Note: Descriptions are shown in the official language in which they were submitted.
r 2 9 ~ ~ ~ 8 7
Azolvlpyrimidine and -triaz~ne derivativ~s
and agents Contain~9Lt
The present invention relates to herbicide~
containing one or more herbicidal active ingredient~ from
the group consisting of the benzothiadiazines of the
formula I
O
~CHICH3) 2
~t2
R 3 R
where
- R3 is hydrogen, halogen, C1-C~-alkyl or C1-C~-alXoxy and
-R4 is hydrogen or cyano~
~ or theis environmentally compatible salts, an azolyl-
pyrimidine of the formula IIa or an azolyltriazine of the
; formula IIb
n n
à~flv--tD mb r d het-roaromatiC radical which is
~15~ bonded vla 1ts~N~atom, contaLns two or three nitro-
gen atom8~and~may~carry a nitro group and/or from
one~tc~three~ of the ~following radicals~ halogen,
,Cl-C~-alkyrl,,~ Ct-C~-haloalkyl,~ Cl-C~-alkoxy, Cl-C~-
h-1oalkoy,::Ct-C~-a1ky1thio, C1-C,-alkoxycarbonyl,
2~0~ aminocar~onyl, C1-C~-alkylaminocarbonyl and/or di-
:C1-C~-al ~ aminocarbonyl,
R2~ is;~halogen~ Cl-C~-a1kyl, C1-C~-haloalkyl, hydroxyl,
Cl-C~-alko~ ,~C~-C~-haloalkoxy, Cl-C"-alkylthio, Cl-C~
h~loalkylthio,:cyano,~nitro,~amino, C1-C,-alkylamino,
5~ C3-Crcyc10alkylam1no, di-CI-C~-alkylamino, phenyl,
pheno ~, phenylamino, benzyl, benzyloxy or benzyl-
r~ . 2 O~Z~ 0050/41130
amino, and these aromati~ radicals in turn may carry
from one to five halogen atom~ and/or from one to
three of the following groups: Cl-C~-alkyl, C1-C~
haloalkyl, Cl-C4-alkoxy, Cl-C~-haloalkoxy, Cl-C~- : -
alkylthio or a radical ~1, and ~ -
n is 0, 1 or 2, and, where n is 2, the radicals R2 may
furthermore be different, -~
or their environmentally compatible salts, and additives
conventionally used for this purpose, and methods for
selectively controlling undesirable plant growth with
these agents.
The present invention furthermore relates to 2-
(l-imidazolyl)-pyrimidine II ~ '
..,, '
and its environmentally compatible salts.
EP-A 257 850 discloses that pyrimidine deriv-
atives monosubstituted or disubstituted by azolyl radi- `~
c~a~ls can be used as drugs. Furthermore, US-A 3 308 122 -~
describes the use of triazines trisubstituted by 1mid~
azo1~ as~:fungicideJ and DE-A 2 051 521 describes the use .
20~ of~ trlazines and~pyrimidine9 monosub~tituted or disub-
stituted~ y imidazole~as additives for rubber/polyester ,`~
composition~. In addition, amino-substituted azolyl-
pyrimidlnes~and triazlne~sèrve a~ drugs, insectivices
;and~ intermQdiate9 (DE-A 3 6Il 427, DE-A 3 639 563, ~r. , -
~2-5~ 2~736~876,~ JP-A~ 49~17675, JP-A 49~17677,
;JP-A~54/40831 and JP-A;56i55 302J.
Herbicidal active ingredients from the group
con8i ting of the benzothiadiazines of the formula I are
used~;for controlllng undesirable plants (DE-A 1 542 836
~30 ~ ~and US~A~4 158 559).
It is ~an ob~ect of the present invention to -- -
pr~ id-~compound8 which are capable of increasing the
actlon of the ~nown herbicides against undesirable plants ;;~
b ' ~ ~ t~ ~ .3
r~ 3 - O.Z. 0050/41130
without los~ of the toleration of these herbicides by
crops. Such compounds are also referred to as synergistic
agents.
We have that this object is achieved by 2~
Lmidazolyl)-pyrimidine II. We have also found that the
azolylpyrimidines and -triazine~ IIa and II~ defined at
the outset are suitable as synergistic agents when
herbLcides from the group consisting of benzothiadiazines
I are used.
2-(1-imidazolyl)-pyrimidine II is particularly
advantageously obtained by reacting a 2-halopyrimidine
III in an inert aprotic nonpolar organic solvent with an
alkali metal salt or alkaline earth metal salt of imid-
azole IV.
~`)~at ~ + 1~ Hal -
~II IV ti
lS In formula III, Hal is a halogen atom, such as fluorine,
- ~ chlorine, bromine or iodine, preferably chlorine, brom- :. ;
ine; in formula IV, M~ is one eguivalent of an alkali ~ :
metal cation or alkaline earth metal cation, such as the
cations of lithium, sodium, potassium, magnesium or :
calcium. .
: The reaction can be carried out continuously or
batchwise under atmospheric pressure or under super-
atmospheric pressures up to 30 bar, preferably under ~- -
atmospheric pressure, and at from 40 to 200C, preferably
25 : :from 70 to 160C.
.: Examples of sultable solvents are ethers, such as
dioxane, tetrahydrofuran, ethylene glycol dimethyl ether
: and dimethylene glycol diethyl ether, alcohol~, such as
m~thanol, ethanol and 2-propanol, ketones, such as
:30 acetono and ethyl methyl ketone, and dimethylformamide,
:` acetonitrile and dimethyl sulfoxlde, as well as mixtures
thereof.
_ 4 _ O.Z. 0050/41130
To increase the reaction rate, it may be advant-
ageous to add an iodide, such as potaQsium iodide.
