CA2051894C - Substituted 5-alkoxy-1,2,4-triazol-3-(thi)ones - Google Patents
Substituted 5-alkoxy-1,2,4-triazol-3-(thi)onesInfo
- Publication number
- CA2051894C CA2051894C CA002051894A CA2051894A CA2051894C CA 2051894 C CA2051894 C CA 2051894C CA 002051894 A CA002051894 A CA 002051894A CA 2051894 A CA2051894 A CA 2051894A CA 2051894 C CA2051894 C CA 2051894C
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- methyl
- alkyl
- chain
- atoms
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
Herbicidal 5-alkoxy-1,2,4-triazol-3-(thi)ones of the gerneral formula (see fig. I) (in which the radicals R1, R2, R3, X and Y have the meanings given in the description), processes for their preparation, and their use as herbicides, and also new intermediates of the formula (II) (see fig. II)
Description
The invention relates to new substituted 5-alkoxy-1, 2, 4 -triazol-3- ( thi ) ones, a plurality of several processes, and also new intermediates for their preparation, and their use as herbicides.
It has been disclosed that certain substituted triazolones such as, for example, 4-amino-5-methyl-2-phenylaminocarbonyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one, have herbicidal properties (cf. EP-A 283,876, EP-A 294,666, EP-A 298,371). However, the herbicidal activity of these c~ ;~ul~ds is not entirely satisfactory in all f ields of application .
New substituted 5-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula ( I ) X Y
Rl_NH_C NJ~N R2 ~ I ) o-R3 in which Rl represents alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, CyAnO~A~ 1 kyl ~
hydroxyalkyl, alkoxyalkyl, alkox i i ~oalkyl, alkoxy-carbonylalkyl, alkoxycarbonylalkenyl, alkylr i nOA 1 kyl or dialkylaminoalkyl, or represents in each case optionally substituted cycloalkyl, Le A 2î 918 - 1 -~ .. 7 ~ cycloalkylalkyl, cycloAlkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclyl-alkyl, or represents alkoxy, alkenyloxy or alkinyl-oxy, or represents in each case optionally ~ub-stituted aralkyl, aryloxyalkyl, aralalkenyl, aryl-alkinyl, aroyl, aryl, aralkyloxy or aryloxy.
R2 represents alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halog~nn~lkinyl, alkoxyalkyl, cyanoalkyl, alkoxy, cycloalkyl or cycloalkylalkyl, R3 represents alkyl, alkenyl, alkinyl, halogeno~lkyl, halogenoalkenyl, halog~no~lki nyl, alkoxyalkyl or cyanoalkyl, X represents oxygen or sulphur and Y represents oxygen or sulphur, have now been found.
Furthermore, it has been found that the new substituted S-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula (I) are obtained when (a) 5-alkoxy-1,2,4-triazol-3-(thi)ones of the ~eneral fo l~ (II) r ~ H-NJ~N-R2 ( I I ) ,~o - R3 Le A 27 918.- - 2 -2 ~
in which R2, R3 and Y have the abov~ -ntioned ,-ningt are reacted with i80 ( thio)cyanates of the general formula (III) R1-N=C=X (III) in which R1 and X have the abov. -ntioned -~nings, if appropriate in the presence of a diluent and if applup~iate in the presence of a basic reaction a~-Yi1i~ry, or when (b) 5-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula (II) y H-N ~ N-R2 (II) ~-R?
in which RZ, R3 and Y have the abov~ ~ntioned --ning lS are reacted with reactive (thio-)carbamates of the general formula (IV) Le A 27 918 - 3 -R1_~ H-C-O-R4 ( IV
in which R1 and X have the abov. ?.~tioned -~nin~ and R4 represents alkyl, aralkyl or aryl, if appropriate in the presence of a diluent and if appropriate in the presence of a basic reaction a~ ry~ or when (c) 5-alkoxy-1,2,4-triazol-3-(thi)one derivatives of the general fo 1~ (V) x Y
R4 - O - C - NJ~'N - R2 ( V ) ~==I~o - R3 in which R2, R3, X and Y have the abov. -ntioned --nin~and R4 represents alkyl, aralkyl or aryl, are reacted with amino compounds of the general Le A 27 918 - 4 -r,,~"~
formula (VI) Rl-NH2 (VI) in which Rl has the abov -~tioned g~ning~
if appropriate in the presence of a diluent and if appropriate in the presence of a basic reaction auxiliary.
Finally, it has been found that the new substituted S-alkoxy-1,2,4-triazol-3-lthi)ones of the general formula (I) are distinguished by powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal ac~vity thanthe compou~d 4-amino-5-methyl-2-phenylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, which is known.
Formula (I) provides a general definition of the sub-stituted 5-alkoxy-1,2,4-triazol-3-(thi)ones according to the invention. Preferred compounds of the formula (I) are those in which Rl represents in each case straight-chain or br~A-n~hed alkyl having 1 to 18 cArhon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoAlkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halog~noAlk~nyl or halogenoalkinyl, each of which Le A 27 91B - 5 -2 ~
has 2 to 8 carbon atoms and 1 to 15 or 13 identical or different halogen atoms, cyanoalkyl having 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, alkoxyalkyl, S alkoYi inoalkyl, alkoxycarbonylalkyl or alkoxy-carbonylalkenyl, each of which has up to 6 carbon atoms in the individual alkyl or alkenyl moieties, alkyl; 1 noA lkyl or dialkylaminoalkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, or represents cycloalkyl, cycloalkylalkyl, cyclo~lkPnyl or cycloalkenylalkyl, each of which has 3 to 8 carbon atoms in the cycloalkyl or cyclo-alkenyl moiety and if appropriate 1 to 6 carbon atoms in the alkyl moiety and each of which is optionally monosubstituted or polysubstituted by identical or different substituents, the following being selected as preferred substituents in the cyclic and optionally in the aliphatic moiety:
halogen, cyano, and in each case straight-chain or br~nch~ alkyl or halogenoalkyl, each of which has l to 4 carbon atoms and if a~pL~pliate 1 to 9 identical or different halogen atoms, or in each case divalent A 1 k~n~ i yl or ~l keneA i yl ~ each of which has up to 4 carbon atoms; R1 furthp ,~e represents heterocyclylalkyl which has l to 6 carbon atoms in the straight-chain or branched alkyl moiety and 1 to 9 carbon atoms as well as 1 to 3 hetero atoms - in particular nitrogen, oxygen and/or sulphur - in the heterocyclyl moiety and each of which is optionally monosubstituted or Le A 27 918 - 6 -polysubstituted by identical or different substit-uents, the following being selected as preferred substituents: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, S alkylthio, halog~nsAlkyl~ halogenoalkoxy, halogeno-alkylthio or alkoxycarbonyl, each of which has 1 to S carbon atoms and if appropriate 1 to 9 identical or different halogen atoms; Rlfurthermore represents in each case straight-chain or branched alkoxy having 1 to 8 carbon atoms, alkenyloxy having 2 to 8 carbon atoms or alkinyloxy having 2 to 8 carbon atoms, and finally represents aralkyl, aryloxyalkyl, arylalkenyl, arylakinyl, aralkyloxy, aryloxy, aroyl or aryl, each of which has 6 or lO carbon atoms in the aryl moiety and if appropriate up to 8 carbon atoms in the alkyl, alkenyl or alkinyl moiety, and each of which is optionally monosubstituted or polysub-stituted by identical or different substituents, suitable aryl substituents in each case being:
halogen, cyano, nitro, hydroxyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, halog~noAlkyl, halogenoalkoxy, halogenoalkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkyl-sulphinyl, halog~noAlkylsulphonyl, alkanoyl or alkoxycArhnnyl, each of which has 1 to 6 carbon atoms and if appropriate 1 to 9 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms and phenoxy, and suitable optibnal alkyl substituents being: halogen or cyano, R2 represents in each case straight-chain or brAn~h~
Le A 27 918 - 7 -r ~
- alkyl having 1 to 8 carbon atom~, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoAlkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl having 2 to 8 carbon atoms and 1 to lS identical or differen~ halogen atoms, halogeno-alkinyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl or alkoxy, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, cyanoalkyl having 1 to 8 carbon atoms, or representR cycloalkylalkyl or cycloalkyl, each of which has 3 to 7 carbon atoms in tha cycloalkyl moiety and if appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl lS moiety, R3 represents in each case straight-chain or br~n~he~
alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halog~no~lkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogeno~lk~nyl having 2 to 8 carbon atoms and 1 to 15 identical or different halogen atoms, halogeno-alkinyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl having 1 to 6 c~rbQn atoms in each of the individual alkyl moieties, or represents cyanoalkyl having 1 to 8 carbon atoms, X represents oxygen or sulphur and Le A 27 918 - 8 -j ? ..r.
- Y repre~ent~ oxygen or sulphur and halogen in the substitution pattern~ mentioned in the case of R1, R2 and R3 represents fluorine, chlorine, bL~ i ne and iodine.
Particularly preferred compouncls of the fo- 1~ (I) are those in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, 8-or t-butyl, in each case straight-chain or brAn~h~
pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl, or represents allyl, propenyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl, propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl, or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9-lS identical or different halogen atoms, in particular fluorine, chlorine or bLr ine~ or represents in each case straight-chain or branched halogenoalkenyl or halogeno2~l ki nyl ~ each of which has 3 to 5 carbon atoms and 1 to 3 halogen atoms, in particular fluorine or chlorine, or represents in each case straight-chain or branched cyAnoalkyl having 1 to 4 ~2~r~o~ atoms in the alkyl moiety, hydroxyalkyl having 1 to 6 carbon atoms and 1 to 3 hydroxyl g.o~ps, alkoxyalkyl, ~1 ko~i inoalkyl~ alkoxy-carbonylalkyl or alkoxycarbonylalkenyl, alky7 2 i noA 1 kyl or dialkylaminoalkyl, each of which has up to 4 carbon atoms in the individual alkyl or Le A 27 918 - 9 -~ Q ~ ~L ~ X
~ alkenyl moietie~, or represents cyclopropyl, cyclo-propylmethyl, cyclopropylethyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclo-pentylmethyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohe~Pnylmethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, the following being selected as particularly preferred sub-stituents in the cyclic and if appropriate in the aliphatic moiety: fluorine, chlorine, bL~ in~
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyano, ~ethAne~iyl, e~ h~n~iyl, butanediyl or butadienediyl; Rl furthermore represents hetero-cyclylmethyl, heterocyclylethyl or heterocyclyl-propyl, each of which is optionally monosubstituted to trisubstituted in the heterocyclyl moiety by identical or different substituents, suitable~
heterocycles in each case beinq:
N--LN ~ - N~ - N~
Z ; N'Z
~ -N O or -N NH
- N~
where Z in each case represents oxygen or sulphur Le A 27 918 - 10 -and where the followin~ are selected as particularly preferred substituents:
fluorine, chlorine, bL~ ine~ cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methy:Lthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio;
R1furthermore represents iII each case straight-chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having 3 to 6 carbon atoms or alkinyloxy having 3 to 6 carbon atoms, or represents benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenyl-pentyl, phenylhexyl, phenylheptyl, phenylcyano-methyl, phenylcyanoethyl, phenylcyanopropyl, phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxy-butyl, phenylethinyl, benzyloxy, phenylethyloxy, phenoxy, benzoyl, phenyl or naphthyl, if appropriate straight-chain or branched, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents in each case being: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylsulphinyl, methyl-sulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, cyclohexyl and phenoxy, RZ represents methyl, ethyl, n- or i-propyl, n-, i-, s-or ~-butyl, n- or i-pentyl, n- or i-hexyl, or represents allyl, propargyl, methoxy, ethoxy, Le A 27 918 ~ methoxymethyl, ethoxymethyl, methoxyethyl or ethoxy-ethyl, or represents str~ight-chain or ~ranched haloge~o~lkyl, halog~noAl kenyl and halogeno~lkinyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or b~ ne~ or represents cyclopentyl, cyclohexyl, cyclopropyl, cyclopropylmethyl, cyclo-pentylmethyl, cyclohexylmethyl or cyclohexylethyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n-, i-, s- or t-pentyl~ n- or i-hexyl, or represents allyl, propargyl, methoxyethyl, ethoxyethyl, fluoroethyl, chloroethyl, fluoropropyl, chloropropyl or cyanoethyl, X represents oxygen or sulphur and 15 Y represents oxygen or sulphur.
