CA2010650A1 - Herbicidal sulphonylated azinyliminoheteroazoles - Google Patents
Herbicidal sulphonylated azinyliminoheteroazolesInfo
- Publication number
- CA2010650A1 CA2010650A1 CA002010650A CA2010650A CA2010650A1 CA 2010650 A1 CA2010650 A1 CA 2010650A1 CA 002010650 A CA002010650 A CA 002010650A CA 2010650 A CA2010650 A CA 2010650A CA 2010650 A1 CA2010650 A1 CA 2010650A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- alkoxy
- fluorine
- chlorine
- bromine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
Abstract
A B S T R A C T
A herbicidal sulphonylated azinyliminoheteroazole of the formula
A herbicidal sulphonylated azinyliminoheteroazole of the formula
Description
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 _ . .
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 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 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 - - :
' 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 - :
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 -(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 ~ :
, 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:
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 S CH3 N CH C-CH3 CH N c~3 N CH c-CH3 N C-c~3 5 CH3 N CH c-CH3 N C-CF3 `5 CH3 N CH C-CH3 Le A 26 728 - 18 -Table 1 - Continuation 2010650 N C-SCH~ S CH3 N CH C-CH3 N C-CHC12 5 CH3 N CH C^CH3 C-Cl C-Cl S CH3 N CH C-CH3 N C~ S OCH3 N CH C-OCH3 Le A 26 728 - 19 -Table 1 - Continuation 2010~0 N C-CH~CH3)2 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 Le A 26 728 - 20 -Table 1 - Continuation 20 N C_CH3 S OCH3 N CH C-OCHF2 N C-SCH3 5 C.Y3 N CH C-OCHF
C-Cl C-Cl S OCHF2 N CH C-ocHF2 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 . .
C-Cl C-Cl S CH3 N N C CH3 N C-c~3 5 C~3 N N C-OCH3 N CH S OCH3 N N C-OCH3 ~ :~
C~ N S OCH3 N N C-OCH3 6 5 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
,.
~ ' ,, : ~ `
: ~
~.
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) 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) 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 -: - . . ., . ,~ -: ~ :; ~ ', ..
--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 -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 _ - ., 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 -, ~'''' .
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 -: - - :: - ~
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 ~
N-N N==~
~=N-~ ~
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.
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 _ . .
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 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 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 - - :
' 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 - :
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 -(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 ~ :
, 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:
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 S CH3 N CH C-CH3 CH N c~3 N CH c-CH3 N C-c~3 5 CH3 N CH c-CH3 N C-CF3 `5 CH3 N CH C-CH3 Le A 26 728 - 18 -Table 1 - Continuation 2010650 N C-SCH~ S CH3 N CH C-CH3 N C-CHC12 5 CH3 N CH C^CH3 C-Cl C-Cl S CH3 N CH C-CH3 N C~ S OCH3 N CH C-OCH3 Le A 26 728 - 19 -Table 1 - Continuation 2010~0 N C-CH~CH3)2 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 Le A 26 728 - 20 -Table 1 - Continuation 20 N C_CH3 S OCH3 N CH C-OCHF2 N C-SCH3 5 C.Y3 N CH C-OCHF
C-Cl C-Cl S OCHF2 N CH C-ocHF2 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 . .
C-Cl C-Cl S CH3 N N C CH3 N C-c~3 5 C~3 N N C-OCH3 N CH S OCH3 N N C-OCH3 ~ :~
C~ N S OCH3 N N C-OCH3 6 5 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
,.
~ ' ,, : ~ `
: ~
~.
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) 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) 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 -: - . . ., . ,~ -: ~ :; ~ ', ..
--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 -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 _ - ., 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 -, ~'''' .
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 -: - - :: - ~
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 ~
N-N N==~
~=N-~ ~
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 ~;
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 ' 8 CH CH S ~ CH3 N CH C-CH3 174 Cl 9 CH CH S ~ -CH3 N CH C-OCH3 193 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 12 CH CH S ~ OCH3 N CH C-OCH3 14?
