Note: Descriptions are shown in the official language in which they were submitted.
2010650
The invention relates to new sulphonylated
azinyliminoheteroazoles, a process and new intermediates
for their preparation and their use as herbicides. "
It is known that 3-amino-1,2,4-triazole (ami-
trole~ can be used as a herbicide (compare Science 145
(1964),497). However, the action of this compound is not
satisfactory in all matters.
The new sulphonylated azinyliminoheteroazoles of
the general formula (I)
Z~
N (I)
R1-SO2`N ~ E
in which-' A v ~:
A represents nitrogen or the grouping C-A1, in which
A1 represents hydrogen, halogen, cyano, nitro or
in each case optionally substituted alkyl,
15 '' '''''~~~~'~~~~'''~alkoxy, alkyIthio, 'alkylsulphinyl,~'alkylsul- ~ '
phonyl, alkylamino, dialkylamino or phenyl, -:
D represents nitrogen or the grouping C-~1, in which
D represents hydrogen, halogen, cyano, nitro or . :~in each ~ase 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 A 26 728 - 1 -
.: . : . . . . . ~ . ~
20~650
E represents oxy~en or sulphur,
R1 represents in each case optionally substituted
alkyl, aralkyl, aryl or heteroaryl,
R2 represents hydrogen, halogen, hydroxyl, amino or in
Seach case optionally substituted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alXylsulphonyl,
alkylamino or dialkylamino,
X represents nitrogen or a CH grouping,
Y represents nitrogen or the grouping C-R3, in which
lOR3 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, zmino
or in each case optionally substituted alkyl,
15alkoxy, alkylthio, alkylsulphinyl, alkylsul-
phonyl, alkylamino or dialkylamino,
have now been found.
The new sulphonylated azinyliminoheteroazoles of
the general formula (I) are obtained when azinylamino-
20heteroazoles of the general formula (II) ~ .
(II)
NH
N~ I
in which A
A, D, E, R2, X, Y and Z have the abovementioned meanings,
are reacted with sulphonyl halides or sulphonic
anhydrides of the general formula (III)
Le A 26 728 - 2 -
20~065~)
R1-SO2-a (III)
in which
R1 has the abovementioned meaning and
Q represents fluorine, chlorine bromine or the group-
ing -O-SO2-R1,
in which
R~ has the abovementioned meanings,
if appropriate in the presence of an acid acceptor and if
appropriate in the presence of a diluent.
The new sulphonylate~ a~inyliminoheteroazoles of
the general formula (I) are characterized by strong her-
bicidal activity. These compounds represent a chemically
novel ~lass of herbicides.
Surprisingly, the new compounds of the formula
(I) show considerably better herbicidal action than the
structurally ~imilar known herbicide aminotriazole
(amitrole).
The invention preferably relates to compounds of
the formula (I), in which
20 A represents nitrogen or the grouping C-Al, in which
Al represents hydro~en, fluorine, chlorine,
bromine, iodine, cyano or nitro, or represents
Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-
C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, C1-C4-
alkylamino or di-tCl-C4)-alkyl-amino in each
case optionally substituted by fluorine and/or
chlorine or Cl-C4-alkoxy, or represents phenyl
optionally substituted by fluorine, ch1orine,
Le A 26 728 - 3 -
` :` 20~0650
bromine, Cl-C4-alkyl, Cl-C2-fluoro- and/or
chloro-alkyl, Cl-C4-alkoxy and/or Cl-C2-fluoro-
and/or -chloro-alkoxy,
D represents nitrogen or the ~rouping 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-
C6-alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-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, 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 '.
R1 represents the radical ~ , in which
~ R5
R5 and R6 are iden~ical or different and represent
2Q hydrogen, fluorine, chlorine, bromine,
iodine, cyano, nitro, Cl-C6-alkyl [which is
optionally substituted by fluorine,
chlorine, bromine, cyano, carboxyl, C~-C~-
alkoxycarbonyl, Cl-C~-alkylamino-carbonyl, ~:
di-(cl-c~-alkyl)aminocarbonyl~ hydroxyl,
Cl-C~-alkoxy, formyloxy, Cl-C~-alkyl~
Le A 26 728 _ 4 _ . .
2010650
carbonyloxy, Cl-C4-alkoxy-carbonyloxy,
Cl-C4-alkylamino-carbonyloxy, Cl-C4-alkyl-
thio, Cl-C~-alkylsulphinyl, Cl-C4-alkylsul-
phonyl, di-(C1-C4-alkyl)-aminosulphonyl,
C3-C6-cycloalkyl or pher.yl], C2-C6-alkenyl
[which is optionally substituted by fluo-
rine, chlorine, bromine, cyano, C1-C4-
alkoxy-carbonyl, carboxy or phenyl], C2-
C6-alkinyl [which i8 optionally ~ubstituted
by fluorine, chlorine, bromine, cyano,
C1-C4-alkoxy-carbonyl,carboxyl or phenyl],
C,-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 Cl-C4-alkylsulphonyl], Cl-C4-
alkylthio [which is optionally substituted
by fluorine, chlorine, bromine, cyano,
carboxyl, Cl-C4-alkoxy-carbonyl, Cl-C4-
alkylthio, Cl-C~-alkylsulphinyl or Cl-C4-
alkylsulphonyl], C3-C6-alkenyloxy [which is
optionally substituted by fluorine, chlo-
rine, bromine, cyano or C1-C4-cyano or
Cl-C4-alkoxy-carbonyl], C2-C6-alkenylthio
twhich is optionally substituted by fluo-
rine, chlorine, bromine, cyano, nitro, C1-
C3-alkylthio or Cl-C4-alkoxycarbonyl], C3-
C6-alkinyloxy, C3-C6-alkinylthio or the
radical -S(o)p-R7, where
` p represents the numbers 1 or 2 and !
Le A 26 728 - S
Z0~0650 ::
R7 represent~ C~-C4-alkyl [which i8
optionally substituted by fluorine,
chlorine, bromine, cyano or C~-C~-
alkoxy-carbonyl], C3-C6-alkenyl, C3-
C6-alkinyl,Cl-C4-alkoxy,C1-C4-alkoxy-
Cl-C4-alkylamino, C~-C4-alkylamino, di-
(Cl-C4-alkyl)-amino or for the radical
-NHOR~, where
R9 represents Cl-C6-alkyl ~which is
optionally sub~tituted by
fluorine~chlorine~ cyano, Cl-C4-
alkoxy, C~-C4-alkylthio, Cl-C4-
alkylsulphinyl, C,-C4-alkylsul-
phonyl, C~-C4-alkyl-carbonyl, .-
Cl-C4-alkoxy-carbonyl, Cl-C4- -
alkylamino-carbonyl or di-( Cl-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-C~-C2-alkyl, phenyl-C~-Ca-
alkyl [which is optionally
substituted by fluorine, chlor-
ine, nitro, cyano, Cl-C4-alkyl, ;.
C~-C4-alkoxy or C1-C~-alkoxy~
carbonyl], benzhydryl or phenyl
[which is optionally ~ubstituted
by fluorine, chlorine, nitro,
cyano, C1-C~-alkyl, trifluorq-
Le A 26 728 - 6 - ~ :
: .