The required salts of imidazole can be prepared
by methods generally known to the killed worker.
With regard to the use of the synergistic agents
in accordance with regulations, in addition to 2-(1-
imidazolyl)-pyrimidine II preferred azolylpyrimidines and
-tri~zines Ia and Ib are those in which the index and the
substituents have the following meaning~:
Rl is hetaryl, such aQ imidazolyl or triazolyl, prefer-
ably imidazol-l-yl or 1,2,4-triazol-l-yl, which may
carry a nitro group and/or from one to three of the
following radicalss halogen, such as fluorine,
chlorine, bromine or iodine, preferably fluorine,~
chlorine or bromine;
alkyl, such as methyl, ethyl, propyl, 1-methylethyl,
butyl, l-methylpropyl, 2-methylpropyl or l,1-di~
methylbutyl, preferably methyl or ethyl;
~-~ haloalkyl, ~uch as fluoromethyl, difluoromethyl,
~ . 20 trifluoromethyl, chlorodifluoromethyl, trichloro~
- ~; methyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoro-
ethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoro-
ethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloro-
ethyl or:pentafluoroethyl, preferably trifluoro-
methyl or trichloromethyl;
:~ alkoxy, such:as methoxy, ethoxy, propoxy, l-methyl-
. etho~y, butoxy, 1-methylpropoxy, 2-methylpropoxy or
l,l-dimethylethoxy, preferably methoxy or ethoxy;
haloalko~y, ~uch as difluoromethoxy, trifluorometh-
oxy, chlorodifluoromethoxy, dichlorofluoromethoxy,
~ 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,
.~ 1,1,2,2-tetrafluoroethoxy,2,2,2-trifluoroethoxy,2-
; chloro-1,1,2-trifluoroethoxy or pentafluoroethoxy,
preferably trifluoromethoxy;
alkylthio, such a~ methylthio, ethylthio, propyl-
thio, l-methylethylthio, butylthio, l-methylpropyl-
thio, 2-methylpropylthio or 1,1-dimethylethylthio,
: ,
" -
ri` - 5 - O.Z. 0050/41130
- ".,
preferably methylthio or ethylthio;
alkoxycarbonyl, ~uch as methoxycarbonyl, ethoxy-
carbonyl, propoxycarbonyl, l-methylethoxycarbonyl,
butoxycarbonyl, l-methylpropoxycarbonyl, 2-methyl-
s propoxycarbonyl or l,l-dimethylethoxycarbonyl,
preferably methoxycarbonyl or ethoxycarbonyl;
aminocarbonyl;
alkylaminocarbonyl, such as methylaminocarbonyl,
ethylaminocarbonyl, propylaminocarbonyl, l-methyl-
ethylaminocarbonyl, butylaminocarbonyl, l-methyl-
propylaminocarbonyl, 2-methylpropylaminocarbonyl or
1,l-dLmethylethylaminocarbonyl, preferably methyl-
aminocarbonyl
~ and~or dialkylaminocarbonyl, N,N-dimethylamino-
:~ 15 carbonyl,N,N-diethylaminocarbonyl,N,N-dipropylami-
nocarbonyl, N,N-di-~l-methylethyl)-aminocarbanyl),
N,N-dibutylaminocarbonyl, N,N-di-(l-methylpropyl)-
~minocarbonyl, N,N-di-(2-methylpropyl~-aminocarbonyl
~ . or N,N-di-(l,l-dimethylethyl)aminocarbonyl, prefer-
`- : ? ably dimethylaminocarbonyl;
R2 ia halogen as stated for Rl, preferably fluorine,
chlorine or bromine;
: alkyl as stated for Rl, preferably methyl or ethyl;
haloalkyl as ~stated for Rl, preferably trifluoro-
methyl or trichloromethyl;
~:: alkoxy as stated in general and in particular for
` Rl;
h~loalkoxy as stated in general and in particular
for Rl;
30~ alkylthio a~ stated in general and in particular for
hal`oalkylthio, such as fluoromethylthio, difluoro-
methylthio, trifluoromethylthio, chlorodifluoro-
methylthio, dichlorofluoromethylthio, trichloro-
methylthio, l-fluoroethylthio, 2-fluoroethylthio,
2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-
; chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoro-
6 - O.Z. 0050/41130
- ethylthio, 2,2,2-trichloroethylthio or pentafluoro-
ethylthio, preferably trifluoromethylthio; cyano;
nitro; aminc;
alkylamino, such as methylamino, ethylamino, propyl-
S amino, l-methylethylamino, butylamino, l-methyl-
propylamino, 2-methylpropylamino or l,l-dimethyl-
ethylamino, preferably methylamino or ethylamino;
cycloalkylamino, such as cyclopropylamino, cyclo-
butylamino, cyclopentylamino, cyclohexylamino or
cycloheptylamino, preferably cyclopropylamino;
dialkylamino, such as N,N-dimethylamino, N,N-di-
ethylamino, N,N-dipropylamino, N,N-di-(l-methyl-
: ethyl)-amino, N,N-dibutylamino, N,N-d~-(l-methyl-
propyl)-amino, N,N-di-(2-methylpropyl)-amino or N,N-
: 15 di-(l~l-dimethylethyl)-amino~ preferably dimethyl-
amino or diethylamino;
phenyl, phenoxy, phenylamino, benzyl, benzyloxy or
~ benzylamino, where the aromatic radical3 in turn may
- ~ carry from 1 to 5 halogen atomQ a3 stated for R~
:~ 20 preferably fluorine or chlorine and/or from one to
three of the following groups~
alkyl a~ stated in general and in particular for R';
~ haloalkyl as stated in general and in part~cular for
2~ :25 alkoxy a~ Rtated in general and in particular for
;
haloalkoxy as ~tated in general and in particular
for R~
alkyIthio a~ ~tated in general and in particular for
: 30 ~ . Rl;
or a radical Rl, and
n i~ 0, 1 or 2, preferably 0 or 1, and, when n is 2,
~r ~ the radicals R2 may be different.
