Note: Descriptions are shown in the official language in which they were submitted.
2010647
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 -
2010647
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 -
2010647
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,
R6
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 R12
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
R17
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
2010647
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
R22
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
R300 -R29
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 -
.. : . , , , :::.:, - , ., ,,,. ,,,.. ~ ~.. . . . . .
2010647
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
R5
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
R 1 2
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)
R1-52-NH
'Y`A tIt)
E - D
A D E R1
. . . _ .
COOCH~
'~ N CH O ~
COOCH3
~;~ N CH S ~
:~
COOCH3
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
A D E R1
.
COOCH3
N C-CH3 O ~
COOCH3
N C-CH3 S ~
~ COOCH3
C-CH3 CH S
COOCH3 :
N C-CF3 S ~
-~ ~ OOCH3
N C-C2H5 5 ~
COOC~3
N C-C~H5 S
COOCH3
N C-SCH3 5 ~
'
',: '
L4 A 26 727 - 18 -
~ ` :
Z01064~ ~
Table 1 - Continuation
a
A D E R1
COOCH3
C-C2H5 CH S ~
COOCH3
N C-CHC12 S ~
COOCH3
C-Cl C-C1 S ~
COOC ~H5
; N CH O ~
1 ~
C OOC 2H5
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 -
X010647
Table 1 - Continuation
A D E R1
. . _ . _ . . _ _
COOC2H5
N C - CH3 o ~
COOC2H5 -,
N ~-CH3 S ~ :
COOC2Hs
N C-SCH3 S ~
~:~ C l :
N CH S
C 1
CH N S
.~ .
C 1
C-CH3 N S ~ - ~ :
CH CH S
~; N C - CH ~ O
.~
LQ A 26 727 - 20 - ~ -
' "'-' -
2010647
TablQ 1 - Continuation
A D E Rl
Cl
N C - CH3 5
Cl
N C-CF3 5
Cl
N C-SCH3 S
~: C l
N C-C6H5 S ~ ~ ~:
N C-CH ~ CH~ ) 2 5 ~
. .- .
C 1
N c-Sc4H9 5
. ~
C l
. C-Cl C-Cl S <~ ~;
N CH S ~
"~ :
,
Le A 26 727 - 21
` ` 2010647
Table 1 - Continuation
A D E R1
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
C-CH3 N S
I~e A 26 727 -22
` ~
Z010647
Table 1 - Continuation
A D E R
Br
CH CH S
8r
N C-CH3 5
CH3
N CH S
CH~ ~
CH N S ~ ;
,~
C - CH 3 N ~3
; ~ N C - CH 3 5 <~3 ~ ;
CH3
CH CH S ~
CH3
N C-SCH3 S
'
;` ~ :
Le A 2 6 7 2 7 - 2 3
zo~0647
Table 1 - Continuation
.`
,.
I A D E R1 --
i
CF3
N CH S
CH N S ~
¦ CF3
C-CH~ N S ~
CF3
N C-CH3 5 ~
OCH3
. ~ N CH S ~
CH N S ~ H3
OCH3 :
. ~=< " ' ~: .' - "
C-CH3 N S ~ ! ;~
OCH~
N C-CH3 5
'
. ~ :
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 ~
OCH3
3 N C - C 6 H 5 S ~
OCHF2
N CH S ~ : :
OCHF2
~ ~ Cll N S
i, ~: :
. ~
. "~ ~ OCHF2
C-CH3 N S ~
~ ~_< 2
i ~ N C-CH3 5 <~
OCHF2
~; C~l CH S
Le A 26 727 - 25 -
Z010647
Table 1 - Continuation
A D E F1
OCHF2
N C-SCH3 S ~
: 2
N C-C6H5 S
OCHF
C-C1 C-Cl S ~
OCF3
N CH S ~
OCF3
:~ CH N S ~ ~ :
OCF3
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 :
OCF3
C-Cl C-Cl S ~
OCH2CH2C 1
N CH S ~
OCH2CH2C 1
CH N S
` OCH2CH2C 1 ;;
C-CH~ N S
0CH2CH2C1
N C-CH3 S ~
OCH2CH2Cl ~ :
; ~ CH CH S ~ : ~.v;.