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
18 N CH S ~ CH3 N CH C-CH3 178 OCF3 :
19 CH CH S ~ CH3 N CH C-CH3 178 :
CH CH S ~ CH3 N CH C-OCH3 171 21 N CH S ~ CH3 N CH C-OCH3 174 22 N CH S ~ OCH3 N CH C-OCH3 128 ~ ~t 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 29 N CH S ~ CH3 N CH C-OCH3 177 :~
~ 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 -, ~
Table 2 - Continuation Ex A D E R1 R2 X y z pOlnin~c 32 N C-CH3 S ~ CH3 N CH C-CH3 179 Cl 33 CH CH S ~ CH3 N CH C-OCH3 190 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 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 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 ~ .
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
47 N CH S ~ CH3 N CH C-OCH3 167 48 N CH S ~ OCH3 N CH C-OCH3 160 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 SS N CH S ~ CH3 N CH C-CH3 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 ~ .
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 63 N CH S ~ _ OCH3 N N C-OCH3 : , , . .' SCH3 -~ . :
64 CH CH S ~ OCH3 N CH C-OCH~ :
N CH S ~ OCH3 N N C-OCH3 5o2N(cH3)2 66 N CH S ~ OCH3 N CH C-OCH3 67 N CH S ~ CH3 N CH C-CH3 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 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 77 N CH S ~ OCH3 N CH C-OCH3 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 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 ~7 C-CH3 N S ~ CH3 N CH C-OCH3 176 .
;~ : , Le A 26 728 - 52 - . ~
,~ .
.
, 20106S() ... ..
~ o _, .~
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~ ~ ~ ~ tq s o o o o o ~, ~, 5~
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.
~ ~: ~ tq ~ ~., N~ O U U U
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~ ': ' "`, ` ''~ ~
~ ~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
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.
X Z Z Z Z Z
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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-3 CH CH S OCH3 N N C-OCH3 ~250 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-12 N C-CH3 S CH3 N CH C-CH3 223- ~-225 ~ ;~
II-14 N C-CH3 S OCH3 N CH C-OCH3 214 ~:
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 the 0 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 _
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 ~;
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 ' 8 CH CH S ~ CH3 N CH C-CH3 174 Cl 9 CH CH S ~ -CH3 N CH C-OCH3 193 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 12 CH CH S ~ OCH3 N CH C-OCH3 14?
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
18 N CH S ~ CH3 N CH C-CH3 178 OCF3 :
19 CH CH S ~ CH3 N CH C-CH3 178 :
CH CH S ~ CH3 N CH C-OCH3 171 21 N CH S ~ CH3 N CH C-OCH3 174 22 N CH S ~ OCH3 N CH C-OCH3 128 ~ ~t 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 29 N CH S ~ CH3 N CH C-OCH3 177 :~
~ 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 -, ~
Table 2 - Continuation Ex A D E R1 R2 X y z pOlnin~c 32 N C-CH3 S ~ CH3 N CH C-CH3 179 Cl 33 CH CH S ~ CH3 N CH C-OCH3 190 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 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 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 ~ .
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
47 N CH S ~ CH3 N CH C-OCH3 167 48 N CH S ~ OCH3 N CH C-OCH3 160 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 SS N CH S ~ CH3 N CH C-CH3 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 ~ .
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 63 N CH S ~ _ OCH3 N N C-OCH3 : , , . .' SCH3 -~ . :
64 CH CH S ~ OCH3 N CH C-OCH~ :
N CH S ~ OCH3 N N C-OCH3 5o2N(cH3)2 66 N CH S ~ OCH3 N CH C-OCH3 67 N CH S ~ CH3 N CH C-CH3 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 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 77 N CH S ~ OCH3 N CH C-OCH3 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 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 ~7 C-CH3 N S ~ CH3 N CH C-OCH3 176 .
;~ : , Le A 26 728 - 52 - . ~
,~ .
.
, 20106S() ... ..
~ o _, .~
~P~
~ .
~ ~ ~ ~ tq s o o o o o ~, ~, 5~
U U U U U
~ ' x z æ æ æ z :~
.
