH C-CH3 175 COOCH
~:; 136 CH CH S ~ CH3 N CH CH

,~ :

~ .
I,e A 26 727 - 64 -- - 20106~7 Startinq substances of_the formula_(II
Exa~e~

~502-NH~ ~
H

A mixture of 10.1 g (0.10 mol) of 2-amino-1,3,4-thiadiazole and 50 ml of pyridine is cooled to -10C and ~ 31.2 g (0.12 mol) of 2-methoxycarbonyl-benzenesulphonyl ! chloride (90~ strength) are added in portions with stirring at this temperature. The reaction mixture is then stirred for a further 2 hours at -lO~C and a further 20 hours at +25C and subsequently concentrated in a water jet vacuum. The residue is taken up in dichloro-methane, ~nd the solution is washed with water, dried ~ using magnesLum sulphate and filtered. The solvent is ¦~ distilled off from the filtrate in a water ~ét vacuum.
The residue is dissolved in 5% strength aqueous sodium hydroxide solution, and the product is precipitated by addition of concentrated hydrochloric acid and isolated by filtering with suction.
21.5 g (71~ of theory) of 2-(2-methoxycarbonyl-phenylsulphonylamino)-1,3,4-thiadiazole of melting point 96C are obtained.
`~

~'` ' ~'''`' :~;
l ~e A ~Ç 7~7 - 65 -I
:', :-~
.~ .
: ~ :

Example ~ 2!

~S 2 - NH~

A mixture of 10.0 g (0.10 mol) of 2-amino-thia-~ole and 50 ml of pyridine is cooled to -10C and 62.4 q (0.24 mol) of 2-methoxycarbonyl-benzenesulphonyl chloride (90~ strength) are added in portions with stirring at this temperature. The reaction mixture is then stirred for a further 2 hours at -10C and a further 20 hours at +25C and subsequently concentrated in a water ~et vacuum. The residue i8 taken up in dichloromethane, and the solution is washed with water, dried using sodium --~ 2, sulphate and filtered. The solvent is distilled off from ; the filtrate in a water jet vacuum, the residue is made ;; to crystallize using ethanol and the product is isolated by filtering off with suction.
;~ 25.8 g (56% of theory) of 2-tbis-(2-methoxycar-bonyl-phenylsulphonyl)-amino)-thiazole of melting point 167C are obtained.
22.9 g (0.05 mol) of 2-(bis-t2-methoxycarbonyl-phenylsulphonyl)-amino)-thiazole are taken up in 100 ml of ethanol and, after addition of 100 ml of concentrated -~
aqueous ammonia, the mixture is boiled under reflux for 30 minutes. It is then concentrated in a water ~et vacuum, the residue is taken up in 200 ml of water and the solution iB ad~usted to pH 6 by adding concentrated ~hydrochloric acld. iThe'product obtained crystalline in : ' ~ Le A 26 727 - 66 -; ~' 20~0647 this way is isolated by filtering with suction.

9.2 g (61% of theory) of 2-(2-methoxycarbonyl-phenylsulphonylamino)-thiazole of melting point 196~C are obtained.
S The compounds of the formula (II) shown in Table 3 below can be prepared analoqously to Example (II-1) or (II-2)- ~-Lo A ~ ?27 - 67 -, .:
~' ~:. , '~ ' ~ ~, 20~0647 Table 3 Examples of the compounds of the formula tII) Ex. A D E R1 Melting point No. (C) II-3 N CH S ~ 160 II-4 N C-CH3 S ~ 143 ~`

Cl II-5 N CH S ~ 132 Cl ~ 6 N C-CH3 5 ~ lP5 `~: OCF3 ~ ; :
~: II-7 N C-CH3 S ~ 135 C1 .
. ~
: II-8 N C-CH3 S ~ 180 !~ . .

~ Il-9 N C-CH3 S ~ 154 '~ .