Special azolylpyrimidine derivative~ IIa and azolyl-
~ triazine derivative~ IIb which were particularly prefer-
rèd as ~ynergistic agent~ in addition to 2-(l-imidazol-
: yl)-pyrimidine II are ~hown in Tables A and B below.
, ~ 0 . Z . 050/41130
- ;: . 7
Table A
Rl 5~ :
6~N> 2 I l a [ R ~ $R ] i -
R2 2
n
Pos Rl X Rm R2n .,
2 CH H 4-R1; 6-CI ~-
2 CH H 4, 6-Rl~ R
2 CH H 4, 6-Cl, Ct
4 CH H 2,4-CI, Cl
10 4 CH H 2-Ct, 6-RI
~: 2 CH H 4-CF 3
2 CH H 4-CI, 6-CH3
4 CH H 2-CI, 6-CH3 - -:~
2 CH H 4-Rl, 6-CH3
5 2 CH H 4-CI - ~ -
~; 4 CH H 2-CI o
:2 CH H 4_R1 : ~:
2 CRm S -N2 H ~-
2 CH 2'-CH3 H
20 2 ~ : CRm 4 5 -Cl, Cl H :-
2 CH 2 -CO2CH3 H ~
: : 2 CH 2'-CH3~ H - -
: 2 CRm 4 -CH3, 5 -Br H : .
2 ~ CH 2'-CONH2 H
~~ ~25` 2 : CRm 2',4',5'-Br,Br,Br H
: 2 CH H 4-CH3
~:H ~ ~ 2 CH H 4-OH, 6-CH3
4 -~ CH H : 6-Rl :
2~ CH H 4-OCH3, 6-CH3
30:4: : : CH H 4-OCH3, 6-CH3
2 ! '! j ; CH j H . ~ 4-OCH3CH3, 6-CH3
.~:: 2 CH H 4-OCH3 ~ - :
:4: ~ CH H 6-OCH3
CH~ H ~ 2-NH2, 6-CH
.-.^, ,~ ::: ~
3 ~
- 8 0,Z. 0050/41130
Table A (contd.)
Pos R1 X Rm R2n
~-
4 CH H 2-NH2, 6-OCH3 :
2 CH H 4,6-CH3, CH3 --
2 CH H 4-NH2, 6-NH ~
2 CH H 4-CI, 6-NH-C3H7 ; ~.
,~ ~ 10 , ,.
2 CH H 4,6-~NHC~CH3)3]
2 CH 2 -CH3 4,6-RI, Rl
2 CH : H 4,6-OH, OH
2 CH H 4-NH2, 6-OH :~
; 15 2 CH H 4,6-NH2, NH2
: 2 CH H 4,6-tNHCH(CH3)2]2
2 ~ CH H 4-NHCH(CH3)2, 6-OCH3 :-~
2 ~ CH H 4,6-~N(CH3)2]2 --~
2 ~ CH H 4~6-(NH-C2Hs)z
20~ ~2 ~ CH H 4-NH2, 6-OCH3
2~ CH H : 4-NH2, 6-CH3
:2 ~ :CH~ 2~-CH3~ 4,6-NH2, NH2
2~ CH : 2 -CH3,~:4 -C2H5 4,6-NH2, NH2 .`
2~ CH~:H ~ 4-Cl, ~-NHcH2cH(cH3)2 ~-.
2~ C ~ 4,6-CH2CH3, CH2CH3
4.~ CH~:~ H ~: : 2-NH2, 6-OCH2CH3
4~ GH~ ~:H ~ 2-NH2, 6-Cl -~
R~ ;H ~ 4-RI, 6-CI
`2~ NN~ l H~ ; 2 4-Cl Cl
2~ N~ ~ H ~ C~, 6-CH3
4~ N H ~ : 2-Cl, 6-CH3
~`'=`~
2 ~5 ~ 3i~ 7
9 O.Z. OOSO/41130
Table A (contd.)
Pos Rl X Rm R2~ :
2 N H 4-Rl, 6-CH3
2 N H 4-Cl
4 N H 2-CI
2 N H 4-RI
2 N 4 -N02 H
~ 2 N 2 -CH3 H
:~ 2 N 2 ,4'-Ct,Cl H
: ~ 2 N 2 -C02CH3 H
~: 2 N 2 -CH3 H
l5 2 N 2'-Br, 4 -CH3 H
2 N 2 -CONHz H
~ . 2 N 2',4 -Br, ~r H
R 2 N H 4-CH3
2 N H 4-OH, 6-CH3
4 N H 6-R1
2 N H 4-oCH3, 6-CH3
4 N H 2-oCH3, 6-CH3
2 N H 4-OCH2CH3, 6-CH3
2 : N H 4-OCH3
:25: 4 : N H 6-OCH3 .
;; 4 N H 2-NH2, 6-CH3
4 N H 2-NH2, 6-OCH3 ~: :
2 H H 4,6-CH3, CH3
! . 9 ,~, :
2 N H 4-NH2, 6-N
; ~:~
2 N H 4-Cl, 6-HH-C3H~
2 N H 4,6-tNHC(CH3)3]2
2~ N 2 -CH3 4,6-Rl, Rl
2 N H 4,6-OH, OH
35~ 2 ~ N H 4-NHz, 6-OH
: 2 : N : H 4,6-NH2, NH2
2 N H 4,6-tNHCH~CH3)2]2
2 N H 4-NHCH(CH3)z, 6-OCH3
2 N H 4,6-tN(CH3)2]2
~ ^, . -, ~ :, .