" 20~0650
methyl, Cl-C4-alkoxy, Cl-C2-
fluoroalkoxy, Cl-C4-alkylthio,
trifluoromethylthio or C~-C4-
alkoxy-carbonyl],
R5 and R6 furthermore represent phenyl or phenoxy,
Cl-C4-alkylcarbonylamino, Cl-C4-alkoxycar-
bonylamino, C,-C4-alkylamino-carbonylamino,
di-(C~-C4-alkyl)-amino-carbonylamino, or
the radical -C0-R~, where
R~ represents Cl-C6-alkyl, Cl-C6-alXoxy,
C3-C6-cycloalkoxy, C3-C6-alkenyloxy,
C1 C4-alkylthio, amino, Cl-C4-alkyl-
amino, C,-C4-alkoxyamino, C~-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 C~-C4-alkylsulphonyl-
oxy, di-(C~-C4-alkyl)-aminosulphonylamino
or the radical -CH=N-R1~, where
R10 represents Cl-C6-alkyl optionally
substituted by fluorine, chlorine,
cyano, carboxyl, C,-C4-alkoxy, C~-C~
alkylthio, C1-C4-alkylsulphinyl or
C1-C4-alkylsulphonyl, benzyl option-
: 25 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- : :
. ~ , . ,
Le A 26 728 - 7 -
20~0650
alkoxy, trifluoromethyl, trifluoro-
methoxy or trifluoromethylthio, Cl-
C6-alkoxy, C3-C6-alkenoxy, C3~C6-
alkinoxy or benzyloxy optionally
substituted by fluorine and/or
chlorine, amino, Cl-C4-alkylamino, di-
(Cl-C4-alkyl)-amino, phenylamino,
Cl-C4-alkyl-carbonyl-amino, C,-C4-
alkoxy-carbonyl-amino, Cl-C4-alkyl-
sulphonylamino or phenylsulphonyl-
amino optionally substituted by
fluorine, chlorine, bromine or
methyl,
in which in addition
15 Rl represents the radical ~l~ ~ , in which
Rll R~2
R11 represents hydrogen or Cl-C4-alkyl,
R12 and R13are identical or different and represent
hydrogen, fluorine, chlorine, bromine,
~ ~ nitro, cyano, C1-C4-alkyl twhich 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-C~-alkyl)-
zminosulphonyl; in which in addition
R~ Fepresents the radical R~4 ~ R15 ~ in whiC
.
...
:: :
Le A 26 728 - 8 ~
i20~0~so
Rl4 and R15are identical or different and represent
hydxogen, fluorine, chlorine, bromine,
nitro, cyano, Cl-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
R~7
Rl represents the radical ~ , in which
R15 and Rl7 are identical or different and represent
hydrogen, fluorine, chlorine, bromine,
nitro, cyano, Cl-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~, Cl C~-alkylthio, Cl-C4-alkylsul-
phinyl or Cl-C4-alkylsulphonyl twhich are ;:
optionally substituted by fluorine and/or
chlorine3, and di-(C~-C4-alkyl)-aminosul~
phonyl, Cl-C~-alkoxy-carbonyl, dimethyl~
aminocarbonyl or dioxolanyl; in which in : .
addition : :: ' '
!
: : '
" ' ': . ': ' ' .
Le A 26 728 _ 3 _ :~
2010~50
Rl represents the radical R19 ~ _RI8 , in which
Rl~ and R1~are identical or different and represent
hydrogen, fluorine, chlorine, bromine,
C1-C~-alkyl [which is optionally substitu-
ted by fluorine and/or bromine], Cl-C4-
alkoxy [which is optionally substituted by
fluorine and/or chlorine], C1-C4-alkyl-
thio,Cl-C~-alkylsulphinyl or Cl-C4-alkylsul-
phonyl [which is optionally substituted by
fluorine and/or chlorine], or di-(Cl-C4-
alkyl)-aminosulphonyl; in which in addi-
tion
RZ0
R1 represents the radi~al ~ ~21 , in which
: R2~ and R2lare identical or different and represent
hydrogen, fluorine, chlorine, bromine, ~ ;
cyano, nitro, C,-C4-alkyl twhich is option- ~ ~:
ally substituted by fluorine, chlorine,
Cl-C4-alkoxy and/or Cl-C4-halogenoalkoxy], :
C1-C~-alkoxy ~which i9 optionally sub-
stituted by fluorine and/or chlorine~
Cl-C~-alkylthio, Cl-C4-alkylsulphinyl or
Cl-C~-~lkylsulphonyl [which i~ optionally
substituted by fluorine and~or chlorine],
di-(Cl-C4-alkyl)-amino-sulphonyl or C~-C~- :
Le A 26 728 - 10 -
- .
alkoxy-carbonyl, and 20106$0
Q' represents oxygen, sulphur or the grouping N-
Q2 ~ where
Q2 represents hydrogen, C~-C4-alkyl [which i
optionally substituted by fluorine, chlor-
ine, bromine or cyano], C3-C6-cycloalkyl,
benzyl, phenyl twhich is optionally sub-
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 represents the radical ~ R23 , in which
R~2 and R23are identical or different and represent
hydrogen, C,-C4-alkyl, halogen, C~-C4-
alkoxycarbonyl, C~-C4-alkoxy or C,-C4-
halogenoalkoxy,
Q3 represents sulphur or the grouping N-R24, where
R24 represents hydrogen or C,-C4-alkyl; in
~ which in addition . -
. ~
20Rl represents the radical ~ , in which
¦ R : .
~25
R25 represents hydrogen, Cl-C~-alkyl, phenyl or
(iso)quinolinyl,
R26 representsl hydrogen, halogen, cyano, nitro,
~e A 26 728 - 11 - - :
'
2010650
Cl-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 Cl-C4-alkoxy-carbonyl
and
R27 represents hydrogen, halogen or C1-C4-alkyl; in
which in addition
Rl represents the radical ~ R28 ~ in which
R2~ represents hydrogen, halogen, Cl-C4-alkyl or
Cl-C4-alkoxy-carbonyl; in which in addition
Rl represents the radical ~ 2 , ; .
R30 _~29
in which
R2~ represents Cl-C4-alkyl and
R30 represents C,-C4-alkyl, in which in addition
: 15 Rl represents the radical ~ , in which - :
R3 1
R31 represents hydrogen or methyl,
in which in addition
R2 represents hydrogen, fluorine, chlorine, bromine,
hydroxyl, amino, Cl-C4-alkyl, Cl-C~-halogenoalkyl, Cl-
C2-alkoxy-Cl-C2-alkyl,bis-(Cl-C2-alkoxy)-Cl-C2-alkyl,
Cl-C"-alkoxy, Cl-C~-halogenoalkoxy, Cl-C~-alkylthio,
~e A 26 728 - 12 ~
~ . .: , .
Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-
alkylamino, dimethyl3mino or diethylamino,
X represen~s nitrogen or a CH grouping,
Y represents nitrogen or the grouping C-R3, in which
R3 represents hydrogenl fluorine, chlorine,
bromine, cyano, methyl, formyl, acetyl, meth-
oxycarb~nyl or ethoxycarbonyl, and
Z represents nitrogen or the grouping C-R4, in which
R4 represents hydrogen, fluorine, chlorine, bromine,
hydroxyl, amino, C~-C4-alkyl, Cl-C4-halogenoalkyl, Cl-
C2-alkoxy-C1-C2-alkyl,bis-(C1-C2-alkoxy)-C1-C2-alkyl,
Cl-C4-alkoxy, Cl-C4-halogenoalkoxy, Cl-C4-alkylthio,
Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-C~-
alkylamino, dimethylamino or diethylamino.
The invention in particular relates to compounds
of the formula (I), in which
A represents nitrogen or the grouping C-A1, in which
Al 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,
Le A 26 728 - 13 -
201Q650
(with the proviso that A and D do not bo~h simultaneously
represent nitrogen),
E representR oxygen or sulphur,
Rl represents the r~dic~l ~ R , in which
R5 represents fluorine, chlorine, bromine, methyl,
trifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, Cl-C3-alkylthio, C1-C3-alkyl-
sulphinyl, Cl-C3-alkylsulphonyl, dimethyl2mino-
sulphonyl, N-methoxy-N-methylaminosulphonyl,
phenyl, phenoxy or Cl-C3-alkox~-carbonyl and
R6 represents hydrogen, fluorine or chlorine; in
which in addition
Rl repr*sents the r~dic~ -Cl~ ~ R13 , ir which
R1l represents hydrogen,
Rl~ 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
~3
R~ represent~ the radical RO-C S , in which
o , . .
.,
Le A 26 728 - 14 - ~
201065(~
R represents C~-C4-alkyl, or
R1 represents the radical
RO - C`- I
~`N'N
CH3 , in which ~:
R represents Cl-C4-alkyl, or
R1 represents the radical ~ :
R28
, in which :
' N`S~
RZ8 represents hydrogen, chlorine, methyl, ethyl, ~ ~ :
methoxycarbonyl or ethoxycarbonyl;
in which in addition ~ ~ ~ :
10 R2 represents hydrogen, fluorine, chlorine, bromine,
methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
difluoromethoxy, methylthio, ethylthio, methylamino,
ethylamino or dimethylamino,
X represents nitroqen or a CH grouping,
Y represents nitrogen or the grouping C-R3, in which :
R3 represents hydrogen, fluor~ne, chlorine or ~:
methyl and I !
,. ' ~';
Le A 26 728 - 15 ~
20~0650
Z represents nitrogen or the grouping C-R4, in which
R4 represents hydrogen, fluorine, chlorine,
bromine, methyl, ethyl, trifluoromethyl,
methoxy, ethoxy, propoxy, isopropoxy, difluoro- :
S methoxy, methylthio, ethylthio, methylamino,
ethylamino or dimethylamino.
If, for example, 2-(4,6-dLmethoxy-pyrimidin-2-yl-
amino)-oxazole and 2-fluoro-benzenesulphonyl chloride are
used as starting substances, then the course of the
reaction in the process according to the invention can be
outlined by the following equation:
OCH3 F
NH ~ ~ ~ ~ S02-
OC~3 F
~ 2
_ > OCH3
- HCl ~ ~=N
OCH~
Formula (II) provide~ a general definition of the
azinylaminoheteroazoles to be used as stsrting substances
for the preparation of compounds of the formula (I) in . --
the process according to the invention. ;~
In formula (II), A, D, E, R2, X, Y and Z prefer~
ably or in particular have those meanings which have ~ ~ -
already been indicated above as particularly preferred
for A, D, E, R2, X, Y and Z in connection with the de-
scription of the compounds of the formula (I) according
to the
.
,
Le A 26 728 - 16 -
invention. ~ ~
Examples of the starting substances of the
formula tII) are shown in the following Table 1.
: ' ~
Le A 26 728 - 17 -
20~065~ :
Table l: Examples of the starting substances of the
formula (II)
z~y ~ 2
N ~
A=--=D
A ~ E R2 X Y Z
_
N CH CH3 N CH C-CH3
: N CH S CH3 N CH C-CH3
CH N c~3 N CH c-CH3
CH N S CH3 N CH C-CH3
CH CH CH3 N CH C-CH3
CH CH S CH3 N CH C-CH3
C-CH3 CH3 N CH C CH3
N C-c~3 5 CH3 N CH c-CH3
C-CH3 CH S CH3 N CH C-CH3
N C-CF3 `5 CH3 N CH C-CH3
N C-C2H5 S CH3 N CH C-CH3
N C-C6H5 S CH3 N CH C-CH3
Le A 26 728 - 18 -
Table 1 - Continuation 2010650
A D E R2 X Y Z
N C-SCH~ S CH3 N CH C-CH3
C-C2H5 CH S CH3 N CH C-CH
N C-CHC12 5 CH3 N CH C^CH3
C-Cl C-Cl S CH3 N CH C-CH3
N CH CH3 N CH C-OCH3
N CH S CH3 N CH C-OCH3
CH N S CH3 N CH C-OCH3
C-CH3 N S CH3 N CH C-OCH3
CH CH S CH3 N CH C-OCH3
N C-CH3 CH3 N CH C-OCH3
C-CH3 5 CH3 N CH C-OCH3
N C-SCH3 5 CH3 N CH C-OCH3
N C~ S OCH3 N CH C-OCH3
CH N S OCH3 N CH C-OCH
C-CH3 N S OCH3 N CH C-OCH3
CH CH S OCH3 N CH C-OCH3
N C-CH3 OCH3 N CH C-OCH3
N C-CH3 5 OCH3 N CH C-OCH
N C-CF3 S OCH3 N CH C-OCH
N C-SCH3 S OCH3 N CH C-OCH
N C-C6H5 S OCH3 N CH C-OCH
Le A 26 728 - 19 -
Table 1 - Continuation 2010~0
A D E R2 X Y Z
N C-CH~CH3)2 S OCH3 N CH C-OCH3
N C-SC4H9 S OCH3 N CH C-OCH3
C-Cl C~Cl S OCH3 N CH C-OCH3
N CH S OCH3 N CH C-Cl
CH N S OCH3 N CH C-Cl
C-CH3 N S OCH3 N CH C-Cl
CH CH S OCH3 N CH C-Cl
N C-CH3 S OCH3 N CH C-Cl i-
N C-SCH3 S OCH3 N CH C-Cl
N CH S H N CH C-CH3
CH N S H N CH C-CH3
C-CH3 N S H N CH C-CH3
CH CH S H N CH C-CH3
N C-CH3 S H N CH C-CH
CH S CF3 N CH C-OCH3
CH N S CF3 N CH C-OCH3
C-CH3 N S CF3 N CH C-OCH3
N C-CH3 3 N CH C-OCH3
CH CH S CF3 N CH C-OCH3
N C-SCH3 S CF3 N CH C-OCH3
N CH S OCH3 N CY C-OCHF2
Le A 26 728 - 20 -
Table 1 - Continuation 20
A D E R2 X Y Z
CH N S OCH3 N CH C-OCHF2
C-CH3 N S OCH3 N CH C-OCHF2
N C_CH3 S OCH3 N CH C-OCHF2
N CH S CH3 N CH C-OCHF2
CH N S CH3 N CH C-OCHF2
C-CH3 N S CH3 N CH C-OCHF2
N C-CH3 5 CH3 N CH C-OCHF2
CH CH S CH3 N CH C-OCHF2
N C-SCH3 5 C.Y3 N CH C-OCHF
N C C6H5 5 CH3 N CH C-OCHF
N CH S OCHF2 N CH C-OCHF2
CH N S OCHF2 N CH C-OCHF2
C-CH3 N S OCHF2 N CH C-OCHF2
N C-CH3 S OCHF2 N CH C-OCHF2
CH CH S OCHF2 N CH C-OCHF2
N C-SCH3 S OCHF2 N CH C OCHF2
N C-C6H5 S OCHF2 N CH C-OCHF2
C-Cl C-Cl S OCHF2 N CH C-ocHF2
N CH S CH3 N N C-CH3
CH N S CH3 N N C-CH~
C-CH3 N S CH~ N N C-CH3
Le A 26 728 - 21 ~
Table 1 - Continuation ~v~5~
A D E R2 X Y ;Z
_
N C-CH3 S CH3 N N C-CH3 . .