~ ~: ~ tq ~ ~., N~ O U U U
: ~
~ ~ob~b~b ~ob 4b~
O U~
~') t" ,:
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
, . `~, ~ b ,, , u~
o , ~ x ~ ls ~
U . . .;
Z Z Z Z Z . " .,."
C . . - . .
~ .. ~ , ~
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-3 CH CH S OCH3 N N C-OCH3 ~250 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-12 N C-CH3 S CH3 N CH C-CH3 223- ~-225 ~ ;~
II-14 N C-CH3 S OCH3 N CH C-OCH3 214 ~:
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 the 0 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 _
Claims (19)
1. A sulphonylated azinyliminoheteroazole of the formula (I) in which A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, halogen, cyano, nitro or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino, dialkylamino or phenyl, D represents nitrogen or the grouping C-D1, in which D1 represents hydrogen, halogen, cyano, nitro or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino, dialkylamino or phenyl, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, R1 represents in each case optionally substituted alkyl, aralkyl, aryl or heteroaryl, R2 represents hydrogen, halogen, hydroxyl, amino or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkyl-amino or dialkylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, halogen, cyano, alkyl, formyl, alkylcarbonyl or alkoxycarbonyl, and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, halogen, hydroxyl, amino or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsul-phonyl, alkylamino or dialkylamino.
2. A sulphonated azinyliminoheteroazole according to claim 1, in which A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, fluorine, chlorine, bromine iodine cyano or nitro or represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl C1-C4-alkylsulphonyl, C1-C4-alkylamino or di-(C1-C4)-alkyl-amino in each case optionally substituted by fluorine and/or chlorine or C1-C4-alkoxy, or represents phenyl optionally substituted by fluorine chlorine bromine C1-C4-alkyl, C1-C2-fluoro- and/or chloro-alkyl, C1-C4-alkoxy and/or C1-C2-fluoro-and/or -chloro-alkoxy, D represents nitrogen or the grouping C-D1, in which D1 represents hydrogen, fluorine, chlorine, bromine, iodine, cyano or nitro, or represents C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino or di-(C1-C4)-alkyl-amino in each case optionally substituted by fluorine and/or chlorine or C1-C6-alkoxy, or represents phenyl optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C2-fluoro- and/or chloro-alkyl, C1-C4-alkoxy and/or C1-C2-fluoro-and/or -chloro-alkoxy, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, R1 represents the radical , in which R5 and R5 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxycarbonyl, C1-C4-alkylamino-carbonyl, di-(C1-C4-alkyl)aminocarbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkyl-thio, C1-C4-alkylsulphinyl, C1-C4-alkylsul-phonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl), C2-C6-alkenyl (which is optionally substituted by fluo-rine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxy or phenyl), C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), C1-C4-alkoxy (which is optionally sub-stituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkoxy, C1-C4 alkylthio, C1-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl), C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), C3-C6-alkenyloxy (which is optionally substituted by fluorine, chlo-rine, bromine, cyano or C1-C4-cyano or C1-C4-alkoxy-carbonyl), C2-C6-alkenylthio (which is optionally substituted by fluo-rine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio or the radical -S(O)p-R7, where p represents the numbers 1 or 2 and R7 represents C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), C3-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkylamino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino or for the radical -NHOR8, where R8 represents C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsul-phonyl, C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylamino-carbonyl or di-(C1-C4-alkyl)-amino-carbonyl), C3-C6-alkenyl (which is optionally substituted by fluorine, chlor-ine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cyclo-alkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substituted by fluorine, chlor-ine, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl), benzhydryl or phenyl (which is optionally substituted by fiuorine, chlorine, nitro, cyano, C1-C4-alkyl, trifluoro-methyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C4-alkylthio, trifluoromethylthio or C1-C4-alkoxy-carbonyl), R5 and R6 furthermore represent phenyl or phenoxy, C1-C4-alkylcarbonylamino, C1-C4-alkoxycar-bonylamino, C1-C4- alkylamino-carbonylamino, di-(C1-C4-alkyl)-amino-carbonylamino, or