O.Z. 0050/41130
Ta~le A (contd.)
Pos Rl X Rm R2n
~
2 N H 4~6-~NH-C2Hs)2
2 N H 4-NH2, 6-OCH3 ~ .
2 H H 4-NH2, 6-CH
2 N 2 -CH3 4,6-NH2, NH2
2 N 2 -CH3, 4 -C2H5 4,6-NH2, NH2
2 N H 4-CI, 6-NHCH2(CH3)2
2 N H 4,6-CH2CH3, CH~CH3
2 N H 4-C6H5
4 N H 2-NH2, 6-OCH2CH3 : :~
4 N H 2-NH2, 6-CI - -~
4 N H 2-NHCH3, 6-CH3
4 N H 2-NHCH3, 6-oCH3 ~ -;
:~ 20 Table B -~
~ ~ 6~N 11~ IRI= ~R ]
Pos RI X Rm R2n
2 CH H 4-R1; 6-CI
~:i 2 CH H 4,6-R1, R
~: ~ 2 ~CH H 4,6-Cl, Cl
2 ;~CH H 4-CF3
2 :CH H 4-CI, 6-CH3
`~; 30 2 CH H 4-R1, 6-CH3 -~
2 CH ;H 4-Cl - -
2~CRm 5 -N2 H ~
2~CW 2 -CW3 H : ~:
:35 2 `CRm 4',5'-CI,~ Cl H
2 : CH 4'-C02CH3 H
~,~r Y~
,
- , :- 11 0.Z. O0S0/41130
Table B (contd. )
POS R1 X Rm R2n
2 CH 4 -CH3 H
2 CRm 4 _CH3, 5 -Br H
2 CH 4 _CONH 2 H
2 CRm 2 ,4 , 5 -Br, Br, Br H
2 CH H 4_CH3
2 CH H 4-OH, 6-CH3
2 CH H 4_0CH3, 6-CH3
2 CH H 4-OCHZCH3, 6-CH3
~: 2 CH H 4-OCH 3
2 CH H 4-NH2, 6-CH3
: 2 CH H 4-NH2, 6-OCH3
2 CH H 4,6-CH3, CH3
: 2 CH H 4-NH2, 6-NH ~ ~-
2 CH H 4-CI, 6-NH-C3H7
~ ; 2 CH H 4,6-tNHC(CH3)3]2
.~:2 2 CH 2 _CH3 4,6-R1, R1
2 ~ CH H 4,6-OH, OH -
2 CH H 4-NH2, 6-OH
~ 25 2 ~ CH H 4,6-NH2, NH2
.- ;:~ 2 ~ CH H 4,6-tNHCH(CH3)2]2
~ 2 CH H . 4-NHCH(CH3)2, 6-OCH3
~ ~ 2 CH H 4,6-tN(CH3)2]2
2~ CH ~ H 4,6-(NH-C2H5)2
30 ~ ~2 ~ CH 2 -CH3 4,6-NH2, NH2
~ 2 ~ ~ CH: 2 -CH3, 4 C2H5 4,6-NH2, NH2
;~H~ ~ 2 CH H 4-C1, 6-NHCH2CH(CH3)2
2 1 CH ; H 4,6-CH2CH3, CH2CH3
2 CH H 4-C6H
~3g~ 2 ~ CH H 4-NH2, 6-OCH2CH3
:2~ ~ CH H 4-NH2, 6-C1
2 ~ CH H 4-NHCH3, 6-CH3
2 ~ :~ CH H 4-NHCH3, 6-OCH3
-40 ~
~ ~ ,
- . . ; ,
12 O.Z. 0050/41130
Tab I e B (contd . )
Pos Rl X Rm R2"
2 N H 4-Rl, 6-Cl .~ j
2 N H 4~6-Rl~ Rl
2 N H 4,6-CI, Cl
2 N H 4-CF3
2 N H 4-CI, 6-CH3
2 N H 4-Rl, 6-CH3
2 N H 4-CI
2 N H 4_Rl
2 N 4 -N02 H
2 N 2 -CH3 H - ;~
2 N 2 -4 -Cl, Cl H :~.2 N 2 -CO2CH3 H
2 N 2'-CH3 H
2 N 2 -Br, 4 -CH3 H - /:.
20 2 N 4 -CONH2 H
2 N 2 ,4 -Br, 8r H
2 N H 4-CH3 ` -
H ~ 2 N H 4-OH, 6-CH3 ~ .
~: 2 N H 4-OCH3, 6-CH3
25 2 N H 4-OCH2CH3, 6-CH3 ~
: 2 N H 4-OCH3 .:.-:
: 2 N H 4-NH2, 6-CH3
i:~ 2 N H 4-NH2, 6-OCH3 ;~
: 2 N H 4,6-CH3, CH3 ~ -
.~
, .
: 2 N H 4-NH2, 6-NH
' 1!~. 1~ 21 i N ~ H 4-CI, 6-NH-C3H7
: 2 N H4,6-[NHC(CH3)3]2
H 35 2 : ~ N 2 -CH3 4,6-Rl, Rl,
2 N H4,6-OH, OH H:
; 2 N H 4-NH2, 6-OH
`2 N H 4,6-NH2, NH2
',:--:: .' ~'"
' ~;. ` ': ' '
. ! : 13 0.Z, 0050/41130
Table B (contd.)