CH CH S CH3 N N C-CH3
C-Cl C-Cl S CH3 N N C CH3
N CH S CH3 N N C-OCH3
CH N S CH3 N N C-OCH3
C-CH3 N S CH3 N N C-OCH3
N C-c~3 5 C~3 N N C-OCH3
CH CH S CH3 N N C-OCH3
NC-SCH3 S CH3 N N C-OCH3
NC-CF3 S CH3 N N C-OCH3
NC-C6H5 S CH3 N N C-OCH3
N CH S OCH3 N N C-OCH3 ~ :~
C~ N S OCH3 N N C-OCH3
-CH3N S OCH3 N N C-OCH3
NC-CH3 S OCH3 N N C-OCH3
NC-SCH3 5 OCH3 N N C-OCH3
NC-CF3 S OCH3 N N C-OCH3
6 5 S OCH3 N N C-OCH3 !
CH CH S OCH3 N N C-OCH3
C-Cl C-Cl S OCH3 N N C-OCH3 ~ ::
N CH S OCH3 N N C-Cl
: '
~e A 26 728 - 22 -
Table 1 - Continuation 20~065(~
A D E R2 x Y Z
N CH S OC2H5 N N C-OC2H5
N CH S C2H5 N N C-OCH3
,.
~ ' ,,
: ~ `
: ~
~.
I.e A 26 728 - 23 - : -
,. '."~ ' -
2~1065()
The starting substances of the formula (II) are
not yet known from the literature.
The new compounds of the formula (II) are .
obtained when
2 ) aminoheteroazoles of the general formula (IV) ~ :
~.H2
I (IV)
N~^~E
A
in which
A, D and E have the abovementioned meanings,
are reacted with azines of the general formula (V)
N - Z~
10~4 ~ ~Y (V)
R2
in which
R2, X, Y and Z have the abovementioned meaninqs and :
Q4 represents halogen or alXylsulphonyl, -.
if appropriate in the presence of an acid acceptor,
such as, for example, potassium carbonate and if
~ appropriate in the presence of a diluent, such as, -:8:-
for exzmple, acetonitrile, tetrahydrofuran, dioxane
: or dimethylformzmide, at temperatures between 10C
:and 50C, or when -~
~) heteroazoles of the general formula (VI)
~5 (VI
N~E
. A~
e A 2~ 728 - 24 -
201~65~
in which
A, D and E have the abovementioned meanings and
Q5 represents haloqen or alkylsulphonyl,
are reacted with aminoazines of the general formula
(VII)
N = Z~ ~ .
H2~_~ ~ y (VII)
R2
in which
RZ, X, Y and Z have the abovementioned meanings,
if appropriate in the presence of an acid acceptor,
such as, for example, potassium carbonate, and if
appropriate in the presence of a diluent, such as,
for example, acetonitrile, tetrahydrofuran, dioxane
or dimethylformamide, at temperatures between O~C
and 150C.
Formula (IV) provides a general definition of the
aminoheteroazoles required as intermediates. In formula
(IV), A, D and E preferably or in particular have those
meanings which have already been indicated above in
connectio~ 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)
which may be mentioned are~
2-amino-oxazole,2-amino-thiazole,2-amino-1,3,4-thiadia~
zole, 5-amino-1,2,4-thladiazole, 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-
L~ A 26 728 - 25 -
:
. .. ., . , ~ ::
` 201065(~
ethyl-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-
thiadiazole.
The aminoheteroaæoles of the formula (IV) areknown and/or can be prepared by methods which are known
per se (compare Comprehensive Heterocyclic Chemistry,
Vol. 6, Pergamon Press 1984).
Formula (V) provides a general definition of the
azines required as intermediates. In formula (v)l R2, X,
Y and Z preferably or in particular have those meanings
which have been indicated above in connection with the
description of the compounds of the formula (I) according
lS to the invention as preferred or as particularly prefer-
red R2, X, Y and Z,and Q4 preferably represents fluorine,
chlorine, bromine or C~-C4-alkylsulphonyl, in particular
chlorine or methylsulphonyl.
Examples of the compounds of the formula (V)
which may be mentioned are:
2-chloro- and 2-methylsulfonyl-4,6-dimethyl-pyrimidine, -
4-methyl-6-methoxy-pyrimidine, -4,6-dimethoxy-pyrimidine, -
-4-methyl-6-ethoxy-pyrimidine, -4-chloro-6-methoxy-
pyrimidine, -4-methyl-pyrimidine, -4-chloro-6-methyl- -
pyrimidine, -4-trifluoromethyl-6-~ethoxy-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,
Le A 26 728 - 26 -
: - . . ., . ,~ -: ~ :; ~ ', ..
-
2010650
-4-ethyl-6-methoxy-pyrimidine, -4,6-dichloro-pyrimidine,
-4-ethyl-6-methoxy-pyrimidine, -5-chloro-4,6-dimethoxy-
pyrLmidine and -4,6-bis-trifluoromethyl-pyrimidine, and
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 (v) are known and/or
can be prepared by proce~ses which are known per se
(compare J. Chem. Soc. 1957, 1830, 1833; J. Org. Chem. 2
(1961) 792; US-P 3,308,119 and US-P 4,711,959).
Formula tVI) provides a general definition of the
heteroazoles further required as intermediates. In
formula (VIj, 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 description of the compounds of the
formula (I) according to the invention and Q5 preferably
represents fluorine, chlorine, bromine or C~-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-chloro-thiazole, 2-chloro- and 2-
methyl-sulphonyl-1,3,4-thiadiazole, 2-chloro-1,3,4-
oxadiazole, S-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-
Le A 26 728 - 27 -
- ~: ~ ~ :: :: . :
- - . . ~
.: : ~ . - : :
- . :. ~ . :, . . , . . ;
- . . . . . . .