the radical -CO-R9, where R9 represents C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkylthio, amino, C1-C4-alkyl-amino, C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino (which are optionally substitu-ted by fluorine and/or chlorine), R5 and R6 furthermore represent C1-C4-alkylsulphonyl-oxy, di-(C1-C4-alky1)-aminosulphonylamino or the radical -CH=N-R10, where R10 represents C1-C6-alkyl optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, benzyl option-ally substituted by fluorine or chlorine, C3-C6-alkenyl or C3-C6-alkinyl optionally substituted by fluorine or chlorine, phenyl option-ally substituted by fluorine, chlor-ine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoro-methoxy or trifluoromethylthio, C1-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy optionally substituted by fluorine and/or chlorine, amino, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C4-alkoxy-carbonyl-amino, C1-C4-alkyl-sulphonylamino or phenylsulphonyl-amino optionally substituted by fluorine, chlorine, bromine or methyl, in which in addition R1 represents the radical , in which R11 represents hydrogen or C1-C4-alkyl, R12 and R13 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is option-ally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine), carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylsulphonyl or di-(C1-C4-alkyl)-aminosulphonyl; in which in addition R1 represents the radical , in which R14 and R15 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is option-ally substituted by fluorine and/or chlorine) or C1-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine); in which in addition R1 represents the radical , in which R16 and R17 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is option-ally substituted by fluorine and/or chlorine), C1-C4-alkenyl (which is option-ally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine), C1 C4-alkylthio, C1-C4-alkylsul-phinyl or C1-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), and di-(C1-C4-alkyl)-aminosul-phonyl, C1-C4-alkoxy-carbonyl, dimethyl-aminocarbonyl or dioxolanyl; in which in addition R1 represents the radical , in which R18 and R19 are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which is optionally substitu-ted by fluorine and/or bromine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkyl-thio,C1-C4-alkylsulphinyl or C1-C4-alklsul-phonyl (which is optionally substituted by fluorine and/or chlorine), or di-(C1-C4-alkyl)-aminosulphonyl; in which in addi-tion R1 represents the radical , in which R20 and R21 are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl (which is option-ally substituted by fluorine, chlorine, C1-C4-alkoxy and/or C1-C4-halogenoalkoxy), C1-C4-alkoxy (which is optionally sub-stituted by fluorine and/or chlorine), C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C1-C4-alkyl)-amino-sulphonyl or C1-C4-alkoxy-carbonyl, and Q1 represents oxygen, sulphur or the grouping N-Q2, where Q2 represents hydrogen, C1-C4-alkyl (which is optionally substituted by fluorine, chlor-ine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally sub-stituted by fluorine, chlorine, bromine or nitro), C1-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl;
in which in addition R1 represents the radical , in which R22 and R23 are identical or different and represent hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxycarbonyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, Q3 represents sulphur or the grouping N-R24, where R24 represents hydrogen or C1-C4-alkyl; in which in addition R1 represents the radical , in which R25 represents hydrogen, C1-C4-alkyl, phenyl or (iso)quinolinyl, R26 represents hydrogen, halogen, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or C1-C4-alkoxy-carbonyl and R27 represents hydrogen, halogen or C1-C5-alkyl; in which in addition R1 represents the radical , in which R28 represents hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy-carbonyl; in which in addition R1 represents the radical , in which R29 represents C1-C4-alkyl and R30 represents C1-C4-alkyl, in which in addition R1 represents the radical , in which R31 represents hydrogen or methyl, in which in addition R2 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, bis-(C1-C2-alkoxy)-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, dimethylamino or diethylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, fluorine, chlorine, bromine, cyano, methyl, formyl, acetyl, meth-oxcarbonyl or ethoxycarbonyl, and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, bis-(C1-C2-alkoxy)-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4,-alkylsulphinyl, C1-C4,-alkylsulphonyl, C1-C4-alkylamino, dimethylamino or diethylamino.