POS Rl X Rm R2n
2 N H 4,6-tNHCH(CH3)2]2
2 N H 4-NHCH(CH3)2, 6-OCH3
2 N H 4,6-tN(CH3)2]2
2 N H 4,6-(NH-C2Hs)2
10 2 N 2 -CH3 4,6-NH2, NH2
2 N 2 -CH3,4'-C2H5 4,6-NH2, NH2
2 N H 4-Cl, 6-NHCH2CH~CH3)2
2 N H 4,6-CH2CH3, CH2CH3
: 2 N H 4-C6H5
:: : 15 4 N H 4-NH2, 6-OCH2CH3
2 N H 4-NH2, 6-CI
: 2 N H 4-NHCH3, 6-CH3
: 2 N H 4-NHCH3, 6-OCH3 :-
Specific examples of herbicidal benzothiaaiazines 1, whose action may be
improved:by 2-~1-imiddzolyl)pyrimidine II and the synergistic azolyl-
pyrimidine~or triazine derivatives lla and lIb, are given in the following
Table C:~
:25
." .,, ,, ~
?J ~ 7
~.
"~
14 O.Z, 0050/41130
O
2
R3 R4
No. R3 R4 Literature
I. 001 H H DE-A 1 542 83$
I. 002 F H DE-A 2 444 383 :
I. 003 Cl H DE-A 2 444 383
I. 004 CH3 H DE-A 2 443 901
10 I. 005 H Na DE-A 1 542 836 .
I. 006 F Na DE-A 2 444 383
I. 007 Cl Na DE-A 2 444 383
I. 008 CH3 Na DE-A 2 443 901 ~ I
; I. 009 H CN OE-A 2 656 289 - :.
lS 1. 010 F CN DE-A 2 656 289
~:~I.` 011 Cl CN DE-A 2 656 289 ~;~
: I. 012 CH3 CN DE-A 2 656 289
"
,, :,
-
~J'~J ?~
- -. 15 O.Z. oosa/4ll30
For herbicidal benzothiadiazines of the formula I, the amount of syner-
gistically active compound varies, depending on the crop. The ratios may
va~y over a wide range, and are also dependent on the structure of the
benzothiadiazines of the for~ula I and on the crop involved. Suitable
5 ratios of synergist to herbiciae are from 0.01:1 to 10:1, preferably from
0.05:1 to 6:1, and particularly from 0.1:1 to 4:1, parts by weight.
The herbicidal active ingredients and synergistic compounds may be applied
separately or together to the leaves and shoots of crop plants and un-
10 desired plants. Preferably, the synergistic aaent is applied simultaneous-
ly with the herbicidal active ingredient. The synergist and herbicidal
active ingredient may be applied simultaneously but separately to the
field, or one after the other. They may be formulated together or separ-
ately as suspensions, emulsions or solutions for use as spray liquors.
It is also possible to treat the crop plant seed with the synergist prior
to sowing. The herbicidal active ingredient is then applied alone in
conventional manner.
; .
20 The amount of pure active ingredient required, i.e., without formulation
auxiliaries, depends on the composition of the stand, the development
stage of the plants, on local climatic conditions, and on the application
technique employed. Generally, application rates are from 0.25 to 5, and
preferably from 0.5 to 2.5, kg/ha.
The crops in which the herbicidal and synergistic agents may be used are
essentially those in which the individual active ingredients of the mix-
ture may be employed. In the case of agents containing benzothiadiazinone
derivatives of the formula I, examples of such crops are barley, sorghum,
30 Indian corn, rice, wheat, peas, groundnuts, soybeans and lawns.
The method of application is also important. If the novel agents are used
; for combating unwanted plants in crops having insufficient tolerance,
special techniques may be emp~oyed by means of which the leaves of the
35 crop plants come as little into contact with the agents as possible,
whereas the unwanted plants growing between or under the crop plants, or
the free area between them, is hit by the agents (post-directed or layby
application).
40 The novel herbicidal agents may, in addition to the azolyl derivative of
-~ the formula lIa and/or ~Ib as synergist and the herbicide from the group
of benzothiadiazines 1, contain further herbicidal and growth-regulating
active ingredients and inert additives.
.~ ~
~ `
. ~: .
16 0.Z O0S0/41130
In addition to the synergistic action evident when the triazole com-
pounds I, IA and IB are used together with benzothiadiazines of the
formula II, they may also be used as synergists with the following
herbicides (trade names in brackets): ::
5-amino-4-chloro-2-phenylpyridazin-3(2H)-one (Pyrazon)
4-chloro-5-methylamino-2-(trifluoromethylphenyl)-3(2H)-pyridazin-3(2H)-one
(Monometfluorazon)
3-(3-chloro-4-methylphenyl)-1,1-dimethylurea (Chlortoluron)
3-(4-bromophenyl)-1-methoxy-1-methylurea (Metobromuron)
3-(4-isopropylphenyl)-1,1-dimethylurea (Isoproturon)
3(3,4-dichlorophenyl)l-metho~y-1-methylurea (Linuron)
3-(3,4-dichlorophenyl)-1,1-dimethylurea (Diuron)
3-(2-benzothiazolyl)1,3-dimethylurea (Methabenzthiazuron)
1,1-dimethyl-3-(3-trifluoromethylphenyl)-urea (Fluometuron) ~ ~:-
methyl-2-t3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonylamino-
sulfonyl]benzoate) (Metsulfuron-methyl)
methyl-2-~3-(4,6-dimethoxypyrimidin-2-yl)aminocarbonylaminosulfonyl]- -~ :
benzoate (Bensulfuron-methyl)
ethyl-2-[3-(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonylaminoSulfonyl]- ' . .:
benzoate (Chlorimuron) ~ .