- : ~ . : .i:, :: :
.
20~1)65()
sulphonyl-S-trifluoromethyl-ll3~4-thiadiazole/ 2-chloro-
and 2-methylsulphonyl-5-difluoromethyl-1,3,4-thiadiazole,
2-chloro- and 2-methylsulphonyl-5-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 se
(compare Comprehensive Heterocyclic Chemistry, Vol 6,
Pergamon Press 1984).
Formula (VII) provides a ~eneral definition of
the aminoazines required as intermediates. In formula
(VII), R2, X, Y and Z preferably or in particular have
those meanings which have been indicated above as pre-
ferred or as particularly preferred for R2, X, Y and Z in
connection with the description of the compounds of the
formula (I) according to the invention.
Examples of the compounds of the formula (VII)
which may be mentioned are:
2-Amino-4,6-dimethyl-pyrimidine, -4-methyl-6-methoxy-
pyrimidine, -4,6-dimethoxy-pyrimidine, -4-methyl-6-
ethoxy-pyrimidine, -4-ethyl-6-ethoxy-pyrimidine, -4-
chloro-6-methoxy-pyrimidine, -4-methyl-pyrimidine, -4-
chloro-6-methyl-pyrimidine, -4-trifluoromethyl-6-methoxy-
pyrimidine, -4-methyl-6-difluoromethoxy-pyrimidine, -4-
methoxy-6-difluoromethoxy-pyrimidine, -4,6-bis-difluoro-
methoxy-pyrimidine, -4-chloro-6-ethoxy-pyrimidine, -4,6-
diethoxy-pyrimidine -4,5-dichloro-6-msthyl-pyrimidine,
-4-methyl-5-chloro-6-methoxy-pyrimidine, -4,6-dichloro-
pyrimidine, 5-chloro-4,6-bis-methoxy-pyrimidine and -4,6i-
Le A 26 728 - 28 -
.
. .
20~
bis-trifluoromethyl-pyrimidine, and in addition 2-amino-
4,6-dimethyl-s-triazine, -4-methyl-6-methoxy-s-triazine,
-4,6-dimethoxy-s-triazine, -4-chloro-6-methoxy-s-
triazine, -4-ethyl-6-methoxy-s-triazine, -4-methyl-6-
ethoxy-s-triazine, -4,6-diethoxy-s-triazine and -5,6-
dimethyl-1,3,4-triazine.
The compounds of the formula (VII) are known
and/or can be prepared by methods which are known per se
(compare J. Chem. Pharm. Bull. 11 (1963), 1382;
US-P 4,299,960).
Formula ~ provides a general definition of
the ~ulphonic acid halides or anhydrides further to be
used as starting substances in the process for the
preparation of the new compounds of the formula (I)
according to the invention. In formula (III), Rl prefer-
ably or in particular has that meaning which has already
been indicated above as preferred or as particularly
preferred in the context of the description of the
compounds of the formula (I) according to the invention,
and Q preferably represent~ chlorine.
Examples of starting substances of the formula
(III) which may be mentioned are:
Benzolsulfonyl chloride, 2-chloro-, 3-chloro-, 4-chloro-,
2!5-dichloro-, 2-fluoro-, 4-fluoro-, 2-brom-, 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-cyclopropyloxycarbonyl-, 2-
phenoxy-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-(c-
chloroethoxy)-, 2-methylthiomethyl-, 2-dimethylamino-
Le A 26 728 - 29 -
Z01065()
sulphonyl-, 2-phenyl-, 2-methoxycarbonyl-, 2-ethoxy-
carbonyl-, 2-dimethylaminocarbonyl- and 2-diethylamino-
carbonyl-phenylsulphonyl chloride and (2-chloro-phenyl)-,
2-(cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and (2-
s trifluromethoxy-phenyl)-methanesulphonyl chloride, 2-
chloro-6-methyl-phenylsulphDnyl chloride and 2,6-dichloro-
phenylsulphonyl chloride.
The sulphonic acid halides and anhydrides of the
formula (III) are known and/or can be prepared by methods
which are known per se (compare J. Org. Chem. 33 (1968);
2104; J. Org. Chem. 25 (196Q), 1824; DE-AS 2,308,262;
EP-O~ 23,140, 23,141, 23,422, 35,893, 48,143, 51,446, 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).
The process for the preparation of the new
compounds 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 as pentane, hexane,
heptane, cyclohexane, petroleum ether, benzine, ligroin,
benzene, toluene, xylene, methylene chloride, ethylene
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,
methyl ethyl ketone, methyl isopropyl ketone and methyl
isobutyl ketone, esters such as methyl acetate and ethyl
acetate, nitriles such as, for example, acetonitrile and
Le A 26 728 _ 30 -
20106S0
propionitrile, amides such as, for example, dimethyl-
formamide, dimethylacetamide and N-methyl-pyrrolidone and
dimethyl sulphoxide, tetramethylene sulphone and hexa-
methylphosphoramide and pyridine.
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
such as, for example, sodium hydroxide and potassium
hydroxide, alkaline earth metal hydroxides such as, for
example, calcium hydroxide, alkali metal carbonates and
alkoxides such as sodium carbonate and potassium car-
bonate, sodium tert-butoxide and potassium tert-butoxide,
and further aliphatic, aromatic or heterocyclic amines,
for example triethylamine, trimethylamine, dimethylani-
line, dimethylbenzylamine, pyridine, picoline, 1,5- -
diazabicyclo-[4~3~o]-non-s-ene (DBN), 1,8-diazabicyclo-
[5,4,0]-undec-7-ene (DBV) and 1,4-diazabicyclo-[2,2,2]-
octane (DABC0).
The reaction temperatures in the process accord-
ing to the invention can be varied within a relatively
laxge range. In general, the reaction is carried out at
temperatures between -50C and ~lOO~C, preferably at tem-
peratures between -20C and l40-C. :
For carrying out the process according to the
invention, between 1 and 5 moles, preferably between 1
and 4 moles, of sulphanyl halide or sulphonic anhydride of
the formula (III) are in general employed per mole of
az~nyl ~ nohetero 7ole of the formula (II).
The reaction components can be combined in any
e A 26 728 - 31 -
.. - .: ~ : ~ , .: .
,.:
.
20~0650
sequence. In a preferred embodiment of the process
according to the invention, the starting substances of
the formulae (II) and in (III) are stirred at room
temperature with a diluent, and - if appropriate after
cooling - the acid acceptor is slowly metered into this
mixture. The reaction mixture is then stirred until
completion of the reaction.
Working up can be carried out in a customary
manner, for example by washing - if appropriate after
concentrating and/or diluting with a virtually water-
immiscible organic solvent, such as, for example, methyl-
ene chloride - with water, drying, filtering and care-
fully distilling off the solvent from the filtrate. The
crude product remaining in the residue can be further
purified in a customary manner, for example by column
chromatography and/or by recrystallization.
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
essentially on the amount used.