in which in addition R1 represents the radical , in which R22 and R23 are identical or different and represent hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxycarbonyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, Q3 represents sulphur or the grouping N-R24, where R24 represents hydrogen or C1-C4-alkyl; in which in addition R1 represents the radical , in which R25 represents hydrogen, C1-C4-alkyl, phenyl or (iso)quinolinyl, R26 represents hydrogen, halogen, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or C1-C4-alkoxy-carbonyl and R27 represents hydrogen, halogen or C1-C5-alkyl; in which in addition R1 represents the radical , in which R28 represents hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy-carbonyl; in which in addition R1 represents the radical , in which R29 represents C1-C4-alkyl and R30 represents C1-C4-alkyl, in which in addition R1 represents the radical , in which R31 represents hydrogen or methyl, in which in addition R2 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, bis-(C1-C2-alkoxy)-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, C1-C4-alkylamino, dimethylamino or diethylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents hydrogen, fluorine, chlorine, bromine, cyano, methyl, formyl, acetyl, meth-oxcarbonyl or ethoxycarbonyl, and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, bis-(C1-C2-alkoxy)-C1-C2-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C4-alkylthio, C1-C4,-alkylsulphinyl, C1-C4,-alkylsulphonyl, C1-C4-alkylamino, dimethylamino or diethylamino.
3. A sulphonated azinyliminoheteroazole according to claim 1, in which A represents nitrogen or the grouping C-A1, in which A1 represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl, trifluoromethyl, di-chloromethyl, trichloromethyl, chlorodifluoro-methyl, fluorodichloromethyl, methylthio, ethylthio, propylthio, butylthio or phenyl, D represents nitrogen or the grouping C-D1, in which D1 represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, difluoromethyl trifluoromethyl, di-chloromethyl, trichloromethyl, chlorodifluoro-methyl, fluorodichloromethyl, methylthio, ethylthio, propylthio, butylthio or phenyl, (with the proviso that A and D do not both simultaneously represent nitrogen), E represents oxygen or sulphur, R1 represents the radical , in which R5 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C1-C3-alkylthio, C1-C3-alkyl-sulphinyl, C1-C3-alkylsulphonyl, dimethylamino-sulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C1-C3-alkoxy-carbonyl and R6 represents hydrogen, fluorine or chlorine; in which in addition R1 represents the radical , in which R11 represents hydrogen, R12 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and R13 represents hydrogen, fluorine or chlorine; in which in addition R1 represents the radical , in which R represents C1-C4-alkyl, or R1 represents the radical , in which R represents C1-C4-alkyl, or R1 represents the radical , in which R28 represents hydrogen, chlorine, methyl, ethyl, methoxycarbonyl or ethoxycarbonyl;
in which in addition R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents, hydrogen, fluorine, chlorine or methyl and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
in which in addition R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen or a CH grouping, Y represents nitrogen or the grouping C-R3, in which R3 represents, hydrogen, fluorine, chlorine or methyl and Z represents nitrogen or the grouping C-R4, in which R4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
4. A compound according to claim 1, wherein such compound is 2-(4,6-dimethylpyrimidin-2-yl-imino)-3-(2-methoxycarbonyl-phenylsulphonyl)-2,3-dihydro-1,3, 4-thiadiazole of the formula
5. A compound according to claim 1, wherein such compound is 2-(4,6-dimethylpyrimidin-2-yl-imino)-3-(2-chloro-phenylsulphonyl)-2,3-dihydro-1,3, 4-thiadiazole of the formula
6. A compound according to claim 1, wherein such compound is 2- (4-methyl-6-methoxy-pyrimidin-2-yl-imino)-3-(2-methoxycarbonyl-phenylsulphonyl)-2,3-dihydro-1,3, 4-thiadiazole of the formula
7. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
8. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a solid diluent or carrier, a liqui-fied normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.
9. A method of combating weeds which comprises apply-ing to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6.
10. A method of combating weeds which comprises apply-ing to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound accord-ing to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
11. A method of combating weeds which comprises apply-ing to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
13. A method of combating weeds which comprises apply-ing to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a pre-emergence herbicide.
14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a post-emergence herbicide.
15. A method of combating weeds which comprises apply-ing to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultiva-tion at a rate of between 0.01 and 10 kg/ha.