Very particularly preferred c~ ~unds of the formula (I) are those in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n-, i-, s- or t-pentyl, n-, i-, s- or t-hexyl, propargyl, n- or i-butinyl, n- or i-pentinyl, or represents straight-chain or branched halog~nn~lkyl having 1 to 4 carbon atoms and 1 to 4 identical or different halogen atoms, in particular fluorine and chlorine, or represents cyanomethyl, cyanoethyl or n- or i-cyanopropyl, or represents Le A 27 918 - 12 -cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclo-pentylmethyl, cyclohexyl o:r cyclohexylmethyl, each of which is optionally monosubstituted to trisub-stituted by identical or different substituents, or represents phenyl, benzyl or phenylethyl, each of which is optionally monosubstituted to trisub-stituted by identical or different substituents from the series comprising fluorine, chlorine, bl~ inP~
methyl, ethyl and/or trifluoromethyl, or represents in each case straight-chain or branched phenyl-propyl, phenylbutyl, phenylpentyl or phenylhexyl, or represents morpholinyl-Cl-C4-alkyl, R2 represents methyl, ethyl, n-, i- or cyclopropyl, n-, i-, s- or t-butyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n- or i-pentyl, X represents oxygen and Y represents oxygen.
Examples of the compounds of the formula (I) according to the invention are listed in Table 1 below.
Rl-NH-C-N ~ N-~o-R3 Le A 27 918 - 13 -~p3 Table 1: Examples of the compoundR of the formula (I) Rl R2 R3 X Y
i C3H7 CH3 CH3 0 0 CF3-ctcH3)2 CH3 C2H5 ~ ~
F-CH2-C(cH3)2 CH3 C2H5 ~ ~
C2H5-C(cH3)2 CH3 CH3 0 0 C3H7-C(cH3)Z CH3 CH3 0 0 i-C3H7-C(CH3)2 CH3 CH3 0 0 (CH3)2- CH3 CH3 0 0 H2-C(cH3)Z CH3 CH3 0 0 /~
(CH2)2-C(cH3)2 CH3 CH3 0 0 CHZ)2-C(CH3)2 CH3 CH3 O O
H2-C(cH3)2 CH3 CH3 0 0 H(CH3)- CH3 CH3 0 0 ~ (CH3)2- CH3 C2H5 ~ ~
CH3 ~ H2-cHz-c(cH3)z CH3 CH3 0 0 Le A 27 918 - 14 -~ If, for example, 5-ethoxy-4-ethyl-2,4-dihydro-3H-1,2,4-triazole-3-thione and isopLo~yl~isocyanate are used as starting substances, the course of the reaction of process (a) according to the invention can be S illustrated by the following e~lation:
(CH3)zCH-N=C=O ~ H-N~N-c2Hs N==L~O - C 2H5 O s (CH3)2cH-NH-c-N ~ N-C2HS
If, for example, 5-isopropoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 0-Methyl-~-tert.-butylthio-cAr~- -te are used as starting substances, the course of the reaction of process tb) according to the invention can be illustrated by the following equation:
s o (CH3)3C-NH-C-O-cH3 H-N N-CH3 ~ O-CH(CH3)z ~ S O
' (CH3)3C-NH-C-N N-CH3 -HOCH3 l l N===l~O-CH(CH3)z Le A 27 918 - lS -~ 3 If, for example, 4-isopropyl-5-methoxy-2-ph~no~y-carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one and cyclo-hexylamine are used as starting substances, the course of the reaction of process (c) according to the invention S can be illustrated by the follo~inq equation:
o o ~3NHz ~ ~-C-N N- CH ( CH3 ) 2 O O
<3NH - C - 7J~N - CH ( CH 3 ) 2 - H~ N=i~o - Cl 1~
Formula (II) provides a general definition of the 5-alkoxy-1,2,4-triazol-3-(thi)ones to be used as starting substances in processes (a) and (b) according to the invention for the preparation of compounds of the formula (I).
In formula (II), R2, R3 and Y preferably, or in par-ticular, have those ~-ni ngs which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or as particularly preferred, for RZ, R3 and Y.
Examples of the starting substances of the formula (II) are listed in Table 2 below.
irJ ~ ~7 ~
N ~ 2 H- N-R (II) N===l~o-R3 Table 2: Examples of the starting substances of the formula (II) CH3 CZH5 ~
CH3 C3H? S
CH3 CH(CH3)2 0 CH3 CH(CH3)2 CH3 -cH2-cH=cH2 0 CH3 -cH2-cH-cH2 S
C2H5 CH(CH3)2 0 C2H5 -CH2-CH=CH2 0 C2H5 CH(CH3)2 S
C2H5 -CHz-CH=CH2 S
Le A 27 91e - 1? -The starting substances of the formula (II) are known in some cases (cf. J. Chem. Soc C 1967, 2700-2704; J.
Heterocycl. Chem. 15 (1978), 377-384).
Those compounds of the general fo 1A (II) in which Y
represents oxygen and R2 and R3 have the abov --tioned -~nings are new and are a subject of the present patent application.
The new 5-alkoxy-1,2,4-triazol-3-ones (II, Y = O) are obtained when hydrazinoformic esters of the general formula (VII) H2N-NH-Co-o-R4 (VII) in which R4 has the abov ~ntioned -~n i ng are reacted with alkyliminocarboxylic diesters of the general fo 1 A (VIII) ,o-R3 R -N=C~ (VIII) o -R3 in which R2 and R3 have the abov~ tioned ~~ning, Le A 27 918 -- 18 -~ if appropriate in the presence of a diluent such as, for example, o-dichlorobenzene, at temperatures between O~C
and 200~C, preferably between 50~C and lS0~C (cf. the Preparation Examples).
The starting substances of the formulae (VII) and (VIII) are known chemicals.
Formula (III) provides the general definition of the iso(thio)cyanates to be used as starting substances in process (a) according to the invention for the prepara-tion of compounds of the formula (I).
In formula (III), R1 and X preferably, or in particular, have those --n i ngs which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being-lS preferred, or as particularly preferred, for R1 and X.
The starting substances of the formula (III) are known chemicals for organic synthesis.
Formula (IV) provides a general definition of the reac-tive (thio)cArh- -tes to be used as starting substances in process (b) according to the invention for the preparation of compounds of the formula (I).
In formula (IV), Rl and X preferably, or in particular, have those -~n i ngs which have already been mentioned above in connection with the description of the compounds Le A 27 918 - 19 ~
~ ~ '';d ~ 3~ , - of the formula (I) according to the invention as being preferred, or as particularly preferred, for R1 and X;
R4 preferably represents methyl, ethyl, phenyl or benzyl.
The starting substances of the formula (IV) are known chemicals for organic synthesis.
Formula (V) provides a g~neral definition of the 5-alkoxy-1,2,4-triazol-3-(thi)one derivatives to be used as starting substances in process (c) according to the invention for the preparation of compounds of the formula (I).
In formula ~V), RZ, R3, X and Y preferably, or in par-ticular, have those - nings which have already been ~ention~ above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or as particularly preferred, for R2, R3, X and Y;
R4 preferably represents methyl, ethyl, phenyl or benzyl.
The starting substances of the formula (V) were hitherto not known from the literature and are a subject of the present patent application.
The new 5-alkoxy-1,2,4-triazol-3-(thi)one derivatives of Le A 27 918 - 20 -2~18~4 the general formula ~V) are obta:ined when S-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula (II) H-NJ~N-R2 ( I I ) ~==I~o - R3 in which R2, R3 and Y have the abov. I~ntioned --nings are reacted with chlorolthio)formic esters of the general formula ~IX) R4-0-C-Cl ( IX) in which R4 and X have the abov. -ntioned ~ nin~, if appropriate in the presence of a diluent such as, for example, tetrahydrofuran, and if appropriate in the presence of an acid acceptor such as, for example, potassium tert-butylate, at temperatures between -20DC
and +100 DC .
Le A 27 918 - 21 -Formula (VI) provides a general definition of the amino cl r"~unds fur~he -re to be used as starting substance~
in proce6s (c) according to the invention for the pre-paration of compounds of the formula (I).
S In formula (~I), R1 preferably, or in particular, ha~ the -sning which has already been mentioned above in connec-tion with the description of the compounds of the formula (I) according to the invention as being preferred, or as particularly preferred, for R1.
The starting substances of the formula (VI) are known chemicals for organic synthesis.
Processes (a), (b) and (c) according to the invention for the preparation of the new compounds of the formula (I) are preferably carried out in each case using diluents.-Suitable diluents for this purpose are virtually allinert organic solvents. These preferably include aliphatic and aromatic, option~lly halogenated hydro-carbons such as pentane, h~Ane~ heptane, cycloh~x~ne, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloro-form, carbon tetrachloride, chlorobenzene and o-dichloro-benzene, ethers such as diethyl ether 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 27 918 - 22 -propionitrile, amides such as, for example, dimethyl-formamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and h~r ~ ~hylphosphoric triamide.