OCH2CH2C 1
~ N C-SCH3 S
; ! oCH2CH2Cl : ~
` N C-CF3 S ~ :~ :
Le A 26 727 - 27 ~
Z010647
Table 1 - Continuation
A D E R1
OCH2cH2c 1
N C-C6H5 S ~
SCH3
~ 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
SCH3
N C-CF3 S
N C-C6H5 S ~ H3
Le A 26 727 - 28 -
Z0~0647 :
Table 1 - Continuation
,
A D E R1
~< 3
CH CH S <~
f SCH3
C-Cl C-Cl S <~
502CH3
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
NH2
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 -
.:
~:;
Z010647
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 -
2010647
:.
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 -
.
::
2010647
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 -
20106A7
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 -
2010647
,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
2010647
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!
Z010647
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
COOCH3
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 ~
, .
2010647
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
COOCH3
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
OCF3
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 :
COOCH3
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
, _
OCHF2
N CH S ~ OCH3 N N C-OCH3 162
COOCH3
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 : ~:
02N
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
COOCH3
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
COOCH3
~: 32 CH CH S ~ OCH3 N CH C-OCH3
~ . .
COOC2H5
33 N CH S ~ CH3 N CH C-OCH3 ~ :
':
` .~
`
: Le A 26 727 - 51 - : ~:
2010647
Table 2 - Continuation
Ex A D E Rl R2 X Y z Meltin~
.. .
COOC2H5
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~
F3
CH CH S ~ CH3 N CH C-OCH3
OCF3 ;~
41 N CH S ~ CH~ N CH C-OCH~
',` ~ ':
'~.
~ Le A 26 727 - 52 - ~ :~
2010647
Table 2 - Continuation
Ex A D E R 1 R2 point ~C
OCF3
42 N CH S ~ OCH3 N CH C-OCH
OCF3
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 -
.: .
' ~',
., ~
2010647
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
CH3
COOCH3
N C-CH3 5 ~ CH3 N CH C-CH3
51 N C-CH3 S ~ CH3 N CH C-CH
OCF3
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
COOCH3
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
COOCH3
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
OCHF2
67 N CH S ~ CH3 N CH C-OCH
OCHF2
68 N CH S ~ OCH3 N CH C-OCH3
COOCH3
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
CF3
74 N CH S ~ CH3 N CH C-CH3
COOC2H5
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
COOC2H5
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
OCF3
N C-SCH3 S ~ OCH3 N N C-OCH3
SCH?
84 CH CH S ~ OCH3 N CH C-OCH3
5O2CH3
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
COOC 2H5
8 8 N CH S ~ OCH3 N CH C-Cl
COOCH3
89 N CH S ~ OCHF2 N CH C-OCHF2
OCF3
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
F2CHO
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
OCHF2
103N CH S ~ C2H5 N N C-0~2H5 132
: ~:
.
A 26 727 - 60 -
~ .
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
COOCH3
106 N CH S ~ OC2H5 N N C-OCH3 9
OCF3
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
C6H5
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
OCF3
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
OCF3
122 CH CHS ~ CH3 N CH C-OCH3
COOC2H5
123 CH CHS ~ ~H3 N CH C-OCH3
124 CH CHS ~ CH~ N CH C-OCH~
S OOCH3
COOCH3
125 CH CH S ~H2- oc2H5 N N C-9C2H5
; COOCH3
126 CH CH S ~ ~2 Oc2~s N N C-OCH3
CF3
127 CH CHS ~ CH3 N CH C-OCH
~`~ Cl
-~ 128 CH CHS ~ OC2H5 N N C-OCH3
CH3
. COOC2H5
129 CH CH S ~ OCH3 N N C-OCH3
OCF3
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
COOC2H5
133 CH CH S ~ OC2H5 N N C-OCH3
COOCH3
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~
COOCH3 N - N
~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
:', :-~
.~ .
: ~ :
2010647
Example ~ 2!
COOCH3 H
~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)
OCF3
II-3 N CH S ~ 160
COOCH3
II-4 N C-CH3 S ~ 143 ~`
Cl
II-5 N CH S ~ 132
CH3
Cl
~ 6 N C-CH3 5 ~ lP5
`~: OCF3 ~ ; :
~: II-7 N C-CH3 S ~ 135
C1 .
. ~
: II-8 N C-CH3 S ~ 180
CH3
!~ . .
~ 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)
COOCH3
~=<
13 N C-CF3 5 ~ 65
COOCH3
¦ 1l-11 N CH S ~ CH2-
I
Br
II-12 N CH 5 ~ 241
C1
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 -