methyl-2-~3-(4-metho~y-6-methyl-1,3,5-triazin-2-yl)-3-methylaminocarbonyl- : .-
aminosulfonyl]benzoate . .:-3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-1-t2-(2-methoxyethoxy)phenyl-
sulfonyl]urea (Cinosulfuron)
methyl-2-t3-(4,6-bis(difluoromethoxy)pyrimidin-2-yl)-aminocarbonylamino- :-
sulfonyl]benzoate (Primisulfuron)
2-(2-chloroethoxy)N-t[(4- methoxy-6-methyl-1,3,5-triazin-2-yl)amino- ~ -
carbonyl]benzenesulfonamide (Triasulfuron)
2-t[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-3-pyridine- :
carboxylic acid-N,H-dimethylamide
S-(4-chlorobenzyt)-N,N-diethylthiocarbamate (Penthiocarb)
S-benzyl-N,N-dipropylthiocarbamate (Prosulfocarb) --
S-ethyl-N,N,-di-iso-butylthiocarbamate (Butylat) :-
S-ethyl-N,N-di-n-propylthiocarbamate (EPTC) .-. ~-
3-(methoxycarbonylamino)phenyl-N-(3-methylphenyl)carbamate --
(Phenmedipham)
3-(ethoxycarbonylamino)phenyl-N-phenylcarbamate (Desmedipham)
isopropyl-N-(3-chlorophenyl)-carbamate (Chloropropham)
2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline (Trifluralin)
3,4-dimethyl-2,6-dinitro-N-l-ethylpropylanilin (Pendimenthalin)
4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (Metamitron)
4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5(4H)-one (Metribuzin)
2-(2-chloro-4-ethylamino-1,3,5-triazin-yl-amino)-2-methylpropionitrile
(Cyanazin)
2-chloro-4-ethylamino-6-iso-propylamino-1,3,5-triazine (Atrazin)
~,, S,? ,'" i
17 O.Z. 0050/41130
2-chloro-4-ethylamino-6-tert.-butylamino-1,3,5-triazine
(Terbutylazin)
3-chloro-4-chromethyl-1-(3-trifluoromethylphenyl)pyrrolidin-2-one
(Fluorochloridin)
5 2-chlor-6-nitro-3-phenoxyaniline (Aclonifen)
3,6-dichlor-2-methoxybenzoic acid ~DicambaJ
2,5-dichloro-3-aminobenzoic acid (Amiben)
2,4-dichloropheno~yacetic acid (2, 4-D)
2-(2,4-dichlorophenoxy)propionic acid (Dichloprop)
10 2-(4-chloro-2-methylphenoxy)propionic acid (Mecoprop)
methyl-~4-(2,4-dichlorophenoxy)-phenoxy]propionate (Diclofop-methyl)
ethyl-2-[4-~6-chloro-2-benzoxazolyloxy)phenoxy]propionate
(Fenoxaprop-ethyl)
ethyl-2-[4-(6-chloro-2-quinoxanyloxy)phenoxy]propionate
15 (Quizalafop-ethyl)
methyl-2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate
(Haloxyfop-methyl)
butyl-2-[4-(5-triftuoromethyl-2-pyridyloxy)phenoxy]propionate
~Fluazifop-bentyl)
~ 20 4-amino-3,5-dichloro-6-fluoro-2-pyridinyloxyacetiC acid (Fluroxypyr),
:~ its salts and esters, e.g. 1-methylheptylester
- ~ 7-chlor-3-methylquinoline-8-carboxylic acid (Quinmerac)
3,7-dichloroquinoline-8-carboxylic acid (Quinclorac)
-(2,4-difluorophenyl)-2-(3-trifluoromethylphenoxy)-3-pyridincarboxamide
25 (Diflufanican)
exo-l-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)-7-oxa-
bicyclo(2.2.1)heptane:(Cinmethlin)
2-(2-chlorophenyl)methyl-4,4-dimethyl-3-is-oxazolidinon (Clomazon)
5-methylamino-2-phenyl-4-(3-trifluoromethylphenyl)furan-312H)-one
~: 30 (Flurtamon)
2-t4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H- imidazol-2-yl]-
-S-ethyl-3-pyridine carboxylic acid (Imazethapyr)
2-t4,~5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-lH-imidazol-2-yl)-
:3-quinolinecarboxylic acid (lmazaquin)
35 4-chloro-2-oxobenzothiazolin-3-ylacetic acid (Benazolin)
2-phenyl~-3,1-benzoxa2in-4-one -~
5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one IFluorobentranil)
3',4'-dichloropropionanilide (Propanil)
5-[2-chloro-4-ttrifluoromethyl)phenoxy]-2-nitrobenzoic acid, sodium salt
~m 4o~ cifluorfen)
methyl-5-12:,4-dichlorophenoxy)-2-nitrobenzoate IBifenox)
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-N-methansulfonylbenzamide
Fomesafen)
: 3,5-di~bromo-4-hydroxybenzonitrile (Bromoxynil)
3,5-diiodo-4-hydroxybenzonitrile tIoxynil).
l~ O.Z. 0050/41130
It may also be useful to apply the mixtures according to the invention in
admixture with other crop protection agents, e.g., agents for combating
pests or phytopathogenic fungi or bacteria. The mixtures may also be mixed ~ -
with solutions of minerals used to remedy nutritional or trace element
5 deficiencies.
: ., :
The agents according to the invention, or the herbicidal active ingredient
and the synergist when applied separately, may be applied for instance in ~ - -
the form of directly sprayable solutions, powders, suspensions (including
10 high-percentage aqueous, oily or other suspensions), dispersions, emul-
sions, oil dispersions, pastes, dusts, broadcasting agents, or granules by
spraying, atomizing, dusting, broadcasting or watering. The forms of ap-
plication depend entirely on the purpose for which the agents are being
used.
The formulations contain from 0.1 to 95, and preferably from 0.5 to 90,
wt% of active ingredient mixture, and may be produced by conventional
methods. -
, ~.