If appropriate, processes (a), ~b) and (c) according to the invention are in each case carried out in the presence of a basic reaction auxiliary. Suitable sub-stances which are employed are preferably basic organic nitrogen compounds. These include, for example, tri-methyl i~e, triethylamine, tripropylr in~ tributyl-amine, diisopLopylamine, dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethylbenzylamine, pyridine, 4-dimethyl-amino-pyridine,1,5-~ hicyclo-(4,3,0]-non-5-ene(DBN), 1,8-~ i ~ 7 ~hiCyC 10 r s, 4,0)-undec-7-ene (DBU) and 1,4-diazab-icyclo-t2,2,2]-octane (DABCO).
When carrying out processes (a), (b) and (c) according to the invention, the reaction temperatures can be varied in each case in a substantial range. In general, the proces-ses are carried out at temperatures between -20~C and +150~C, preferably at temperatures between 0~C and 100~C.
In general, processes (a), (b) and (c) according to the invention are carried out under atmospheric pressure.
However, it is also possible to carry out the processes under increased or reduced pressure.
For carrying out processes (a), (b) and (c) according to the invention, the starting substances required in each Le A 27 918 - 23 - - -- case are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components employed in each case in a larger excess.
In general, the reactions are carried out in a ~uitable diluent in the presence of a ~asic reaction a~Yili~ry~
and the reaction mixture is stirred for several hour3 at the particular temperature required. Working-up in the processes according to the invention is carried out in each case by customary methods.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying 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 un-desired. Whether the substances according to the inven-tion act as total or selective herbicides depends essen-tially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
DicotYledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, seg~AniA, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, ~otala, ~in~ernia~ T-- i , Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Le A 27 918 - 24 -~ ~,J i 3 Ranunculus and Taraxacum.
DicotYledon cultures of the qenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, ~leusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Aylo~on~ Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, I~ch~ , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the qenera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, ~n~n~C ~ Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same -nner to other plants.
The compounds are suitable, dep~n~i ng on the concentra-tion, 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 c~ -unds can be employed for combating weeds in peren-nial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, hAn~n~ plantations, coffee plantations, tea Le A 27 918 - 25 -$ eJ ',I~t plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective combating of weeds in an~ual cultures.
S ~he compounds of the formula (I) according to the inven-tion are suitable for selectively combating monocotyledon and dicotyledon weeds, mainly in monocotyledon cultures, by the pre- and the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emul6ions, wettable powders, ~uspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concen-trates, natural and synthetic materials Lmpregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known -nn~rl for example by i~i ng the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsify ing 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 suitable in the main: aromatics, such as xylene, toluene, or alkyl-naphthalenes, chlorinated aromatics and chlorinated Le A 27 918 - 26 - -aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocA~ho~R, such as cycloh~Ane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as ~heir ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cycloh~Anone, strongly polar solvents, such as dimethylfo ~ide and dimethyl sulph-oxide, as well as water.
As solid carriers there are suitable: for example am-monium salts and ground natural minerals, such as kao-lins, clays, talc, chalk, quartz, attapulgite, montmoril-lonite 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, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize 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, polyoxy-ethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products;
as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Le A 27 918 - 27 -CA 020~1894 1998-12-10 Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, 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 dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds, the active compounds according to the invention, as such or in the form of their formula-tions, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, such as, for example, l-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione(A~ ~Y~IONE*) or N-(2-benzothiazolyl)-N,N'-dimethylurea(METABENZTHIAZURON*) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one(METAMITRON*) for combating weeds in *Trade-mark CA 020~1894 1998-12-10 sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN*) for combating weeds in soya beans; furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D*); 4-(2,4-dichlorophenoxy)-butyric acid (2,4-DB*); 2,4-dichlorophenoxypropionic acid (2,4-DP*); 2-chloro-2',6'-diethyl-N-methoxy-methylacetanilide (ALACHLOR*); methyl-6,6-dimethyl-2,4-dioxo-3-[1-(2-propenyloxyamino)-butylidene]-cyclohexanecarboxylic acid (ALLOXYDIM*); 4-amino-benzenesulphonyl methyl carbamate (ASULAM*); 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (ATRAZINE*); methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-methyl]-benzoate (BENSULFURON*); 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BENTAZONE*); 3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL*); N-(butoxymethyl)-2-chloro-N(2,6-diethylphenyl)-acetamide (BUTACHLOR*); 5-amino-4-chloro-2-phenyl-2,3-dihydro-3-oxy-pyridazine (CHLORIDAZONE*);
isopropyl N-(3-chlorophenyl)-carbamate (CHLORPROPHAM*); 2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON*); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON*); exo-1-methyl-4-(1-methylethyl)-2-(2-methylphenyl-methoxy)-7-oxabicyclo-(2,2,1)-heptane (CINMETHYLIN*); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID*); 2-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine (CYANAZINE*); N,S-diethyl-N-cyclohexyl-thiolcarbamate (CYCLOATE*); 2-[1-(ethoximino)-butyl]-3-hydroxy-5-[tetrahydro-(2H)-thiopyran-3-*Trade-mark CA 020~1894 1998-12-10 yl]-2-cyclohexane-1-one (CYCLOXYDIM*); 2-~4-(2,4-dichloro-phenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP*); 2-[(2-chlorophenyl)-methyl]-4,4-dimethylisoxazolidin-3-one (DIMETHAZONE*); S-ethyl N-N-di-n-propyl-thiocarbamidate (EPTAME*); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN*); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP*); 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP*); 1-methyl-3-phenyl-5-(3-trifluoro-methylphenyl)-4-pyridone (FLURIDONE*); [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its 1-methylheptyl ester (FLUROXYPYR*); 2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]-phenoxy}-propanoic acid or its ethyl ester (HALOXYFOP*); 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione (HEXAZINONE*); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-lH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ*); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL*); N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON*); (2-methyl-4-chlorophenoxy)-acetic acid (MCPA*); (4-chloro-2-methyl-phenoxy)-propionic acid (MCPP*);
N-methyl-2-(1,3-benzo-thiazol-2-yloxy)-acetanilide (MEFENACET*); 2-chloro-N-(2,6-dimethylphenyl)-N-[(lH)-pyrazol-l-yl-methyl]-acetamide (METAZACHLOR*); 2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide (METOLACHLOR*); 2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-*Trade-mark CA 020~1894 1998-12-10 amino]-sulphonyl}-benzoic acid or its methyl e~ter (METSULFURON*); S-ethyl N,N-hexamethlyenethiocarbamate (MOLINATE*); 1-(3-trifluoromethylphenyl)-4-methylamino-5-chloro-6-pyridazone (NORF~URAZON*); 4-(di-n-propylamino)-3,5-dinitrobenzenesulphonamide (ORYZA~IN*); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN*); 3-(ethoxycarbonylaminophenyl)-N-(3'-methylphenyl)-carbamate (PHENMEDIPHAM); 2-chloro-N-isopropylacetanilide (PROPACHLOR);
isopropyl N-phenyl-carbamate (PROPHAM*); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octylthiocarbonate (PYRIDATE*); ethyl 2-[4-(6-chloroquinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL*); 2-[1-(etho~Am;nQ)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM*); 2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine (SIMAZINE*); 2,4-bis-[N-ethylamino]-6-methylthio-1,3,5-triazine (SIMETRYNE*); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE*); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate (THIAMETURON*); S-[(4-chlorophenyl)-methyl] N,N-diethylthiocarbamate (THIOBENCARB*); S-(2,3,3-trichloroallyl) N,N-diisopropylthiocarbamate (TRIALLATE*); 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN*).
Surprisingly, some mixtures also show a synergistic action.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird *Trade-mark repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of - 31a -their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and gr~nul~.
They are used in the customary ~nn~r, for example by S watering, spraying, atomising 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 d~p~n~c essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 10 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Preparation Examples:
Example 1 o o Il a (CH3)~C-NH-C-N ~ N-CH3 . -CH3 Le A 27 918 - 32 -~ 3 A mixture of 1.3 g (0.01 mol) of 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 0.1 g of 1,8-diazabi-cyclo[5.4.0]undec-7-ene (DBU3, 1.0 g (0.01 mol) of tert-butyl isocyanate and 50 ml of acetonitrile is stirred for 12 hours at 20~C and subsequently concentrated under a water pump vacuum. The residue is taken up in methylene chloride, and the mixture is washed with wate~, dried with magnesium sulphate and filtered. The filtrate is concentrated under a water pump vacuum, the residue is brought to crystallisation by trituration with petroleum ether, and the product is isolated by filtration with suction.
1.4 g (61% Of theory) of 2-tert-butyl-amino-carbonyl-5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of lS melting point 167~C are obtained.
Other examples of the compounds of the formula (I) which can be prepared analogously to Example 1 and corresponding to the general description of the prepara-tion processes according to the invention are those listed in Table 3 below.
x Y
Rl-NH-C-N N_R2 ( I ) -R
Le A 27 918 - 33 -Table 3: Preparation examples of the compounds of the formula (I) No. R2 R3 X Y Melting ClCHzl- CH3 CH3 O ~ 153 3 H3C ~ CH2CH- C3H7 CH3 0 (oil) 4Cl ~ H2CH21 C3H7 CH3 o 0 (oil) SCl ~ H2CH21- CH3 C2H5 o (oil) Cl ~ IH3 (oil) 7 Cl ~ H2CH 1 H- CH3 C2HS ~ ~ (oil) Le A 27 918 - 34 -Table 3: continuation 5 Example Rl RZ R3 X r Melting No. ~ point (~C) 8~ H2~CH2CIH- CH3 C2H5 ~ (oil) 9H3C ~ HzCH2CH- CH3 C2H5 0 0 (oil~
o ~ H2CH2CIH- CH3 Cz~5 ~ (oil) 11 H3C ~ CH2lCH- CH3 C2H5 ~ ~ (oil) 12 Cl ~ H2CH - CIH- CH3 C2H5 o (oil) 3013 C1 ~ H2CH21CH- CH3 C2H5 ~ (oil) Le A 27 918 35 Table 3: continuation 5 Ex~nple Rl RZ R3 ~ point ( C) 14 ~ H3 ~ CH3 CH3 ~ ~ 166 15 ~ IH3 120 16 ~ C- CM3 CH3 o o 176 17 Cl ~ CH2CH2- CH3 CH3 0 ~ 130 18 Cl ~ H- CH3 CH3 ~ ~ 104 Cl CH3 19 ~ IH3 117 _5 CH3 Le A 27 918 - 36 -~ , . ~ . . . . .... . .
2 6~3 ~
Table 3: continuation Melting 5 Example Rl R2 R3 point ( C) H3C ~ H ~ CH3 CH3 0 ~100 . CH3 21 (CH3~3c CH3 C3H7 0 ~ 75 22 ClCH2C- CH3 C3H7 0 ~
23 ~ H2 1I H3 CH3 CH3 ~ ~142 24 H9C~-C- CH3 CH3 0 0135 25 H3C ~ H2CH2l- CH3 CH3 0 0106 Le A 27 918 ~ 37 ~ . . ...
