IL86668A

IL86668A - Substituted triazolinones, their preparation and their use as herbicides

Info

Publication number: IL86668A
Application number: IL8666888A
Authority: IL
Original assignee: Bayer Ag
Priority date: 1987-06-12
Filing date: 1988-06-09
Publication date: 1994-04-12
Also published as: EP0294666B1; DK317088D0; CZ281651B6; DK172104B1; HUT49862A; KR890000446A; TR27663A; IE61260B1; KR960012205B1; EP0294666A3; IL86668A0; IE881758L; JP2682643B2; DK317088A; PL153302B1; PL273002A1; ES2061559T3; DE3803523A1; EP0294666A2; SK279720B6

Description

Substituted triazollnones , their .preparation and their use as herbicides BAYER AKTIENGESELLSCHAFT C . 74668 The invention relates to new substituted triazol-inones, several processes for their preparation and their use as herbicides.

It has been disclosed that certain nitrogen hetero-cycles such as, for example, -amino-3-methy1 - 6 -pheny1 -1 , 2 ,4- triaz in-5-one or N-isobutyl-2-oximidazol idine-1-carboxamide (compare, for example, DE-OS (German Published Specification) 2,364,474 and R. Wegler "Chemie der Pf lanzenschutz- und Schadl ingsbekampfungsmi t el , Vol, 5, 219 (1977)) possess herbicidal properties.

However, the herbicidal activity of these previously known compounds with respect to problem weeds as well as their tolerability with respect to important cultivated plants is not completely satisfactory in all areas of application. Furthermore, certain substituted t r i azol i nones , such as, for example, 1-(N,N-dimethyl- carbamoyl)-3-phenyl-4-amino-1,2,4-triazolin-5-one have been disclosed (compare J . Heterocycl. Chem. J_7, 1691- 1696 [19803; Org. Mass. Spectrom. J_4, 369-378 [1979]). Nothing has hitherto been disclosed about a herbicidal activity of these previously known tr azol inones .

New substituted t r azol nones of the general formul a ( I ) ch R1 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, alkoxyalkyl, cycloalkyl, cyclo-alkylalkyl, tetrahydrofuranyl, tetrahydrofuranylalkyl, or represents benzyl or phenyl, which are in each case optionally monosubstituted, disubstituted or trisubstituted by identical or different substituents, - l— ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, R2 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkyl-aminoalkyl, dialkylaminoalkyl, or represents cycloalkyi having 11 carbon atoms, or represents cycloalkyi, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl in each case having 3 to 8 carbon atoms in the cycloalkyi or cycloalkenyl part and where appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl part, and which are in each case optionally monosubstituted or polysubstituted by identical or different substituents selected from halogen, cyano and also in each case straight-chain or branched alkyl or halogenoalkyl in each case having 1 to 4 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms or represents straight-chain or branched halogenoalkenyl having up to 4 carbon atoms and 1 to 5 halogen atoms or in each case bivalent bonded alkanediyl or alkenediyl in each case having up to 4 carbon atoms; furthermore, R2 represents heterocyclylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part and 1 to 9 carbon atoms and also 1 to 3 hetero atoms - in particular nitrogen, oxygen and/or sulphur - in the heterocyclic part, and which is optionally monosubstituted or polysubstituted in the heterocyclic part by identical or different substituents selected from halogen, cyano, nitro, and also in each case straight-chain or branched alkyl, alkoxy, alkylthio halogenoalkyl, halogeno alkoxy, halogenoalkylthio or alkoxycarbonyl in each case having 1 to 5 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms; furthermore, R2 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, or represents optionally straight-chain or branched benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenylcyano- methyl, phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenyl- ethyloxy, phenoxy, benzoyl, phenyl or naphthyl, which are in each case optionally monosubstituted, disubstituted or trisubstituted on the phenyl ring by identical or different substituents selected from flourine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethylsulphinyi, trifluoromethylsulphonyl, methylsulphinyl, methylsulphonyl, acetyl, propiony 1, methoxycarbonyl, ethoxycarbonyl, cyclohexyl or phenoxy, or represents alkoxy, alkenyloxy or alkinyloxy, X represents oxygen or sulphur and Y represents oxygen or sulphur, have been found.