The active compounds according to the invention
can be used, for example, in connection with the follow-
ing plants:
Dicotvledon weeds of the ~enera: Sinapis,
Lepidium, Galium, Stellaria, ~atricaria, Anthemis,
Galinsoga,; Chenopodium, Urtica, Senecio, Amaranthu~i,
e A 26 728 - 32 -
20~0650
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,
Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.
Dicotyledon cultures of ths aenera: Gossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,
Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras-
sica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the aenera: Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,
Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, A~ropyron, Cynodon, Monochoria, Fimbristylis,
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
Apera.
Monocotvledon cultures of the qenera: Oryza,
Zea, Triticum, Hordeum, A~ena, Secale, Sorghum, Panicum,
Saccharum, Ananas, Asparagus and Allium.
However, the use of the ac,tive compounds accord-
ing to the invention i~ in no way restricted to these
genera, but also extends in the same manner to other
plants.
The compounds are suitable, depending on the
concentration, for the total combating of weeds, for
example on industrial terrain and rail tracks, and on
paths and squares with or without tree plantings.
Equally, the compounds can be employed for combating
weed~ in perennial cultures, for example afforeqtations,
decorative tree plantings, orchards, vineyards, citrus
groves, nut orchards, banana plantations, coffee
Le A 26 728 _ 33 _
- .,
2010650
plantations, tea plantations, rubber plantations, oil
palm plantations, cocoa plantations, soft fruit plantings
and 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 and
dicotyledon cultures both in the pre-emergence and in the
post-emergence method.
Some of the compounds according to the invention
also show fungicidal action, in particular against
Pyricularia oryzae on rice.
The active compounds can be converted into the
customary formulations, such as solutions, emulsions,
wettable powders, suspensions, powders, dusting agents,
pastes, soluble powders, granules, suspension-emulsion
concentrates, natural and synthetic materials impregnated
with active compound, and very fine capsules in polymeric
substances.
These formulations are produced in a known
manner, for example by mixing the active compounds with
extenders, that is liquid solvents and/or solid carriers,
optionally with the use of surface-active agents, that is
emulsifying agents and/or dispersing agents and/or 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
alkylnaphthalenesj chlorinated aromatics and chlorinated
Le A 26 728 - 34 -
, ~'''' .
2010650
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,
ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar sol-
vents, such as dimethylformamide and dimethyl sulphoxide,
as well as water.
As solid carriers there are suitable: for example
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
silicates, as solid carriers for granules there are
suitable: for example crushed and fractionated natural
minerals such as calcite, marble, pumiice, sepiolite and
dolomite, as well as synthetic granules of inorganic and
organic meals, and qranules of organic material such as
sawdust, coconut shells, com cobs and tobacco stalks;
as emulsifying and/or foam-forming agents there are
suitable: for example non-ionic and anionic emulsifiers,
such as polyoxyethylene fatty acid esters, polyoxyethyl-
ene fatty alcohol ethers, for example alkylaryl poly- -
glycol ethers, alkylsulphonates, alkyl sulphates, aryl-
sulphonates as well as al~u~n hydrolysis products; as
dispersing agents there are suitable: for ex~mple lignin-
sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and
natural and synthetic polymers in the form of powders,
Le A 26 728 - 35 -
: - - :: - ~
2010650
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 used in the formulations. Further
additives can be mineral and vegetable oils.
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-
stuffs, and trace nutrients such as salts of iron,
man~anese, boron, copper, cobalt, molybdenum an~ zinc.
The formulations in general contain between 0.1
and 95 per cent by weight of active compound, preferably
bet.ween 0.5 and 904.
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 components for the mixtures are known
herbicides, such as, for example, 1-amino-6-ethylthio-3-
(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione
(AMElHYDIONE) 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-
MITRON) for combating weeds in sugar bee~ 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-DB); 2,4-dichlorophen-
Le A 26 728 - 36 -
:. :
oxypropionic acid (2,4-DP); 2-chloro-4-ethylamino-6-
isopropylamino-1,3,5-triazine (ATRAZINE); 3,5-dibromo-4-
hydroxy-benzonitril (BROMOXYNIL); 4-amino-6-t-butyl-3-
ethylthio-1l2,4-triazine-5(4H)-on(ETHIOZINE);N-phospho-
nomethylglycin (GLYPHOSATE); 3-cyclohexy1-6-dimethyl-
amino-l-methyl-1,3,5 triazine-2,4-dione (HEXAZINONE~; 2-
(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-lH-imidazol-2-
yl)-pyridine-3-carboxylic acid (IMAZAPYR); 3~5-diiode-4-
hydroxybenzonitrile (IOXYNIL); (2-Ethoxy-l~methyl-2-oxo-
ethyl-5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitro-
benzoate (LACTOFEN); (2-methyl-4-chlorophenoxy)-acetic
acid (MCPA); (4-chloro-2-methylphenoxy)-propionic acid
(MCPP); N-methyl-2-(1,3-benzthiazol-2-yloxy)-acetanilide
(NEFENACET); 2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-
yl)-amino)-carbonyl]-amino]-sulfonyl}-benzoic acid or its
methyl ester (METSULFURON); N-(l-ethylpropyl)-3,4-
dimethyl-dinitroaniline (PENDIMETHALIN); 2-chloro-4,6-
bis-(ethyl-amino)-1,3,5-triazine (SIMAZINE); methyl-2-
{[(4,6-dimethyl-2-pyrimidinyl)-aminocarbonyl]-amino-
sulfonyl}-benzoate (SULFONETURON); 2,6-dinitro-4-tri-
fluoromethyl-N,N-dipropylaniline(TRIFLURALINE);surpris-
ingly, some mixtures also show a synergistic action.
Nixtures with other known active compounds, such
a~ fungicides, insecticides, acaricides, nematicides, -
bird repellents, plant nutrients and agents which improve
Qoil structure, are also possible.
The active compounds can be used as such, in the
form of their formulations or in the use forms prepared
therefrom by further dilution, such a~ ready-to-use
~0 solutions, ~uspen~ions,~emulsions, powders, paste~ and
Le A 26 728 - 37 _
20~0650
granules. They are used in the customary manner, for
example by watering, spraying, atomizing or scattering.
The active compounds according to the invention
can be applied either before or after emergence of the
plants.
They can also be incorporated into the soil
before sowing.
The amount of active compound used can vary
within a substantial range. It depends essentially on the
nature of the desired effect. In general, the amounts
used are between 0.01 and 10 kg of active compound per
hectare of 80il surface, preferably between 0.05 and
S kg per ha.
The preparation and use of the active compounds
according to the invention can be seen from the following
examples.
Le A 26 728 - 38 -
Preparation Exam~les 2010650
Example 1 COOCH3
f 2 ~
CH3
N-N N==~
~=N-~ ~
CH3
7.0 g (0~03 mol) of 2-methoxycarbonylbenzene-
sulphDnyl chloride are added to a SUSpQnSion of 2.1 g
(0.01 mol) of 2-(4,6-dimethyl-pyrimidin- 2-yl-amino)-
1,3,4-thiadiazole in 100 ml of dichloromethane and 3 g
(0.05 mol) of trimethylamine are then introduced into
this mixture with stirring ànd cooling with ice water.