Table 3: continuation No. R2 R3 ~ point ( C) ~CH3 26 ~ H2CH2CH2l CH3 CH3 00 137 27~ H211- CH3 CH3 0 0 131 28Cl ~ H2CH2C~ CH3 CH3 0 0 1 lB
29 F2CH ~ -C-C- CH3 CH3 0 0 82 30 (CH3)3c CH2-CH=CH2 CH3 0 0 87 Le A 27 918 - 38 -$ ~:
Startin~ substances of the formula (II):
Example tII-1) J~N
H-N l-C1~3 N~oCH3 In 100 ml of absolute o-dichlorobenzene, 50.2 g (0.33 mol) of phenyl hydrazinoformate and 36.6 g (0.33 mol, 93%) of ~rimethyl iminoc~hon~te are heated to 60~C, and the mixture is stirred for 2 hours, during which process a clear solution forms. ~his solution is heated to 120-C
in the course of two hours, during which process methanol distils off. A vacuum is applied carefully, during which process more methanol and finally phenol distil off. Upon further distillation, there is formed a fraction which solidifies in the receiver in crystalline form.
After recrystallisation from toluene, 7.0 g (0.054 mol, 16% of theory) of 4-methyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are obt~i n~ in the form of colour-less crystals of melting point 142-144~C.
Le A 27 918 - 39 -Use Examples:
In the Use Examples, the following compound (A) is used as c~ -rison substance:
o o ~ 11 11 ~NH - C - N~N - NH2 ~ A ) 4-amino~5-methyl-2-phenylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3 one 15(disclosed in EP-A 294,666).
~0 Le A 27 918 - 40 -ExamPle A
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of al~ylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound~
desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 1000 1 of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0~ = no action (like untreated control) 100% = total destruction In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds of Preparation Examples 1 and 2.
Le A 27 918 - 41 - -Example B
Prc ~ ?rgence test 5O1vent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the s~ated amount of solvent, the stated 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 development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction In this test, a powerful action against weeds combined with good tolerance by crop plants such as, for example, barley, is shown, for example, by the compound of Preparation Example 2.
It will be apprecia~dthat the instant sper;f;c~tion is set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the ~s~lL invention.
- Le A 27 918 - 42 -
It has been disclosed that certain substituted triazolones such as, for example, 4-amino-5-methyl-2-phenylaminocarbonyl-2, 4-dihydro-3H-1, 2, 4-triazol-3-one, have herbicidal properties (cf. EP-A 283,876, EP-A 294,666, EP-A 298,371). However, the herbicidal activity of these c~ ;~ul~ds is not entirely satisfactory in all f ields of application .
New substituted 5-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula ( I ) X Y
Rl_NH_C NJ~N R2 ~ I ) o-R3 in which Rl represents alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, CyAnO~A~ 1 kyl ~
hydroxyalkyl, alkoxyalkyl, alkox i i ~oalkyl, alkoxy-carbonylalkyl, alkoxycarbonylalkenyl, alkylr i nOA 1 kyl or dialkylaminoalkyl, or represents in each case optionally substituted cycloalkyl, Le A 2î 918 - 1 -~ .. 7 ~ cycloalkylalkyl, cycloAlkenyl or cycloalkenylalkyl, or represents optionally substituted heterocyclyl-alkyl, or represents alkoxy, alkenyloxy or alkinyl-oxy, or represents in each case optionally ~ub-stituted aralkyl, aryloxyalkyl, aralalkenyl, aryl-alkinyl, aroyl, aryl, aralkyloxy or aryloxy.
R2 represents alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halog~nn~lkinyl, alkoxyalkyl, cyanoalkyl, alkoxy, cycloalkyl or cycloalkylalkyl, R3 represents alkyl, alkenyl, alkinyl, halogeno~lkyl, halogenoalkenyl, halog~no~lki nyl, alkoxyalkyl or cyanoalkyl, X represents oxygen or sulphur and Y represents oxygen or sulphur, have now been found.
Furthermore, it has been found that the new substituted S-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula (I) are obtained when (a) 5-alkoxy-1,2,4-triazol-3-(thi)ones of the ~eneral fo l~ (II) r ~ H-NJ~N-R2 ( I I ) ,~o - R3 Le A 27 918.- - 2 -2 ~
in which R2, R3 and Y have the abov~ -ntioned ,-ningt are reacted with i80 ( thio)cyanates of the general formula (III) R1-N=C=X (III) in which R1 and X have the abov. -ntioned -~nings, if appropriate in the presence of a diluent and if applup~iate in the presence of a basic reaction a~-Yi1i~ry, or when (b) 5-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula (II) y H-N ~ N-R2 (II) ~-R?
in which RZ, R3 and Y have the abov~ ~ntioned --ning lS are reacted with reactive (thio-)carbamates of the general formula (IV) Le A 27 918 - 3 -R1_~ H-C-O-R4 ( IV
in which R1 and X have the abov. ?.~tioned -~nin~ and R4 represents alkyl, aralkyl or aryl, if appropriate in the presence of a diluent and if appropriate in the presence of a basic reaction a~ ry~ or when (c) 5-alkoxy-1,2,4-triazol-3-(thi)one derivatives of the general fo 1~ (V) x Y
R4 - O - C - NJ~'N - R2 ( V ) ~==I~o - R3 in which R2, R3, X and Y have the abov. -ntioned --nin~and R4 represents alkyl, aralkyl or aryl, are reacted with amino compounds of the general Le A 27 918 - 4 -r,,~"~
formula (VI) Rl-NH2 (VI) in which Rl has the abov -~tioned g~ning~
if appropriate in the presence of a diluent and if appropriate in the presence of a basic reaction auxiliary.
Finally, it has been found that the new substituted S-alkoxy-1,2,4-triazol-3-lthi)ones of the general formula (I) are distinguished by powerful herbicidal activity.
Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal ac~vity thanthe compou~d 4-amino-5-methyl-2-phenylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, which is known.
Formula (I) provides a general definition of the sub-stituted 5-alkoxy-1,2,4-triazol-3-(thi)ones according to the invention. Preferred compounds of the formula (I) are those in which Rl represents in each case straight-chain or br~A-n~hed alkyl having 1 to 18 cArhon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoAlkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halog~noAlk~nyl or halogenoalkinyl, each of which Le A 27 91B - 5 -2 ~
has 2 to 8 carbon atoms and 1 to 15 or 13 identical or different halogen atoms, cyanoalkyl having 1 to 8 carbon atoms, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, alkoxyalkyl, S alkoYi inoalkyl, alkoxycarbonylalkyl or alkoxy-carbonylalkenyl, each of which has up to 6 carbon atoms in the individual alkyl or alkenyl moieties, alkyl; 1 noA lkyl or dialkylaminoalkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, or represents cycloalkyl, cycloalkylalkyl, cyclo~lkPnyl or cycloalkenylalkyl, each of which has 3 to 8 carbon atoms in the cycloalkyl or cyclo-alkenyl moiety and if appropriate 1 to 6 carbon atoms in the alkyl moiety and each of which is optionally monosubstituted or polysubstituted by identical or different substituents, the following being selected as preferred substituents in the cyclic and optionally in the aliphatic moiety:
halogen, cyano, and in each case straight-chain or br~nch~ alkyl or halogenoalkyl, each of which has l to 4 carbon atoms and if a~pL~pliate 1 to 9 identical or different halogen atoms, or in each case divalent A 1 k~n~ i yl or ~l keneA i yl ~ each of which has up to 4 carbon atoms; R1 furthp ,~e represents heterocyclylalkyl which has l to 6 carbon atoms in the straight-chain or branched alkyl moiety and 1 to 9 carbon atoms as well as 1 to 3 hetero atoms - in particular nitrogen, oxygen and/or sulphur - in the heterocyclyl moiety and each of which is optionally monosubstituted or Le A 27 918 - 6 -polysubstituted by identical or different substit-uents, the following being selected as preferred substituents: halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, S alkylthio, halog~nsAlkyl~ halogenoalkoxy, halogeno-alkylthio or alkoxycarbonyl, each of which has 1 to S carbon atoms and if appropriate 1 to 9 identical or different halogen atoms; Rlfurthermore represents in each case straight-chain or branched alkoxy having 1 to 8 carbon atoms, alkenyloxy having 2 to 8 carbon atoms or alkinyloxy having 2 to 8 carbon atoms, and finally represents aralkyl, aryloxyalkyl, arylalkenyl, arylakinyl, aralkyloxy, aryloxy, aroyl or aryl, each of which has 6 or lO carbon atoms in the aryl moiety and if appropriate up to 8 carbon atoms in the alkyl, alkenyl or alkinyl moiety, and each of which is optionally monosubstituted or polysub-stituted by identical or different substituents, suitable aryl substituents in each case being:
halogen, cyano, nitro, hydroxyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, halog~noAlkyl, halogenoalkoxy, halogenoalkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkyl-sulphinyl, halog~noAlkylsulphonyl, alkanoyl or alkoxycArhnnyl, each of which has 1 to 6 carbon atoms and if appropriate 1 to 9 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms and phenoxy, and suitable optibnal alkyl substituents being: halogen or cyano, R2 represents in each case straight-chain or brAn~h~
Le A 27 918 - 7 -r ~
- alkyl having 1 to 8 carbon atom~, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoAlkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl having 2 to 8 carbon atoms and 1 to lS identical or differen~ halogen atoms, halogeno-alkinyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl or alkoxy, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, cyanoalkyl having 1 to 8 carbon atoms, or representR cycloalkylalkyl or cycloalkyl, each of which has 3 to 7 carbon atoms in tha cycloalkyl moiety and if appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl lS moiety, R3 represents in each case straight-chain or br~n~he~
alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halog~no~lkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogeno~lk~nyl having 2 to 8 carbon atoms and 1 to 15 identical or different halogen atoms, halogeno-alkinyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl having 1 to 6 c~rbQn atoms in each of the individual alkyl moieties, or represents cyanoalkyl having 1 to 8 carbon atoms, X represents oxygen or sulphur and Le A 27 918 - 8 -j ? ..r.
- Y repre~ent~ oxygen or sulphur and halogen in the substitution pattern~ mentioned in the case of R1, R2 and R3 represents fluorine, chlorine, bL~ i ne and iodine.