20 For the preparation of solutions, emulsions, pastes and oil dispersions to ;
be sprayed direct, mineral oil fractions of medium to high boiling point,
such as kerosene or diesel oil, further coal-tar oils, and oils of
vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons
such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkyl-
25 ated naphthalenes and their derivatives such as methanol, ethanol, propan- -ol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexan- ~- -
one, chlorobenzene, isophorone, etc., and strongly polar solvents such as
dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc.
are suitable. -
Aqueous formulations may be prepared from emulsion concentrates, pastes,
oil dispersions or wettable powders by adding water. To prepare emulsions,
pastes and oil dispersions the herbicidal active ingredient and/or
~-~ antidote as SUch or dissolved in an oil or solvent may be homogenized in
35 water by means of wetting or dispersing agents, aCherents or emulsifiers.
Concenitrates which are suitable for dilution with water may be prepared
from herbicidal active ingredient and/or antidote, wetting agent,
adherent, emulsifying or dispersing agent and possibly solvent or oil.
40 Examples of surfactants are: alkati metal, alkaline earth metal and
- ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,
phenolsulfonic acids, alkytaryt sutfonates, alkyl sulfates, and alkyl
sulfonates, alkali metal and alkaline earth metal salts of dibutyl-
naphthatenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates,
~ 3
19 O.Z. 0050/41130
alkali metal and alkaline earth metal salts of fatty acids, salts of
sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated
fatty alcohol glycol ethers, condensation products of sulfonated
naphthalene and naphthalene derivatives with formaldehyde, condensation
5 products of naphthalene or naphthalenesulfonic acids with phenol and
formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-
phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol
polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether
alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates,
10 ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-
oxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
lignin-sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or
lS grinding the herbicidal active ingredient and/or antidote with a solid
carrier. -
Granules, e.g., coated, impregnated or homogeneous granules, may be
prepared by bonding the active ingredients to solid carriers. Examples of
20 solid carriers are mineral earths such as silicic acid, silica gels,
silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,
loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium
sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium
sulfate, ammonium phosphate, ammonium nitrate, and ureaS, and vegetable
25 products such as grain flours, bark meal, wood meal, and nutshell meal,
cellulosic powders, etc.
The herbicidal and synergiStic agents according to the invention may
additionally be mixed and applied together With numerous representatives
of further herbicidal and growth-regulating active ingredient groups.
Manufacturing example
2-1-lmidazolylpyrimidine
, ~ .
At 25~, a solution of 136.2 g ~2.0 mol) of imidazole and 1.5 liters of
ethanol was added to a mixture of 127.5 9 of potassium hydroxide and l.0
liter of ethanol. ~fter a further 2 hours at this temperature, the solvent
was stripped off under reduced pressure. The residue was dissotved in l.5
liters~of dimethylformamide, and 10 9 of potassium iodide and then a
solution of 229 9 ~2.0 moles) of 2-chloropyrimidine and 1.0 liter of
~ `
0.Z. 0050/41130
dimethylformamide were added to this solution. The reaction mixture -
obtained in this manner was kept at 100C for 2 hours, and the solid
components were then filtered off. The product was then isolated from the --
filtrate as a solid. ---
5 M.p.: 128 - 130C; yield: 280 9 (96%); active ingredient no. 1.001.
The compounds listed in the tables below may be obtained analogously to
the synthesis example or in accordance with the cited literature by
appropriately modifying the starting materials.
,'
' . "
~ 2S
: " '
~
.
. :~ - ' .,
,~
- - 0 . Z . 0050/4'1130
.~ I I I I ' ' I I ' ' ' I ' ' .
:
,. ID
O o o~-J o ~ ~ t ~ CO ~
t~l t~l ~ 01~ trl ~ O O ~ O
. 0 o o~
~t 0 _ ~ t
. T ~
~: ~t ~ -t ~ ~ ~ -t ~ ~ ~ . _ T ~ .
- ~ 4~ 17
., .
0 . Z . 0050/41130
L
L
. ',' '
: .'
U~ . , '.
O
O~ *
0~ ~ C.
:, ~
CO O
. ~ O
~ <X~ O ~ .. :,
/~
- , -- ~ S
T ~ T
C.J O ~ O O O O ~ ~ O Z Z Z ~D -
;X~ ~ S Z z z c.~ J U Z Z JJ ~ E
s i ~ ' ~ i c
~ u : ~ : : z
~ O ~ o ~ o ~ o o O O O O O O O O O O O O E
.
0. Z. 0050/4'1130
~ ~ '
L
C~
.. ~ * , :"
' , ~ ,"'~
S ~ ~ O ~ ~
: O O ~ O 0 ~ .
J ,`~ ~ W W W ~ W W
: ~ Z ~ Z ~ ~ Z ~z ~ Z Z Z , ' .'''~ ,. ',~,~: .
; ~ o
~ Z~ ~ ~ ~ ~ ~'
2 ~ ~ ~ J l1 ~
1,, O.Z. 0050/41130
L O
CO
~ .,
o~ ":
:~ Ul ~
1~ ~ o
r~
~z7 ~ T
~- ~ ~0 2 V~ ~: cc Z D
C^~ Z ~ _ I = Z Z
Z -- I I I I I I T l l
E : .
S I ~I S I I I S S S S
S : -'
E
h ~ ._
O
~ ~ ~ ~ ':
~ o o ~ ~ ~ ~ ~ ~o ~
; ' ~J ~
0 . Z, 0050/41130
_ _ _ _
' -~."','
''~
U~ ,: :
0~
~ ,
~: ~ I I I I ~
; ~ ' . ff
_ .
~ .
S ~
, :: ~::-.:.. :
: o S S S Z o ~ ~ -~
(~ ff ~
_~ S ~ S ~ S
: : Z Z ~ Z Z ~ Z
~ ~:t l ~ t` t~ ~S t .