The reaction mixture is stirred for 20 hours at 20C to
25C, then washed with saturated sodium bicarbonate
solution, dried over magnesium sulphate and filtered. The
solvent is distilled off from the filtrate in a water jet
vacuum and the residue is stirred with methanol. The
crystalline product is isolated by filtering with
suction.
3.0 g (75% of theory) of 2-~4,6-dLmethyl-
pyrimidin-2-yl-imino)-3-(2-methoxycarbonyl-phenyl-
sulphnnyl)-2,3-dihydro-1,3,4-thiadiazole of melting point
(with decomposition) of l66C 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 26 728 _ 39 _
z~R2 201o650
Rl - 502`NJ~E ( I )
A LJ
~rable 2
ExampleR of the compounds of the formula ( I )
Ex- A D E Rl R2 X Y Z Meltin~
No. point C
Cl
2 CH C~ S <~ CH3 N CH C-CH3 188
Cl
3 N CH S ~ CH3 N CH C-CH3 254
. ~
I~ A 26 728 - 40
~;
20106S0
Table 2 - Continuation
Ex- A D E R1 ~2 X Y z Meltin~
No. point C
Cl
4 CH CH S ~ CH3 N CH C-CH3 129
02N Cl
S CH CH S ~ CH3 N CH C-CH3
Cl
~ Cl
6 CH CH S ~ OCH3 N CH C-OCH~ 176 ~ ;
Cl :
7 CH CH S ~ OCH3 N CH C-OCH3 250
~1 '
COOCH3
8 CH CH S ~ CH3 N CH C-CH3 174
Cl
9 CH CH S ~ -CH3 N CH C-OCH3 193
COOCH3
iO CH CH S ~ CH3 N CH C-OCH3 191
i
LQ A 26 728 - 41 - ~ ~
201(~6S0
Table 2 - Continuation
Ex. A D E Rl R2 X Y z Meltin~
No. point C
Cl
11 CH CH Cl CH3 N CH C-OCH3 161
COOCH3
12 CH CH S ~ OCH3 N CH C-OCH3 14?
COOCH3
13 N CH S ~ r~3 N CH C-OCH3 168
COOC~3 :
14 CH CH S ~ OCH3 N N C-OCH3 168
Cl ,'
CH CH S ~ OCH3 N N C-OCH3 '78
COOCH
r==~ 3 . -
16 N CH S ~ OCH3 N CH C-OCH3 156
Cl
17 N CH S ~ OCH3 N CH C-OCH3 169 ~
l~e A 26 728 - 42 - ~ :
20~06S0
Table 2 - Continuation :
Ex. A D E ~1 R2 X Y z Meltin~
No. point C
- OCF3
18 N CH S ~ CH3 N CH C-CH3 178
OCF3 :
19 CH CH S ~ CH3 N CH C-CH3 178 :
OCF3
CH CH S ~ CH3 N CH C-OCH3 171
OCF3
21 N CH S ~ CH3 N CH C-OCH3 174
OCF3
22 N CH S ~ OCH3 N CH C-OCH3 128 ~ ~t
OCF3
23 CH CH S ~ OCH3 N CH C-OCH3 155 ~-
F -
24 CH CH S ~ OCH3 N CH C-OCH3 173
,, j , , . . ;.. ' ' ~'~
~e A 26 ?28 - 43 -
20~065(~
Table 2 - Continuation
Ex. A D E R1 R2 X Y z Meltin~
No. point C
F
N CH s ~ c~3 N CH C-CH3 15B
F :~
26 CH CH S ~ CH3 N CH C-CH3 197
27 N CH S ~ OCH3 N CH C-OCH3 168
28 N CH S ~ CH3 N CH C-CH3 168
CH3
29 N CH S ~ CH3 N CH C-OCH3 177 :~
CH3
~ COOCH3 ~ .
N C-CH3 S ~ CH3 N CH C-CH3 171
Cl
31 N C-CH3 S ~ CH3 N CH C-CH3 188
Le A 26 728 - 44 -
, ~
2010650
Table 2 - Continuation
Ex A D E R1 R2 X y z pOlnin~c
OCF3
32 N C-CH3 S ~ CH3 N CH C-CH3 179
Cl
33 CH CH S ~ CH3 N CH C-OCH3 190
FH3
34 CH CH S ~ CH3 N CH C-OCH3 160
COOCH3 :
N C-CH3 S ~ OCH3 N CH C-OCH3 170
Cl
36 N C-CH3 S ~ CH3 N CH C-OCH3 150
COOCH3
37 N C-CH3 S ~ CH3 N CH C-OCH3 173 ;~
Cl
38 N C-CH3 5 ~ CH3 N CH C-OCH3 198 ;-;~
,
La A 26 728 _ 45 _ ~
Table 2 - Continuation 20~06S0
Ex. A D E Rl RZ X Y z Meltin~
No. point
~ Br
39 N CH S ~ CH3 N CH C-OCH3 180
Br
N CH S ~ OCH3 N CH C-OCH3 140
COOCH3
41 N C-C2H5 S ~ CH3 N CH C-OCH3 161
~ OCF3
42 N C-C2H5 S ~ CH3 N CH C-OCH3 150
43 N CH S ~ OOCH3 CH3 N CH C-CM3 158
44 N CH S ~ oOCH3 CH3 N CH C-OCH3 168
N CH S ~ OOCH3 OCH3 N CH C-OCH3 148
OCHF2
~ .
46 N CH S ~ CH3 N CH C-OCH3 153
. ' ! ` ' ~ ~
~ ~ .
Le A 2 6 7 2 8 - 4 6 - ~ ~
~able 2 - Continuation 20106S0
Ex . A D E R 1 R2 X Y z Meltin~
No. point C
OCHF2
47 N CH S ~ CH3 N CH C-OCH3 167
OCHF2
48 N CH S ~ OCH3 N CH C-OCH3 160
COOCH3
49 N C-SCH3 S ~ CH3 N CH C-CH3 160
Cl
N CH S ~ CH3 N CH C-OCH3 175
F
51 N CH S ~ CH3 N CH C-OCH3 170 - -~
~ ? ~
Br
52 N CH S ~ CH3 N CH C-CH3 200
: '
53 N CH S ~ 3 CH3 N CH C-OCH3 :
` ~ :
~ .
Le A 2 6 7 2 8 - 4 7 _
Table 2 - Continuation 20106S0
Ex. A D E R1 R2 X Y z Meltin~
No. point C
_ CF3
54 N CH S ~ CH3 N CH C-CH3
COOC2H5
SS N CH S ~ CH3 N CH C-CH3
COOCH3
56 N CH S ~ H2- OCH3 N CH C-OCH3
Cl
57 N CH S ~ CH3 N N C-OCH3
Cl
58 N CH S ~ OCH3 N N C-OCH3
COOCH3
~ .