Particularly preferred compouncls of the fo- 1~ (I) are those in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, 8-or t-butyl, in each case straight-chain or brAn~h~
pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl, or represents allyl, propenyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl, propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl, or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9-lS identical or different halogen atoms, in particular fluorine, chlorine or bLr ine~ or represents in each case straight-chain or branched halogenoalkenyl or halogeno2~l ki nyl ~ each of which has 3 to 5 carbon atoms and 1 to 3 halogen atoms, in particular fluorine or chlorine, or represents in each case straight-chain or branched cyAnoalkyl having 1 to 4 ~2~r~o~ atoms in the alkyl moiety, hydroxyalkyl having 1 to 6 carbon atoms and 1 to 3 hydroxyl g.o~ps, alkoxyalkyl, ~1 ko~i inoalkyl~ alkoxy-carbonylalkyl or alkoxycarbonylalkenyl, alky7 2 i noA 1 kyl or dialkylaminoalkyl, each of which has up to 4 carbon atoms in the individual alkyl or Le A 27 918 - 9 -~ Q ~ ~L ~ X
~ alkenyl moietie~, or represents cyclopropyl, cyclo-propylmethyl, cyclopropylethyl, cyclobutyl, cyclo-pentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclo-pentylmethyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohe~Pnylmethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, the following being selected as particularly preferred sub-stituents in the cyclic and if appropriate in the aliphatic moiety: fluorine, chlorine, bL~ in~
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyano, ~ethAne~iyl, e~ h~n~iyl, butanediyl or butadienediyl; Rl furthermore represents hetero-cyclylmethyl, heterocyclylethyl or heterocyclyl-propyl, each of which is optionally monosubstituted to trisubstituted in the heterocyclyl moiety by identical or different substituents, suitable~
heterocycles in each case beinq:
N--LN ~ - N~ - N~
Z ; N'Z
~ -N O or -N NH
- N~
where Z in each case represents oxygen or sulphur Le A 27 918 - 10 -and where the followin~ are selected as particularly preferred substituents:
fluorine, chlorine, bL~ ine~ cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methy:Lthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio;
R1furthermore represents iII each case straight-chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having 3 to 6 carbon atoms or alkinyloxy having 3 to 6 carbon atoms, or represents benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenyl-pentyl, phenylhexyl, phenylheptyl, phenylcyano-methyl, phenylcyanoethyl, phenylcyanopropyl, phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxy-butyl, phenylethinyl, benzyloxy, phenylethyloxy, phenoxy, benzoyl, phenyl or naphthyl, if appropriate straight-chain or branched, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents in each case being: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylsulphinyl, methyl-sulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, cyclohexyl and phenoxy, RZ represents methyl, ethyl, n- or i-propyl, n-, i-, s-or ~-butyl, n- or i-pentyl, n- or i-hexyl, or represents allyl, propargyl, methoxy, ethoxy, Le A 27 918 ~ methoxymethyl, ethoxymethyl, methoxyethyl or ethoxy-ethyl, or represents str~ight-chain or ~ranched haloge~o~lkyl, halog~noAl kenyl and halogeno~lkinyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or b~ ne~ or represents cyclopentyl, cyclohexyl, cyclopropyl, cyclopropylmethyl, cyclo-pentylmethyl, cyclohexylmethyl or cyclohexylethyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n-, i-, s- or t-pentyl~ n- or i-hexyl, or represents allyl, propargyl, methoxyethyl, ethoxyethyl, fluoroethyl, chloroethyl, fluoropropyl, chloropropyl or cyanoethyl, X represents oxygen or sulphur and 15 Y represents oxygen or sulphur.
Very particularly preferred c~ ~unds of the formula (I) are those in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n-, i-, s- or t-pentyl, n-, i-, s- or t-hexyl, propargyl, n- or i-butinyl, n- or i-pentinyl, or represents straight-chain or branched halog~nn~lkyl having 1 to 4 carbon atoms and 1 to 4 identical or different halogen atoms, in particular fluorine and chlorine, or represents cyanomethyl, cyanoethyl or n- or i-cyanopropyl, or represents Le A 27 918 - 12 -cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclo-pentylmethyl, cyclohexyl o:r cyclohexylmethyl, each of which is optionally monosubstituted to trisub-stituted by identical or different substituents, or represents phenyl, benzyl or phenylethyl, each of which is optionally monosubstituted to trisub-stituted by identical or different substituents from the series comprising fluorine, chlorine, bl~ inP~
methyl, ethyl and/or trifluoromethyl, or represents in each case straight-chain or branched phenyl-propyl, phenylbutyl, phenylpentyl or phenylhexyl, or represents morpholinyl-Cl-C4-alkyl, R2 represents methyl, ethyl, n-, i- or cyclopropyl, n-, i-, s- or t-butyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n- or i-pentyl, X represents oxygen and Y represents oxygen.
Examples of the compounds of the formula (I) according to the invention are listed in Table 1 below.
Rl-NH-C-N ~ N-~o-R3 Le A 27 918 - 13 -~p3 Table 1: Examples of the compoundR of the formula (I) Rl R2 R3 X Y
i C3H7 CH3 CH3 0 0 CF3-ctcH3)2 CH3 C2H5 ~ ~
F-CH2-C(cH3)2 CH3 C2H5 ~ ~
C2H5-C(cH3)2 CH3 CH3 0 0 C3H7-C(cH3)Z CH3 CH3 0 0 i-C3H7-C(CH3)2 CH3 CH3 0 0 (CH3)2- CH3 CH3 0 0 H2-C(cH3)Z CH3 CH3 0 0 /~
(CH2)2-C(cH3)2 CH3 CH3 0 0 CHZ)2-C(CH3)2 CH3 CH3 O O
H2-C(cH3)2 CH3 CH3 0 0 H(CH3)- CH3 CH3 0 0 ~ (CH3)2- CH3 C2H5 ~ ~
CH3 ~ H2-cHz-c(cH3)z CH3 CH3 0 0 Le A 27 918 - 14 -~ If, for example, 5-ethoxy-4-ethyl-2,4-dihydro-3H-1,2,4-triazole-3-thione and isopLo~yl~isocyanate are used as starting substances, the course of the reaction of process (a) according to the invention can be S illustrated by the following e~lation:
(CH3)zCH-N=C=O ~ H-N~N-c2Hs N==L~O - C 2H5 O s (CH3)2cH-NH-c-N ~ N-C2HS
If, for example, 5-isopropoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 0-Methyl-~-tert.-butylthio-cAr~- -te are used as starting substances, the course of the reaction of process tb) according to the invention can be illustrated by the following equation:
s o (CH3)3C-NH-C-O-cH3 H-N N-CH3 ~ O-CH(CH3)z ~ S O
' (CH3)3C-NH-C-N N-CH3 -HOCH3 l l N===l~O-CH(CH3)z Le A 27 918 - lS -~ 3 If, for example, 4-isopropyl-5-methoxy-2-ph~no~y-carbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one and cyclo-hexylamine are used as starting substances, the course of the reaction of process (c) according to the invention S can be illustrated by the follo~inq equation:
o o ~3NHz ~ ~-C-N N- CH ( CH3 ) 2 O O
<3NH - C - 7J~N - CH ( CH 3 ) 2 - H~ N=i~o - Cl 1~
Formula (II) provides a general definition of the 5-alkoxy-1,2,4-triazol-3-(thi)ones to be used as starting substances in processes (a) and (b) according to the invention for the preparation of compounds of the formula (I).
In formula (II), R2, R3 and Y preferably, or in par-ticular, have those ~-ni ngs which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or as particularly preferred, for RZ, R3 and Y.
Examples of the starting substances of the formula (II) are listed in Table 2 below.
irJ ~ ~7 ~
N ~ 2 H- N-R (II) N===l~o-R3 Table 2: Examples of the starting substances of the formula (II) CH3 CZH5 ~
CH3 C3H? S
CH3 CH(CH3)2 0 CH3 CH(CH3)2 CH3 -cH2-cH=cH2 0 CH3 -cH2-cH-cH2 S
C2H5 CH(CH3)2 0 C2H5 -CH2-CH=CH2 0 C2H5 CH(CH3)2 S
C2H5 -CHz-CH=CH2 S
Le A 27 91e - 1? -The starting substances of the formula (II) are known in some cases (cf. J. Chem. Soc C 1967, 2700-2704; J.
Heterocycl. Chem. 15 (1978), 377-384).
Those compounds of the general fo 1A (II) in which Y
represents oxygen and R2 and R3 have the abov --tioned -~nings are new and are a subject of the present patent application.
The new 5-alkoxy-1,2,4-triazol-3-ones (II, Y = O) are obtained when hydrazinoformic esters of the general formula (VII) H2N-NH-Co-o-R4 (VII) in which R4 has the abov ~ntioned -~n i ng are reacted with alkyliminocarboxylic diesters of the general fo 1 A (VIII) ,o-R3 R -N=C~ (VIII) o -R3 in which R2 and R3 have the abov~ tioned ~~ning, Le A 27 918 -- 18 -~ if appropriate in the presence of a diluent such as, for example, o-dichlorobenzene, at temperatures between O~C
and 200~C, preferably between 50~C and lS0~C (cf. the Preparation Examples).
The starting substances of the formulae (VII) and (VIII) are known chemicals.
Formula (III) provides the general definition of the iso(thio)cyanates to be used as starting substances in process (a) according to the invention for the prepara-tion of compounds of the formula (I).
In formula (III), R1 and X preferably, or in particular, have those --n i ngs which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being-lS preferred, or as particularly preferred, for R1 and X.
The starting substances of the formula (III) are known chemicals for organic synthesis.
Formula (IV) provides a general definition of the reac-tive (thio)cArh- -tes to be used as starting substances in process (b) according to the invention for the preparation of compounds of the formula (I).
In formula (IV), Rl and X preferably, or in particular, have those -~n i ngs which have already been mentioned above in connection with the description of the compounds Le A 27 918 - 19 ~
~ ~ '';d ~ 3~ , - of the formula (I) according to the invention as being preferred, or as particularly preferred, for R1 and X;
R4 preferably represents methyl, ethyl, phenyl or benzyl.
The starting substances of the formula (IV) are known chemicals for organic synthesis.
Formula (V) provides a g~neral definition of the 5-alkoxy-1,2,4-triazol-3-(thi)one derivatives to be used as starting substances in process (c) according to the invention for the preparation of compounds of the formula (I).
In formula ~V), RZ, R3, X and Y preferably, or in par-ticular, have those - nings which have already been ~ention~ above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or as particularly preferred, for R2, R3, X and Y;
R4 preferably represents methyl, ethyl, phenyl or benzyl.
The starting substances of the formula (V) were hitherto not known from the literature and are a subject of the present patent application.
The new 5-alkoxy-1,2,4-triazol-3-(thi)one derivatives of Le A 27 918 - 20 -2~18~4 the general formula ~V) are obta:ined when S-alkoxy-1,2,4-triazol-3-(thi)ones of the general formula (II) H-NJ~N-R2 ( I I ) ~==I~o - R3 in which R2, R3 and Y have the abov. I~ntioned --nings are reacted with chlorolthio)formic esters of the general formula ~IX) R4-0-C-Cl ( IX) in which R4 and X have the abov. -ntioned ~ nin~, if appropriate in the presence of a diluent such as, for example, tetrahydrofuran, and if appropriate in the presence of an acid acceptor such as, for example, potassium tert-butylate, at temperatures between -20DC
and +100 DC .