¦~ Le A 26 727 - 68 ~

20~0647 Table 3 - Continuation Examples of the compounds of the formula (II) ¦~
~x. A D E R1 ~elting point No. ( C) ~=<
13 N C-CF3 5 ~ 65 ¦ 1l-11 N CH S ~ CH2-I

Br II-12 N CH 5 ~ 241 II-13 C-C1 N O ~ ~
~: :

.~
:~ ~ .
",~

~: ~
~ . ~ '', i I ~ ' ` :' :' :: :
~ , , - :

Le A 2~_727 - 69 ~
~' :

Example A ~3~4~

Post-emergence test Solvent: 5 parts by weight of acetone i Emulsifier: 1 part by weight of alkylaryl polyglycol ether ¦ To produce a suitable preparation of active com-pound, 1 part by weight of active compound is mixed with I the stated amount of solvent, the stated amount of I 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 I such a way as to apply the particular amounts of active I com~ound desired per unit area. The concentration of the ¦ 15 spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 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:
~ 20 0% = no action (like untreated control) i 100% = total destruction ~ ;
A clearly superior action compared to the prior '~
art is shown in this test, for example, by the compounds ~ according to Preparation Examples 1 and 5.
1``-' .

~, ''" ~
~ ,"-'.
~ Le A 26 ~2~ _ 70 _ --~`

Exam~le B 20~0647 Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a sui~able preparation of active com-pound, l part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier i8 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 constant the amount of water per unit area. The concentration of the active compound in ths preparat~on is of no importance, only the amount of active compound applied per unit area being decisive. ~fter 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 A clearly superior action compared to the prior art is shown in this test, for example, by the compounds ~ according to Preparation Examples 2 and 5.
I `,~
It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other emobdiments within the spirit and scope of the invention will suggest themselves to those ` skilled in the art.

~e A 26 727 - 71 -

Claims

1. A sulphonylimino-azinylheteroazole of the formula I

(I) in which A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, halogen, cyano, nitro or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino, dialkylamino or phenyl, D represents nitrogen or the grouping C-D1, in which D1 represents hydrogen, halogen, cyano, nitro or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino, dialkylamino or phenyl, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, R1 represents in each case optionally substituted alkyl, aralkyl, aryl or heteroaryl, R2 represents hydrogen, halogen, hydroxyl, amino or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkyl-amino or dialkylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, halogen, cyano, alkyl, formyl, alkylcarbonyl or alkoxycarbonyl, and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, halogen, hydroxyl, amino or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino or dialkylamino.