16. A method of combating weeds which comprises apply-ing to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultiva-tion at a rate of between 0.05 and 5 kg/ha.
17. A process for preparing a compound of formula I
as defined in claim 1, which process comprises reacting an azinylamino-heteroazole of the general formula (II) (II) in which A, D, E, R2, X, Y and Z are as defined in claim 1, with a sulphonyl halide or sulphonic anhydride of the general formula (III) R1-SO2-Q (III) in which R1 is as defined in claim 1, and Q represents fluorine, chlorine, bromine or the grouping -O-SO2-R1, in which R1 has the abovementioned meanings.
as defined in claim 1, which process comprises reacting an azinylamino-heteroazole of the general formula (II) (II) in which A, D, E, R2, X, Y and Z are as defined in claim 1, with a sulphonyl halide or sulphonic anhydride of the general formula (III) R1-SO2-Q (III) in which R1 is as defined in claim 1, and Q represents fluorine, chlorine, bromine or the grouping -O-SO2-R1, in which R1 has the abovementioned meanings.
18. An azinylamino-heteroazole of the formula (II) in which A, D, E, X, Y, Z and R2 are as defined in claim 1.
19. A process for preparing a compound of formula II as defined in claim 18, which process comprises reacting an aminoheteroazole of the general formula (IV) (IV) in which A, D and E are as defined in claim 18, with an azine of the general formula (V) (V) in which R2, X, Y and Z are as defined in claim 18 and Q4 represents halogen or alkylsulphonyl, or reacting a heteroazole of the general formula (VI) (VI) in which A, D and E have the abovementioned meanings and Q5 represents halogen or alkylsulphonyl, with an amino-azine of the general formula (VII) (VII) in which R2, X, Y and Z have the abovementioned meanings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3905763A DE3905763A1 (en) | 1989-02-24 | 1989-02-24 | SULFONYLATED AZINYLIMINOHETEROAZOLES, METHODS AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
| DEP3905763.1 | 1989-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010650A1 true CA2010650A1 (en) | 1990-08-24 |
Family
ID=6374856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002010650A Abandoned CA2010650A1 (en) | 1989-02-24 | 1990-02-22 | Herbicidal sulphonylated azinyliminoheteroazoles |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0384250A2 (en) |
| JP (1) | JPH02264775A (en) |
| AU (1) | AU4988190A (en) |
| BR (1) | BR9000865A (en) |
| CA (1) | CA2010650A1 (en) |
| DE (1) | DE3905763A1 (en) |
| ZA (1) | ZA901388B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020027635A (en) * | 1999-09-10 | 2002-04-13 | 폴락 돈나 엘. | Tyrosine kinase inhibitors |
| ES2255621T3 (en) | 2001-06-22 | 2006-07-01 | MERCK & CO., INC. | THYROSINE KINASE INHIBITORS. |
| US6872724B2 (en) | 2002-07-24 | 2005-03-29 | Merck & Co., Inc. | Polymorphs with tyrosine kinase activity |
| KR102328682B1 (en) * | 2018-08-27 | 2021-11-18 | 주식회사 대웅제약 | Novel heterocyclicamine derivatives and pharmaceutical composition comprising the same |
-
1989
- 1989-02-24 DE DE3905763A patent/DE3905763A1/en not_active Withdrawn
-
1990
- 1990-02-10 EP EP90102642A patent/EP0384250A2/en not_active Withdrawn
- 1990-02-16 AU AU49881/90A patent/AU4988190A/en not_active Abandoned
- 1990-02-20 JP JP2037509A patent/JPH02264775A/en active Pending
- 1990-02-22 CA CA002010650A patent/CA2010650A1/en not_active Abandoned
- 1990-02-22 BR BR909000865A patent/BR9000865A/en unknown
- 1990-02-23 ZA ZA901388A patent/ZA901388B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3905763A1 (en) | 1990-09-06 |
| BR9000865A (en) | 1991-02-13 |
| AU4988190A (en) | 1990-08-30 |
| EP0384250A2 (en) | 1990-08-29 |
| JPH02264775A (en) | 1990-10-29 |
| ZA901388B (en) | 1990-11-28 |
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