Le A 27 918 - 21 -Formula (VI) provides a general definition of the amino cl r"~unds fur~he -re to be used as starting substance~
in proce6s (c) according to the invention for the pre-paration of compounds of the formula (I).
S In formula (~I), R1 preferably, or in particular, ha~ the -sning which has already been mentioned above in connec-tion with the description of the compounds of the formula (I) according to the invention as being preferred, or as particularly preferred, for R1.
The starting substances of the formula (VI) are known chemicals for organic synthesis.
Processes (a), (b) and (c) according to the invention for the preparation of the new compounds of the formula (I) are preferably carried out in each case using diluents.-Suitable diluents for this purpose are virtually allinert organic solvents. These preferably include aliphatic and aromatic, option~lly halogenated hydro-carbons such as pentane, h~Ane~ heptane, cycloh~x~ne, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloro-form, carbon tetrachloride, chlorobenzene and o-dichloro-benzene, ethers such as diethyl ether 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 27 918 - 22 -propionitrile, amides such as, for example, dimethyl-formamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and h~r ~ ~hylphosphoric triamide.
If appropriate, processes (a), ~b) and (c) according to the invention are in each case carried out in the presence of a basic reaction auxiliary. Suitable sub-stances which are employed are preferably basic organic nitrogen compounds. These include, for example, tri-methyl i~e, triethylamine, tripropylr in~ tributyl-amine, diisopLopylamine, dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethylbenzylamine, pyridine, 4-dimethyl-amino-pyridine,1,5-~ hicyclo-(4,3,0]-non-5-ene(DBN), 1,8-~ i ~ 7 ~hiCyC 10 r s, 4,0)-undec-7-ene (DBU) and 1,4-diazab-icyclo-t2,2,2]-octane (DABCO).
When carrying out processes (a), (b) and (c) according to the invention, the reaction temperatures can be varied in each case in a substantial range. In general, the proces-ses are carried out at temperatures between -20~C and +150~C, preferably at temperatures between 0~C and 100~C.
In general, processes (a), (b) and (c) according to the invention are carried out under atmospheric pressure.
However, it is also possible to carry out the processes under increased or reduced pressure.
For carrying out processes (a), (b) and (c) according to the invention, the starting substances required in each Le A 27 918 - 23 - - -- case are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components employed in each case in a larger excess.
In general, the reactions are carried out in a ~uitable diluent in the presence of a ~asic reaction a~Yili~ry~
and the reaction mixture is stirred for several hour3 at the particular temperature required. Working-up in the processes according to the invention is carried out in each case by customary methods.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying 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 un-desired. Whether the substances according to the inven-tion act as total or selective herbicides depends essen-tially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
DicotYledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, seg~AniA, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, ~otala, ~in~ernia~ T-- i , Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Le A 27 918 - 24 -~ ~,J i 3 Ranunculus and Taraxacum.
DicotYledon cultures of the qenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the qenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, ~leusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Aylo~on~ Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, I~ch~ , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the qenera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, ~n~n~C ~ Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same -nner to other plants.
The compounds are suitable, dep~n~i ng on the concentra-tion, 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 c~ -unds can be employed for combating weeds in peren-nial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, hAn~n~ plantations, coffee plantations, tea Le A 27 918 - 25 -$ eJ ',I~t plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective combating of weeds in an~ual cultures.
S ~he compounds of the formula (I) according to the inven-tion are suitable for selectively combating monocotyledon and dicotyledon weeds, mainly in monocotyledon cultures, by the pre- and the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emul6ions, wettable powders, ~uspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concen-trates, natural and synthetic materials Lmpregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known -nn~rl for example by i~i ng the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsify ing 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 suitable in the main: aromatics, such as xylene, toluene, or alkyl-naphthalenes, chlorinated aromatics and chlorinated Le A 27 918 - 26 - -aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocA~ho~R, such as cycloh~Ane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as ~heir ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cycloh~Anone, strongly polar solvents, such as dimethylfo ~ide and dimethyl sulph-oxide, as well as water.
As solid carriers there are suitable: for example am-monium salts and ground natural minerals, such as kao-lins, clays, talc, chalk, quartz, attapulgite, montmoril-lonite 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, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize 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, polyoxy-ethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products;
as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Le A 27 918 - 27 -CA 020~1894 1998-12-10 Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, 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 dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds, the active compounds according to the invention, as such or in the form of their formula-tions, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, such as, for example, l-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione(A~ ~Y~IONE*) or N-(2-benzothiazolyl)-N,N'-dimethylurea(METABENZTHIAZURON*) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one(METAMITRON*) for combating weeds in *Trade-mark CA 020~1894 1998-12-10 sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN*) for combating weeds in soya beans; furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D*); 4-(2,4-dichlorophenoxy)-butyric acid (2,4-DB*); 2,4-dichlorophenoxypropionic acid (2,4-DP*); 2-chloro-2',6'-diethyl-N-methoxy-methylacetanilide (ALACHLOR*); methyl-6,6-dimethyl-2,4-dioxo-3-[1-(2-propenyloxyamino)-butylidene]-cyclohexanecarboxylic acid (ALLOXYDIM*); 4-amino-benzenesulphonyl methyl carbamate (ASULAM*); 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (ATRAZINE*); methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-methyl]-benzoate (BENSULFURON*); 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BENTAZONE*); 3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL*); N-(butoxymethyl)-2-chloro-N(2,6-diethylphenyl)-acetamide (BUTACHLOR*); 5-amino-4-chloro-2-phenyl-2,3-dihydro-3-oxy-pyridazine (CHLORIDAZONE*);
isopropyl N-(3-chlorophenyl)-carbamate (CHLORPROPHAM*); 2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON*); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON*); exo-1-methyl-4-(1-methylethyl)-2-(2-methylphenyl-methoxy)-7-oxabicyclo-(2,2,1)-heptane (CINMETHYLIN*); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID*); 2-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine (CYANAZINE*); N,S-diethyl-N-cyclohexyl-thiolcarbamate (CYCLOATE*); 2-[1-(ethoximino)-butyl]-3-hydroxy-5-[tetrahydro-(2H)-thiopyran-3-*Trade-mark CA 020~1894 1998-12-10 yl]-2-cyclohexane-1-one (CYCLOXYDIM*); 2-~4-(2,4-dichloro-phenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP*); 2-[(2-chlorophenyl)-methyl]-4,4-dimethylisoxazolidin-3-one (DIMETHAZONE*); S-ethyl N-N-di-n-propyl-thiocarbamidate (EPTAME*); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN*); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP*); 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP*); 1-methyl-3-phenyl-5-(3-trifluoro-methylphenyl)-4-pyridone (FLURIDONE*); [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its 1-methylheptyl ester (FLUROXYPYR*); 2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]-phenoxy}-propanoic acid or its ethyl ester (HALOXYFOP*); 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione (HEXAZINONE*); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-lH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ*); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL*); N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON*); (2-methyl-4-chlorophenoxy)-acetic acid (MCPA*); (4-chloro-2-methyl-phenoxy)-propionic acid (MCPP*);
N-methyl-2-(1,3-benzo-thiazol-2-yloxy)-acetanilide (MEFENACET*); 2-chloro-N-(2,6-dimethylphenyl)-N-[(lH)-pyrazol-l-yl-methyl]-acetamide (METAZACHLOR*); 2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide (METOLACHLOR*); 2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-*Trade-mark CA 020~1894 1998-12-10 amino]-sulphonyl}-benzoic acid or its methyl e~ter (METSULFURON*); S-ethyl N,N-hexamethlyenethiocarbamate (MOLINATE*); 1-(3-trifluoromethylphenyl)-4-methylamino-5-chloro-6-pyridazone (NORF~URAZON*); 4-(di-n-propylamino)-3,5-dinitrobenzenesulphonamide (ORYZA~IN*); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN*); 3-(ethoxycarbonylaminophenyl)-N-(3'-methylphenyl)-carbamate (PHENMEDIPHAM); 2-chloro-N-isopropylacetanilide (PROPACHLOR);
isopropyl N-phenyl-carbamate (PROPHAM*); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octylthiocarbonate (PYRIDATE*); ethyl 2-[4-(6-chloroquinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL*); 2-[1-(etho~Am;nQ)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM*); 2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine (SIMAZINE*); 2,4-bis-[N-ethylamino]-6-methylthio-1,3,5-triazine (SIMETRYNE*); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE*); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate (THIAMETURON*); S-[(4-chlorophenyl)-methyl] N,N-diethylthiocarbamate (THIOBENCARB*); S-(2,3,3-trichloroallyl) N,N-diisopropylthiocarbamate (TRIALLATE*); 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN*).
Surprisingly, some mixtures also show a synergistic action.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird *Trade-mark repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of - 31a -their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and gr~nul~.
They are used in the customary ~nn~r, for example by S watering, spraying, atomising 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 d~p~n~c essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 10 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
Preparation Examples:
Example 1 o o Il a (CH3)~C-NH-C-N ~ N-CH3 . -CH3 Le A 27 918 - 32 -~ 3 A mixture of 1.3 g (0.01 mol) of 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 0.1 g of 1,8-diazabi-cyclo[5.4.0]undec-7-ene (DBU3, 1.0 g (0.01 mol) of tert-butyl isocyanate and 50 ml of acetonitrile is stirred for 12 hours at 20~C and subsequently concentrated under a water pump vacuum. The residue is taken up in methylene chloride, and the mixture is washed with wate~, dried with magnesium sulphate and filtered. The filtrate is concentrated under a water pump vacuum, the residue is brought to crystallisation by trituration with petroleum ether, and the product is isolated by filtration with suction.
1.4 g (61% Of theory) of 2-tert-butyl-amino-carbonyl-5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of lS melting point 167~C are obtained.