2. A sulphonylimino-azinylheteroazole according to claim 1, in which A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, fluorine, chlorine, bromine, iodine, cyano or nitro, or represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino or di-(C1-C4)-alkyl-amino in each case optionally substituted by fluorine and/or chlorine or C1-C4-alkoxy, or represents phenyl optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C2-fluoro- and/or chloro-alkyl, C1-C4-alkoxy and/or C1-C2-fluoro-and/or -chloro-alkoxy, D represents nitrogen or the grouping C-D1, in which D1 represents hydrogen, fluorine, chlorine, bromine, iodine, cyano or nitro, or represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino or di-(C1-C4)-alkyl-amino in each case optionally substituted by fluorine and/or chlorine or C1-C4-alkoxy, or represents phenyl optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl. C1-C2-fluoro- and/or chloro-alkyl, C1-C4-alkoxy and/or C1-C2-fluoro-and/or -chloro-alkoxy, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, R1 represents the radical , in which R5 and R6 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxycarbonyl, C1-C4-alkylamino-carbonyl, di-(C1-C4-alkyl)aminocarbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-car-bonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl), C2-C6-alkenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxy or phenyl), C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl , C1-C4-alkoxy (which is optionally sub-stituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl), C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), C3-C6-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-cyano or C1-C4-alkoxy-carbonyl), C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(O)p-R7, where p represents the numbers 1 or 2 and R7 represents C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkylamino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino or for the radical -NHOR8, where R8 represents C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsul-phonyl, C1-C4-alkyl-carbonyl, C1-C4 alkoxy-carbonyl, C1-C4-alkylamino-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl), C3-C6-alkenyl (which is optionally substituted by fluorine, chlor-ine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cyclo-alkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substituted by fluorine, chlor-ine, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl), benzhydryl or phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, trifluoro-methyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C4-alkylthio, trifluoromethylthio or C1-C4-alkoxy-carbonyl), R5 and R6 furthermore represent phenyl or phenoxy, C1-C4-alkylcarbonylamino, C1-C4-alkoxycar-bonylamino, C1-C4-alkylamino-carbonylamino, di-(C1-C4-alkyl)-amino-carbonylamino, or the radical -CO-R9, where R9 represents C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkylthio, amino, C1-C4-alkyl-amino, C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino (which are optionally substitu-ted by fluorine and/or chlorine), R5 and R6 furthermore represent C1-C4-alkylsulphonyl-oxy, di-(C1-C4-alkyl)-aminosulphonylamino or the radical -CH=N-R10, where R10 represents C1-C6-alkyl optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, benzyl option-ally substituted by fluorine or chlorine, C3-C6-alkenyl or C3-C6-alkinyl optionally substituted by fluorine or chlorine, phenyl option-ally substituted by fluorine, chlor-ine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoro-methoxy or trifluoromethylthio, C1-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy optionally substituted by fluorine and/or chlorine, amino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C4-alkoxy-carbonyl-amino, C1-C4-alkyl-sulphonylamino or phenylsulphonyl-amino optionally substituted by fluorine, chlorine, bromine or methyl, in which in addition R1 represents the radical , in which R11 represents hydrogen or C1-C4-alkyl, R12 and R13 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is option-ally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine), carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylsulphonyl or di-(C1-C4-alkyl)-aminosulphonyl; in which in addition R1 represents the radical , in which R14 and R15 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is option-ally substituted by fluorine and/or chlorine) or C1-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine); in which in addition R1 represents the radical , in which R16 and R17 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is option-ally substituted by fluorine and/or chlorine), C2-C4-alkenyl (which is option-ally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-C4-alkylsul-phinyl or C1-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), and di-(C1-C4-alkyl)-aminosul-phonyl, C1-C4-alkoxy-carbonyl, dimethyl-aminocarbonyl or dioxolanyl; in which in addition R1 represents the radical in which R18 and R19 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which is optionally substitu-ted by fluorine and/or bromine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkyl-thio,C1-C4-alkylsulphinyl or C1-C4-alkylsul-phonyl (which is optionally substituted by fluorine and/or chlorine), or di-(C1-C4-alkyl)-aminosulphonyl; in which in addi-tion R1 represents the radical , in which R20 and R21 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl (which is option-ally substituted by fluorine, chlorine, C1-C4-alkoxy and/or C1-C4-halogenoalkoxy), C1-C4-alkoxy (which is optionally sub-stituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C1-C4-alkyl)-amino-sulphonyl or C1-C4-alkoxy-carbonyl, and Q1 represents oxygen, sulphur or the grouping N-Q2, where Q2 represents hydrogen, C1-C4-alkyl (which is optionally substituted by fluorine, chlor-ine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally sub-stituted by fluorine, chlorine, bromine or nitro), C1-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl;
in which in addition R1 represents the radical , in which R22 and R23 are identical or different and represent hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxycarbonyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, Q3 represents sulphur or the grouping N-R24, where R24 represents hydrogen or C1-C4-alkyl; in which in addition R1 represents the radical , in which R25 represents hydrogen, C1-C4-alkyl, phenyl or (iso)quinolinyl, R26 represents hydrogen, halogen, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or C1-C4-alkoxy-carbonyl and R27 represents hydrogen, halogen or C1-C4-alkyl; in which in addition R1 represents the radical , in which R28 represents hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy-carbonyl; in which in addition R1 represents the radical , in which R29 represents C1-C4-alkyl and R30 represents C1-C4-alkyl, in which in addition R1 represents the radical , in which R31 represents hydrogen or methyl, R2 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, bis-(C1-C2-alkoxy)-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, dimethylamino or diethylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, fluorine, chlorine, bromine, cyano, methyl, formyl, acetyl, meth-oxycarbonyl or ethoxycarbonyl, and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, bis-(C1-C2-alkoxy)-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, dimethylamino or diethylamino.