59 . N CH S ~ CH3 N N C OCH3
: COOCH3
N CH S ~ OCH3 N N C-OCH3
Le A 26 728 - 48 -
Ta~ e 2 - Continuation 2010650
Ex. A D E R1 R2 % y z Meltin~
No. point C
61 N CH S ~ OOCH3 CH3 N N C-OCH3
S
62 N CH S ~ OOCH3 OCH3 N N C-OCH3
OCF3
63 N CH S ~ _ OCH3 N N C-OCH3
: , , . .'
SCH3 -~ . :
64 CH CH S ~ OCH3 N CH C-OCH~ :
502CH3
N CH S ~ OCH3 N N C-OCH3
5o2N(cH3)2
66 N CH S ~ OCH3 N CH C-OCH3
OCH3
67 N CH S ~ CH3 N CH C-CH3
COOC 2H5
68 N CH S ~ OCH3 N CH C-Cl ~ ~ `
~e A 26 728 - 49 _
201065()
Table 2 - Continuation
Ex. A D E R1 R2 X Y z Meltin~ ~:
No. point C
_ COOCH3
69 N CH S ~ OCHF2 N CH C-OCHF2
~CF3
N CH S ~ H2- OCH3 N CH C-OCH3
OCF3
71 N CH S ~ H2- OCH3 N N C-OCH3
N
72 N CH S ¦ ~ OOCH3 OCH3 N CH C-OCH3
~ .'
CH3 -:.
N==~
73 N CH S ¦ ~ OOC2H5 OCH3 N CH C-OCH3
~74 N CH S ~ OOCH3 OCH3 N N C-OCH3
~ CH3
~e A 26 728 _ 50 -
;: ' ' ~ :'
20~065~
Table ? - Continuation
~x. ~ D E R1 R2 X Y z Meltin~
No. point C
. . .
N
N CH N ~ OOC2H5 OCH3 N N C-OCH3
CH3 : :
COOCH(CH3)2
76 N CH S ~ OCH3 N N C-OCH3
Cl
COOC2H5
77 N CH S ~ OCH3 N CH C-OCH3
F2CHO
CF3
78 N CH S ~ OCH3 N CH C-OCH
CON(CH3)2
79 N CR S ~ N ~ OCH3 N CH C-OCH3
C6H5 '~" " '-'' ';
80 N CH S ~ OCH3 N CH C-OCH3 ~ ~
'' '~'':
L~ A 26 ?~8 - 5~
201065()
Ta~le 2 - Continua~ion
Ex A D E Rl R2 X y z Meltnin~c
.
~ COOCH3
81 N C-CH3 O ~ CH3 N CH C-OCH3
COOCH3
82 N C-CH3 O ~ OCH3 N CH C-OCH3
~ COOCH3 ` :
83 C-Cl N O ~ OCH3 N CH C-OCH3 97
~ Cl
84 C-Cl N O ~ OCH3 N CH C-OCH3 125
Cl
: 85 C-Cl N O ~ OCH3 N CH C-OCH3 152
~ CH3
86 C-CH3 N S ~ CH3 N CH C-OCH3 177
COOCH3
~7 C-CH3 N S ~ CH3 N CH C-OCH3 176 .
;~ : ,
Le A 26 728 - 52 - . ~
,~ .
.
,
20106S()
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~ o
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~ ~ ~ ~ tq
s
o o o o o
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x z æ æ æ z :~
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N~ O U U U
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~ ~ob~b~b ~ob 4b~
O U~
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S
~ ': ' "`, ` ''~ ~
~ ~le z z z z z
D . . ~:
E~ X Z 0 o~ O ~ N ~ ;
' : ' ' ' ~:
I.e A 2 6 7 2 8 _ 5 3 _ - - -- ~: . . . .
' ' ~
.
20~065C~
.,, .,
.
P~
" :I: S
Z
.
X Z Z Z Z Z
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,,
,
u~
o
, ~ x ~ ls ~
U . . .;
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C . . - . .
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Le A26 728 - 54 -
,' ,. ':
,.
Starting substances of the formula (II~ 2010650
ExamPle (
CH~
N - N N==~
~-NH~
S N--~
C~3
A mixture of 18.6 g (0.10 mol) of 2-methylsulphonyl-4,6-
dimethyl-pyrimidine, 14.0 (O.10 mol) of potassium
carbonate, 10.1 g (0.010 mol) of 2-amino-1,3,4-thia-
diazole and 200 ml of acetonitrile is heated to boiling ~`
under reflux for 30 hours. After cooling, the solid is
filtered off with suction, washed with 150 ml of water
and dried in a water ~t vacuum at 40C.
19 g (92% of theory) of 2-(4,6-dimethylpyrimidin-
2-yl-amino)-1,3,4-thiadiazole of melting point < 250C
are obtained.
The compounds of the formula (II) shown in Table
3 below can be prepared analogously.
~.
~ ,
Le A 26 728 - 55 _
2010~5~) ~
Table 3
Examples of the compounds of the formula ~
Ex. A D E R2 X Y Z Melting
No. point
_ _ . ; ( Dc)
II-2 CH CH S CH3 N CH C-CH3 189
II-3 CH CH S OCH3 N N C-OCH3 ~250
II-4 CH CH S OCH3 N CH C-OCH3 213
II-5 N CH S OCH3 N CH C-OCH3 248
II-6 CH CH S CH3 N CH C-OCH3 197
II-7 N CH S CH3 N CH C-OCH3 231
Il-8 C-CH3 CH S CH3 N CH C-OCH3 165
II-9 N C-CF3 5 c~3 N CH C-CH3 250
II-10 N C C2H5 S CH3 N CH C-OCH3 184
II-11 C-CH3 CH S CH3 N CH C-CH3 134
II-12 N C-CH3 S CH3 N CH C-CH3 223- ~-
225 ~ ;~
II-13 N C-CH3 5 CH3 N CH C-OCH3 230
II-14 N C-CH3 S OCH3 N CH C-OCH3 214 ~:
II-15 N C-C6H5 S CH3 N CH C-CH3 255
II-16 N C-SCH3 5 CH3 N CH C-CH3 194
II-17 N C-CH3 CH3 N CH C-OCH3 ~ ; .
II-18 N C-CH3 0 OCH3 N CH C-OCH3 ~ :
. ' ,:
.
Le A 26 728 - 56 -
Use Exam~les
Exam~le A
Pre-emergence test
Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active com-
pound, 1 part by weight of active compound i5 mixed with
the stated amount of solvent, the 6tated amount of
emulsifier is added and the concentrate is diluted with
water to the desired concentration.
Seeds of the test plants are sown in normal soil
and, after 24 hours, watered with the preparation of the
active compound. It is expedient to keep constant the
amount of water per unit area. The concentration of the
active compound in the preparation is of no importance,
only the amount of active compound applied per unit area
being decisive. After three weeks, the degree of damage
to the plants is rated in % damage in comparison to the0 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
2S according to Preparation Example~ 1, 3 and 13.
It is understood that the specification and examples
are illustrative but not limitative of the present
invention and that other embodiments within the spirit and
scope of the invention will suggest themselves to those
skilled in the art.
Le A 26 728 - 57 _