Other examples of the compounds of the formula (I) which can be prepared analogously to Example 1 and corresponding to the general description of the prepara-tion processes according to the invention are those listed in Table 3 below.
x Y
Rl-NH-C-N N_R2 ( I ) -R
Le A 27 918 - 33 -Table 3: Preparation examples of the compounds of the formula (I) No. R2 R3 X Y Melting ClCHzl- CH3 CH3 O ~ 153 3 H3C ~ CH2CH- C3H7 CH3 0 (oil) 4Cl ~ H2CH21 C3H7 CH3 o 0 (oil) SCl ~ H2CH21- CH3 C2H5 o (oil) Cl ~ IH3 (oil) 7 Cl ~ H2CH 1 H- CH3 C2HS ~ ~ (oil) Le A 27 918 - 34 -Table 3: continuation 5 Example Rl RZ R3 X r Melting No. ~ point (~C) 8~ H2~CH2CIH- CH3 C2H5 ~ (oil) 9H3C ~ HzCH2CH- CH3 C2H5 0 0 (oil~
o ~ H2CH2CIH- CH3 Cz~5 ~ (oil) 11 H3C ~ CH2lCH- CH3 C2H5 ~ ~ (oil) 12 Cl ~ H2CH - CIH- CH3 C2H5 o (oil) 3013 C1 ~ H2CH21CH- CH3 C2H5 ~ (oil) Le A 27 918 35 Table 3: continuation 5 Ex~nple Rl RZ R3 ~ point ( C) 14 ~ H3 ~ CH3 CH3 ~ ~ 166 15 ~ IH3 120 16 ~ C- CM3 CH3 o o 176 17 Cl ~ CH2CH2- CH3 CH3 0 ~ 130 18 Cl ~ H- CH3 CH3 ~ ~ 104 Cl CH3 19 ~ IH3 117 _5 CH3 Le A 27 918 - 36 -~ , . ~ . . . . .... . .
2 6~3 ~
Table 3: continuation Melting 5 Example Rl R2 R3 point ( C) H3C ~ H ~ CH3 CH3 0 ~100 . CH3 21 (CH3~3c CH3 C3H7 0 ~ 75 22 ClCH2C- CH3 C3H7 0 ~
23 ~ H2 1I H3 CH3 CH3 ~ ~142 24 H9C~-C- CH3 CH3 0 0135 25 H3C ~ H2CH2l- CH3 CH3 0 0106 Le A 27 918 ~ 37 ~ . . ...
Table 3: continuation No. R2 R3 ~ point ( C) ~CH3 26 ~ H2CH2CH2l CH3 CH3 00 137 27~ H211- CH3 CH3 0 0 131 28Cl ~ H2CH2C~ CH3 CH3 0 0 1 lB
29 F2CH ~ -C-C- CH3 CH3 0 0 82 30 (CH3)3c CH2-CH=CH2 CH3 0 0 87 Le A 27 918 - 38 -$ ~:
Startin~ substances of the formula (II):
Example tII-1) J~N
H-N l-C1~3 N~oCH3 In 100 ml of absolute o-dichlorobenzene, 50.2 g (0.33 mol) of phenyl hydrazinoformate and 36.6 g (0.33 mol, 93%) of ~rimethyl iminoc~hon~te are heated to 60~C, and the mixture is stirred for 2 hours, during which process a clear solution forms. ~his solution is heated to 120-C
in the course of two hours, during which process methanol distils off. A vacuum is applied carefully, during which process more methanol and finally phenol distil off. Upon further distillation, there is formed a fraction which solidifies in the receiver in crystalline form.
After recrystallisation from toluene, 7.0 g (0.054 mol, 16% of theory) of 4-methyl-5-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are obt~i n~ in the form of colour-less crystals of melting point 142-144~C.
Le A 27 918 - 39 -Use Examples:
In the Use Examples, the following compound (A) is used as c~ -rison substance:
o o ~ 11 11 ~NH - C - N~N - NH2 ~ A ) 4-amino~5-methyl-2-phenylaminocarbonyl-2,4-dihydro-3H-1,2,4-triazol-3 one 15(disclosed in EP-A 294,666).
~0 Le A 27 918 - 40 -ExamPle A
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of al~ylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound~
desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 1000 1 of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0~ = no action (like untreated control) 100% = total destruction In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds of Preparation Examples 1 and 2.
Le A 27 918 - 41 - -Example B
Prc ~ ?rgence test 5O1vent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the s~ated amount of solvent, the stated 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 development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction In this test, a powerful action against weeds combined with good tolerance by crop plants such as, for example, barley, is shown, for example, by the compound of Preparation Example 2.
It will be apprecia~dthat the instant sper;f;c~tion is set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the ~s~lL invention.
- Le A 27 918 - 42 -
Claims (19)
1. A 5-alkoxy-1,2,4-triazol-3-(thi)one of the formula in which R1 represents in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkenyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl or halogenoalkinyl, each of which has 2 to 8 carbon atoms and 1 to 15 or 13 identical or different halogen atoms, cyano-C1-8 alkyl, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, alkoxyalkyl, alkoximinoalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, each of which has up to 6 carbon atoms in the individual alkyl or alkenyl moieties, alkylaminoalkyl or dialkylaminoalkyl, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, or represents cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, each of which has 3 to 8 carbon atoms in the cycloalkyl or cycloalkenyl moiety and up to 6 carbon atoms in the alkyl moiety and each of which is optionally substituted by halogen, cyano, and in each case straight-chain or branched alkyl or halogeno-halogenoalkyl, each of which has 1 to 4 carbon atoms and up to 9 identical or different halogen atoms, or in each case divalent alkanediyl or alkenediyl, each of which has up to 4 carbon atoms; R1 furthermore represents heterocyclylalkyl which has -43a-1 to 6 carbon atoms in the straight-chain or branched alkyl moiety and 1 to 9 carbon atoms as well as 1 to 3 hetero atoms - selected from nitrogen, oxygen and sulphur - in the heterocyclyl moiety and each of which is optionally substituted by halogen, cyano, nitro, and in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio or alkoxycarbonyl, each of which has 1 to 5 carbon atoms and, if appropriate, up to 9 identical or different halogen atoms; R1 furthermore represents in each case straight-chain or branched alkoxy having 1 to 8 carbon atoms, alkenyloxy having 2 to 8 carbon atoms or alkinyloxy having 2 to 8 carbon atoms, and finally represents aralkyl, aryloxyalkyl, arylalkenyl, arylalkinyl, aralkyloxy, aryloxy, aroyl or aryl, each of which has 6 or 10 carbon atoms in the aryl moiety and up to 8 carbon atoms in the alkyl, alkenyl or alkinyl moiety, and each of the aryl moieties is optionally substituted by halogen, cyano, nitro, hydroxyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, alkylsulphinyl, alkylsulphonyl, halogenoalkylsulphinyl, halogenoalkylsulphonyl, alkanoyl or alkoxycarbonyl, each of which has 1 to 6 carbon atoms and, if appropriate, up to 9 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms and phenoxy, and each of the alkyl moieties optionally substituted by halogen or cyano, R2 represents in each case straight-chain or branched alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl having 2 to 8 carbon atoms and 1 to 15 identical or different halogen atoms, halogenoalkinyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl or alkoxy, each of which has 1 to 6 carbon atoms in the individual alkyl moieties, cyano-C1-8 alkyl, or represents cycloalkylalkyl or cycloalkyl, each of which has 3 to 7 carbon atoms in the cycloalkyl moiety and up to 6 carbon atoms in the straight-chain or branched alkyl moiety, R3 represents in each case straight-chain or branched alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, alkinyl having 2 to 8 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl having 2 to 8 carbon atoms and 1 to 15 identical or different halogen atoms, halogenoalkinyl having 2 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, alkoxyalkyl having 1 to 6 carbon atoms in each of the individual alkyl moieties, or represents cyano-C1-8 alkyl, X represents oxygen or sulphur and Y represents oxygen or sulphur wherein halogen in the substitution of R1, R2 and R3 represents fluorine, chlorine, bromine or iodine.
2. A 5-alkoxy-1,2,4-triazol-3-(thi)one of the general formula (I) according to Claim 1, in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, in each case straight-chain or branched pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl, or represents allyl propenyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl, propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl, or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 atoms of fluorine, chlorine or bromine, or represents in each case straight-chain or branched halogenoalkenyl or halogenoalkinyl, each of which has 3 to 5 carbon atoms and 1 to 3 atoms of fluorine or chlorine, or represents in each case straight-chain or branched cyanoalkyl having 1 to 4 carbon atoms in the alkyl moiety, hydroxyalkyl having 1 to 6 carbon atoms and 1 to 3 hydroxyl groups, alkoxyalkyl, alkoximinoalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, alkylaminoalkyl or dialkylaminoalkyl, each of which has up to 4 carbon atoms in the individual alkyl or alkenyl moieties, or represents cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl, cyclohexenyl or cyclohexenylmethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, the following being selected as substituents in the cyclic or aliphatic moiety: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; cyano, methanediyl, ethanediyl, butanediyl or butadiene-diyl;
R1 furthermore represents heterocyclylmethyl, heterocyclylethyl or heterocyclylpropyl, each of which is optionally mono-substituted to trisubstituted in the heterocyclyl moiety by identical or different substituents, wherein the heterocycles in each case being:
;
;
or where Z in each case represents oxygen or sulphur and where the substituents are fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethyl-thio;
R1 furthermore represents in each case straight-chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having
R1 furthermore represents heterocyclylmethyl, heterocyclylethyl or heterocyclylpropyl, each of which is optionally mono-substituted to trisubstituted in the heterocyclyl moiety by identical or different substituents, wherein the heterocycles in each case being:
;
;
or where Z in each case represents oxygen or sulphur and where the substituents are fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethyl-thio;
R1 furthermore represents in each case straight-chain or branched alkoxy having 1 to 6 carbon atoms, alkenyloxy having
3 to 6 carbon atoms or alkinyloxy having 3 to 6 carbon atoms, or represents benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenylcyanomethyl, phenylcyanoethyl, phenylcyanopropyl, phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxybutyl, phenylethinyl, benzyloxy, phenylethyloxy, phenoxy, benzoyl, phenyl or naphthyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents in each case being: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethyl-thio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylsulphinyl, methylsulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, cyclohexyl or phenoxy, R2 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, or represents allyl, propargyl, methoxy, ethoxy, methoxymethyl, ethoxy-methyl, methoxyethyl or ethoxyethyl, or represents straight-chain or branched halogenoalkyl, halogenoalkenyl and halogenoalkinyl having 1 to 4 carbon atoms and 1 to 9 identical or different atoms of fluorine, chlorine or bromine, or represents cyclopentyl, cyclohexyl, cyclopropyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl or cyclohexylethyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, n- or i-hexyl, or represents allyl, propargyl, methoxyethyl, ethoxyethyl, fluoroethyl, chloroethyl, fluoropropyl, chloropropyl or cyanoethyl, X represents oxygen or sulphur and Y represents oxygen or sulphur.
3. A 5-alkoxy-1,2,4-triazol-3-(thi) one of the general formula (I) according to claim 1, in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, n-, i-, s- or t-hexyl, propargyl, n- or i-butinyl, n- or i-pentinyl, or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 4 identical or different atoms of fluorine or chlorine, or represents cyanomethyl, cyanoethyl or n- or i- cyanopropyl, or represents cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cyclohexyl-methyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, or represents phenyl, benzyl or phenylethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, and trifluoromethyl, or represents in each case straight-chain or branched phenylpropyl, phenyl-butyl, phenylpentyl or phenylhexyl, or represents morpholinyl-C1-C4-alkyl, R2 represents methyl, ethyl, n-, i- or cyclopropyl, n-, i-, s- or t-butyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, X represents oxygen and Y represents oxygen.