3. A sulphonylimino-azinylheteroazole according to claim 1, in which A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl, trifluoromethyl, di-chloromethyl, trichloromethyl, chlorodifluoro-methyl, fluorodichloromethyl, methylthio, ethylthio, propylthio, butylthio or phenyl, D represents nitrogen or the grouping C-D1 in which D1 represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl, trifluoromethyl, di-chloromethyl, trichloromethyl, chlorodifluoro-methyl, fluorodichloromethyl, methylthio, ethylthio, propylthio, butylthio or phenyl, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, R1 represents the radical , in which R5 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C1-C3-alkylthio, C1-C3-alkyl-sulphinyl, C1-C3-alkylsulphonyl, dimethylamino-sulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C1-C3-alkoxy-carbonyl and R6 represents hydrogen, fluorine or chlorine; in which in addition R1 represents the radical , in which R11 represents hydrogen, R12 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and R13 represents hydrogen, fluorine or chlorine; in which in addition R1 represents the radical , in which R represents C1-C4-alkyl, or R1 represents the radical , in which R represents C1-C4-alkyl, or R1 represents the radical , in which R28 represents hydrogen, chlorine, methyl, ethyl, methoxycarbonyl or ethoxycarbonyl;
in which in addition R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, fluorine, chlorine or methyl and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.

4. A compound according to claim 1, wherein such compound is 2-(2-methoxycarbonyl-phenylsulphonylimino)-3-(4,6-diethoxy-triazin-2-yl)-2,3-dihydro-1,3,4-thiadiazole of the formula .

5. A compound according to claim 1, wherein such compound is 2-(2-methoxycarbonyl-phenylsulphonylimino)-3-(4,6-dimethoxy-triazin-2-yl)-2,3-dihydro-1,3,4-thiadiazole of the formula .

6. A compound according to claim 1, wherein such compound is 2-(2-trifluoromethoxy-phenylsulphonylimino)-3-(4,6-dimethoxy-triazin-2-yl)-2,3-dihydro-1,3,4-thiadi-azole of the formula .

7. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

8. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a solid diluent or carrier, a liqui-fied normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.

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 any one of claims 1 to 6.

10. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

11. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a pre-emergence herbicide.

14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a post-emergence herbicide.

15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 0.005 and 5 kg/ha.

16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 0.01 and 3 kg/ha.

17. A process for preparing a compound of formula I
according to claim 1 which comprises reacting a compound of formula II

(II) in which A, D, E and R1 are as defined in claim 1, with an azine of formula III

(III) in which X, Y, Z and R2 are as defined in claim 1 and Q is halogen or alkylsulphonyl.

18. A sulphonylamino-heteroazole of the formula (II) in which A, D, E and R1 are as defined in claim 1.

19. A process for preparing a compound of formula II
as defined in claim 18, wherein A, D, E and R1 are as de-fined in claim 18, which process comprises:
.alpha.) reacting an aminoheteroazole of the general formula (IV) (IV) in which A, D and E have the abovementioned meanings, with a sulphonyl halide or sulphonic anhydride of the general formula (V) R1-SO2-Q4 (V) in which R1 has the abovementioned meaning and Q4 represents chlorine, bromine or the grouping -O-SO2-R1, in which R1 has the abovementioned meaning, and, where required, the reaction product is treated with ammonia, or .beta.) reacting a heteroazole of the general formula (VI) (VI) in which A, D and E have the abovementioned meanings and Q5 represents halogen or alkylsulphonyl, with a sulphonyl amide of the general formula (VII) R1-SO2-NH2 (VII) in which R1 has the abovementioned meaning.