E:~ : ~ r~z ~s ~
~ ;`"X~ ~ Z'~ ZZS ,.",~":,
~ n~ ~ `0~O 0~0~0~0 0
: 26 O.Z. 0050/41130
Literature: . -
5 TAKEDA KENKYUSHO 22, 27-46 (1963), cited after CA 60: 12 011 a/b .- -
2)
EP-A 257 850 . .
3)
10 DE-A 3 639 563
4)
J. Org. Chem. 43, 3957 (1978)
15 5)
DE-A 2 736 876
6) .-
Ookl. Akad. Nauk SSR, 228 (6), 1358-61
- :- -
DE-A 3 611 427
8)
25 US-A 3 308 122
JP 49/1767S ~May 2, 1975)
30 10)
Science (Washtngton, D.C.) 158 (3807), 1462-3 (1967)
JP 49/17677 (May 2, 1974)
35 12
JP~56/55~0~ y 15, 1981~
40 JP~54/40831 A 79/40831 V (Oct. 31, 1979)
OE-A 2:051 521 ~- -
5' 7
~ . . ....
27 0.Z. 0050/41130
Use examples
The vessels employed were plastic flowerpots ha~ing a volume of 300 cm3
and filled with a sandy loam ~ontaining about 3.0% humus. The seeds of the
5 test plants were sown separately, according to species. -'
For the preemergence treatment, the formulated active ingredients were
applied to the surface of the soil immediately after the seeds had been
sown. The compounds were emulsified or suspended in water as vehicle, and
10 sprayed through finely distributing nozzles.
After the agents had been applied, the vessels were lightly sprinkler-
irrigated to induce germination and growth. Transparent plastic covers
were then placed on the vessels until the plants had taken root. The cover
15 ensured uniform germination of the plants, insofar as thiS waS not - ~ -
impaired by the active ingredients.
For the postemergence treatment, the plants were gro~n, depending on;~
^ growth form, to a height of 3 to 15 cm before being treated with emulsions -~
20 or suspensions of the active ingredients in water. In thiS treatment
method, either plants which had been Sown in the pots and grown there were
selected, or they were cultivated separately as seedlings and transplanted
to the pots a few days before being treated. The application rates for
postemergence treatment were 0.l25 to 2.5 kg/ha.
The test plants were tended in accordance with their natural requirements ;~
~; at temperatures of 20 to 35C, or lO to 25C for from 2 to 4 weeks. Their -~
reactions to the various treatments were assessed. The assessment scale
was 0 to 100, 100 denoting nonemergence or complete destruction of at
30 least the visible plant parts, and 0 denoting no damage or normal growth.
~, ~ :: .
The plants~used in the greenhouse experiments were Amaranthus retroflexus,
Solanum nigrum, Cassia tora, Glycine max. and Zea mays.
35 The fo~lowlng active ingredients or mixtures thereof were used in the -~ ;
experiments~
:: . ~ ,: .
Compourd~1.005 was used aS benzothiadiazone I:
CH ( CH 3 ) 2 I . 005
N--SO 2
Na :.
; 40 ` `.:
. . ` .
~; ~
s, ~ 7
.
,, .~
28 0,Z. 0050/~1130
The active ingredient was formulated as an aqueous solution at a concen- --
tration of 480 g/l.
The active ingredient 2-tl-imidazolyl)-pyrimidine (1.001) was used as
5 representative of the Synergistic azolylpyrimidines lIa. It was formulated
as a 10% emulsion concentrate in a system consisting of 70% solvent, 20~o
emulsifier and 10% surfactant. All the formulations adaitionally contained
surfactant additives (5.6 l/ha).
10 In these examples, the method of S.R. Colby (Weeds 15, 20) was used to
calculate the value E which is to be expected if the combined action of
the individual components of the mixture is merely additive.
The formula employed is
XY ''
E = X + Y -
100
20 where X is the percentage action with active ingredient A at concentration
~- a; Y is the percentage action with active ingredient B at concentration b;
and E iS the expected aFtion (in #) of A+8 at application rates a+b.
Table I
Synergistic herbicidal action of the mixture according to the invention
consisting of 2-(1-imidazolyl)pyrimidine (1.001) and the herbicide I.005
on postemergence application in the greenhouse ~ -
30 Herbicide SynergiSt Amaranthus retroflexus
No. 1.005 No. 1.001 Damage in % E
kg/ha kg/ha
, , .
1.25 - 78
35 0.625 - ~o
0.5 0
- 0.125 0
1.25 ` 0.5 100 78
1.25 0.125 98 78
40 0.625 0.5 95 50
.625 0.125 80 50
:,
~, :
s; ~ ) 7
. ::
29 O.Z. 0050/41130
Table II
Synergistic herbicidal action of the mixture according to the invention
consisting of 2~ imiddzolyl)pyrimidine (1.001) and the herbicide 1.005 ~ ~ -5 on postemergence application in the greenhouse
Herbicide Synergist Amaranthus retroflexus
No. I.005 No. 1.001 Damage in % E ~ -
kg/ha kg/ha
"
0.625
- 0.25 0
0.625 0.25 98 45
-
* All formulations additionally contained 11.2 l/ha of an ammonium ~
nitrate/urea solution (28~ nitrogen) as an additive. ~ -
" rable III
:~ ~ `
Synergistic herbicidal action of the mixture according to the invention
consisting of 2-(1-imidazolyl)pyrimidine (1.001) and the herbicide 1.005
on postemergence application in the greenhouse
25 HerbicideSynergist Amaranthus retroflexus
No. I.005No. 1.001 Oamage in % E - ~ ~-
kg/ha kg/ha
0.25 - 70
30 0.125 - 25
- 0.5 0
0.25 0.5 90 70
0.125 0.5 70 25
-
,,:~ ~ ' :
`. ~, ~ ' : , . `
~ 40
: ..
~; ~
:: : ,: . , .
, .