3. A 5-alkoxy-1,2,4-triazol-3-(thi) one of the general formula (I) according to claim 1, in which R1 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, n-, i-, s- or t-hexyl, propargyl, n- or i-butinyl, n- or i-pentinyl, or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 4 identical or different atoms of fluorine or chlorine, or represents cyanomethyl, cyanoethyl or n- or i- cyanopropyl, or represents cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cyclohexyl-methyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents, or represents phenyl, benzyl or phenylethyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, and trifluoromethyl, or represents in each case straight-chain or branched phenylpropyl, phenyl-butyl, phenylpentyl or phenylhexyl, or represents morpholinyl-C1-C4-alkyl, R2 represents methyl, ethyl, n-, i- or cyclopropyl, n-, i-, s- or t-butyl, R3 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, X represents oxygen and Y represents oxygen.
4. A 5-methoxy-1,2,4-triazol-3-one of the formula in which R1 is alkyl having up to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, each optionally substituted by phenyl, halophenyl, cycloalkyl having 3 to 8 carbon atoms, methylcycloalkyl having 3 to 8 carbon atoms in the cycloalkyl moiety or alkynyl having 2 to 8 carbon atoms.
5. 2-tert.-Butylaminocarbonyl-5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of the formula .
6. 2-tert.-Chlorbutylaminocarbonyl-5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of the formula -50a-
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 liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.
9. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6.
10. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
11. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95 % by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90 % by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.
13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a pre-emergence herbicide.
14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a post-emergence herbicide.
15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 1 g and 10 kg/ha.
16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 10 g and 5 kg/ha.
17. A process for preparing a compound of formula I as defined in Claim 1 wherein R1, R2, R3, X and Y are as defined in Claim 1, which process comprises reacting (a) a 5-alkoxy-1,2,4-triazol-3-(thi)one of the general formula (II) in which R2, R3 and Y have the abovementioned meaning, with an iso(thio)cyanate of the general formula (III) R1-N=C=X (III) in which R and X have the abovementioned meanings, or (b) a 5-alkoxy-1,2,4-triazol-3-(thi)one of the general formula (II) in which R2, R3 and Y have the abovementioned meaning with a reactive (thio-)carbamate of the general formula (IV) in which R1 and X have the abovementioned meanings and R4 represents alkyl, aralkyl or aryl, or (c) a 5-alkoxy-1,2,4-triazol-3-(thi)one derivative of the general formula (V) in which R2, R3, X and Y have the abovementioned meanings and R4 represents alkyl, aralkyl or aryl, with an amino compound of the general formula (VI) R1-NH2 (VI) in which R1 has the abovementioned meaning.
18. A 5-alkoxy-1,2,4-triazol-3-one of the general formula (II) in which R2 and R3 are as defined in claim 1, excluding the compound 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one.
19. A process for preparing a compound of formula (II) as defined in claim 18 wherein R2 and R3 are as defined in claim 18 and further including the compound 5-methoxy-4-methyl-2,4-dihydro-3-H-1,2,4-triazol-3-one which process comprises reacting a hydrazinoformic ester of the general formula (VII) H2N - NH - COOR4 (VII) in which R4 represents alkyl, aralkyl or aryl with an alkyliminocarboxylic diester of the general formula (VIII) in which R2 and R3 have the above-mentioned meanings at temperatures between 0°C and 200°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4030063.3 | 1990-09-22 | ||
| DE4030063A DE4030063A1 (en) | 1990-09-22 | 1990-09-22 | SUBSTITUTED 5-ALKOXY-1,2,4, -TRIAZOL-3- (THI) ONE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2051894A1 CA2051894A1 (en) | 1992-03-23 |
| CA2051894C true CA2051894C (en) | 1999-07-13 |
Family
ID=6414774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002051894A Expired - Lifetime CA2051894C (en) | 1990-09-22 | 1991-09-19 | Substituted 5-alkoxy-1,2,4-triazol-3-(thi)ones |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0477646B1 (en) |
| JP (2) | JP3034091B2 (en) |
| BR (1) | BR9104035A (en) |
| CA (1) | CA2051894C (en) |
| DE (2) | DE4030063A1 (en) |
| DK (1) | DK0477646T3 (en) |
| ES (1) | ES2069791T3 (en) |
| ZA (1) | ZA917516B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300480A (en) * | 1989-04-13 | 1994-04-05 | Bayer Aktiengesellschaft | Herbicidal sulphonylaminocarbonyltriazolinones having two substituents bonded via oxygen |
| DE4316430A1 (en) * | 1993-05-17 | 1994-11-24 | Bayer Ag | Substituted triazolinones |
| DE4433969A1 (en) | 1994-09-23 | 1996-03-28 | Bayer Ag | Process for the preparation of alkoxytriazolinones |
| DE4433968A1 (en) | 1994-09-23 | 1996-03-28 | Bayer Ag | Process for the preparation of alkoxytriazolinones |
| DE4433966A1 (en) | 1994-09-23 | 1996-03-28 | Bayer Ag | Process for the preparation of alkoxytriazolinones |
| DE4433967A1 (en) * | 1994-09-23 | 1996-03-28 | Bayer Ag | Process for the preparation of alkoxytriazolinones |
| DE19508118A1 (en) * | 1995-03-08 | 1996-09-12 | Bayer Ag | Sulfonylaminocarbonyltriazolines with haloalkoxy substituents |
| EP1147096A1 (en) * | 1999-01-25 | 2001-10-24 | E. I. du Pont de Nemours and Company | Herbicidal oxadiazolidines |
| US6737383B1 (en) | 1999-01-25 | 2004-05-18 | The Regents Of The University Of California | Herbicidal oxadiazolidines |
| BR102018075132A2 (en) | 2018-12-04 | 2020-06-16 | UPL Corporation Limited | WIDE SPECTRUM SYNERGISTIC HERBICIDE COMPOSITION FOR THE CONTROL OF WEEDS IN AGRICULTURAL CROPS, USE OF THESE COMPOSITION FOR PREPARATION OF PRODUCT, PRODUCT AND APPLICATION METHOD |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0719042B2 (en) * | 1986-11-12 | 1995-03-06 | コニカ株式会社 | Silver halide photographic light-sensitive material containing novel yellow coupler |
| DE3709574A1 (en) * | 1987-03-24 | 1988-10-06 | Bayer Ag | SUBSTITUTED TRIAZOLINONES |
| DE3934081A1 (en) * | 1989-10-12 | 1991-04-18 | Bayer Ag | SULFONYLAMINOCARBONYLTRIAZOLINONE |
| DE3722821A1 (en) * | 1987-07-10 | 1989-01-19 | Bayer Ag | SUBSTITUTED TRIAZOLINONES |
-
1990
- 1990-09-22 DE DE4030063A patent/DE4030063A1/en not_active Withdrawn
-
1991
- 1991-09-10 EP EP91115237A patent/EP0477646B1/en not_active Expired - Lifetime
- 1991-09-10 DK DK91115237.9T patent/DK0477646T3/en active
- 1991-09-10 ES ES91115237T patent/ES2069791T3/en not_active Expired - Lifetime
- 1991-09-10 DE DE59104765T patent/DE59104765D1/en not_active Expired - Lifetime
- 1991-09-17 JP JP3262595A patent/JP3034091B2/en not_active Expired - Fee Related
- 1991-09-19 CA CA002051894A patent/CA2051894C/en not_active Expired - Lifetime
- 1991-09-20 ZA ZA917516A patent/ZA917516B/en unknown
- 1991-09-20 BR BR919104035A patent/BR9104035A/en not_active IP Right Cessation
-
1999
- 1999-11-30 JP JP34014599A patent/JP3172518B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| BR9104035A (en) | 1992-06-02 |
| EP0477646B1 (en) | 1995-03-01 |
| JP2000128870A (en) | 2000-05-09 |
| JP3034091B2 (en) | 2000-04-17 |
| ZA917516B (en) | 1992-06-24 |
| JPH04288062A (en) | 1992-10-13 |
| CA2051894A1 (en) | 1992-03-23 |
| EP0477646A1 (en) | 1992-04-01 |
| ES2069791T3 (en) | 1995-05-16 |
| DE4030063A1 (en) | 1992-03-26 |
| DE59104765D1 (en) | 1995-04-06 |
| JP3172518B2 (en) | 2001-06-04 |
| DK0477646T3 (en) | 1995-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2398159C (en) | Sulphonylaminocarbonyltriazolinones having substitutents bonded via oxygen | |
| US5234897A (en) | Herbicidal 3-amino-5-aminocarbonyl-1,2,4-triazoles | |
| EP0412358B1 (en) | 3-amino-5-aminocarbonyl-1,2,4-triazole derivatives | |
| CA2302058C (en) | A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one | |
| US4931084A (en) | Herbicidal substituted triazolinones | |
| JP2768944B2 (en) | Substituted triazolinone compounds, their preparation and herbicides containing them | |
| CA2074144A1 (en) | Substituted triazoles | |
| KR960012205B1 (en) | Substituted triazolinones | |
| US5021081A (en) | Herbicidal substituted triazoles | |
| CA2051894C (en) | Substituted 5-alkoxy-1,2,4-triazol-3-(thi)ones | |
| US5356865A (en) | Substituted 5-alkoxy-1,2,4-triazol-3-(thi)ones | |
| US5021080A (en) | Herbicidal substituted 4-amino-5-alkylthio-1,2,4-triazol-3-ones | |
| US4948417A (en) | Herbicidal substituted triazolinones | |
| CA2003208C (en) | Substituted triazolinones | |
| US5244865A (en) | Substituted imidazolinylpyrimidines | |
| JP2931368B2 (en) | Substituted triazolinones, their production methods and their use as herbicides and fungicides | |
| US5194084A (en) | Herbicidal substituted triazolones | |
| US5217522A (en) | Herbicidal sulphonylguanidinoazines | |
| US5006156A (en) | Herbicidal sulfonylaminoazines | |
| US5234899A (en) | Substituted 2,2-difluoro-1,3-benzodioxyl-4-ketone herbicides | |
| US5185026A (en) | Herbicidal naphthalene derivatives | |
| US5262389A (en) | Substituted triazolinone herbicides and plant growth regulators | |
| US4941910A (en) | Herbicidal pyrimidine derivatives | |
| US4960455A (en) | Herbicidal triazolodihydropyrimidine-2-sulphonamides | |
| US5209769A (en) | Substituted triazolinones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKEC | Expiry (correction) |
Effective date: 20121202 |