The compounds of the formula (I) can optionally exist as geometric and/or optical isomers or isomer mixtures of different composition, depending on type of the substituents R^ and R^. Both the pure isomers and the isomer mixtures are claimed according to the invention.

Furthermore, it has been found that the new substituted t r i azol i nones of the general formula ( I ) above are obtained when ~" (a) hydrazones of the formula (II) in wh c R , R , X and Y have the abovement ioned meaning and R^ and * independently of one another in each case represent hydrogen, alkyl, aralkyl or aryl, are reacted with an acid, if appropriate in the presence of a diluent, or in that b) lH-triazol inones of the formula (III), Le A 25 302 in which R and X have the above mentioned meaning are reacted with iso( thio ) cyanates of the formula (IV), R2-N=C=Y (IV) in which and Y have the above mentioned meaning, if appropriate, in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary, or in that c) triazol inones of the formula (V) Y 0-R5 in which R1 , X and Y have the above mentioned meaning and R5 represents alkyl , aryl or arylalkyl, are reacted with amines of the formula (VI), F2-NH2 (VI) in which R^ has the above mentioned meaning, if appropriate, in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary.

Le A 25 302 c tuted tr iazol nones of the general formula (I) possess herbicidal properties.

Surpr is ingly , the substituted t r i azo I i nones of the general formula (I) according to the invention show a considerably higher herbicidal potency against problem weeds than the nitrogen heterocycles known fro the prior art such as, for example, 4-am ino-3-methyl-6 pheny 1-1,2, 4-tr iazin-5-one, which are related compound chemically and with respect to action.

Formula (I) provides a general def inition of t substituted tr iazol nones according to the invention. Preferred compounds of the formula (I) are those in wh R1 represents hydrogen, or 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 the individual alkyl parts, or represents cycloalkyl or cycloalkylalkyl in each case having 3 to 7 carbon atoms in the cycloalkyl part and where appropriate 1 to 6 carbo atoms in the straight-chain or branched alkyl part, or represents tetrahydrofuranyl, or represents tetrahydrofuranylalkyl optionally having 1 to 4 carbon atoms in the straight-chain or branched alkyl part, or represents benzyl or phenyl, which are in each case optionally monosubstituted, disubstituted or trisubstituted by identical or different substituents, selected from: flourine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, R2 represents hydrogen, or 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, halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, halogenoalkenyl or halogenoalkinyl in each case having 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, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxy-carbonylalkenyl in each case having up to 6 carbon atoms in the individual alkyl or alkenyl parts, alkylaminoalkyl or dialkylamino-alkyl in each case having 1 to 6 carbon atoms in the individual alkyl parts, cycloalkyl having 11 carbon atoms, or represents cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl in each case having 3 to 8 carbon atoms in the cycloalkyl or cycloalkenyl part and where appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl part, and which are in each case optionally monosubstituted or polysubstituted by identical or different substituents selected from halogen, cyano and also in each case straight-chain or branched alkyl or halogenoalkyl in each case having 1 to 4 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms or represents straight-chain or branched halogenoalkenyl having up to 4 carbon atoms and 1 to 5 halogen atoms or in each case bivalent bonded alkanediyl or alkenediyl in each case having up to 4 carbon atoms; furthermore, R2 represents heterocyclylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part and 1 to 9 carbon atoms and also 1 to 3 hetero atoms - in particular nitrogen, oxygen and/or sulphur - in the heterocyclic part, and which is optionally monosubstituted or polysubstituted in the heterocyclic part by identical or different substituents selected from halogen, cyano, nitro, and also in each case straight-chain or branched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio or alkoxycarbonyl in each case having 1 to 5 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms; furthe*more, R2 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, or R2 furthermore represents heterocyclylmethyl, heterocyclylpropyl or heterocyclylethyl, which are optionally monosubstituted, disubstituted or trisubstituted in the heterocyclic part by identical or different substituents.the heterocycles in each case being selected from where Z in each case represents oxygen or sulphur, and where the optional substituents in each case are: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoro- methylthio; X represents oxygen or sulphur; and Y represents oxygen or sulphur.

Particularly preferred compounds of the formula those in which represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, or represents allyl, propargyl, straight-chain or branched halogenoal ky I having 1 to carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or bromine, or represents methoxymethy I , ethoxymethyl , propoxymethyl, cyclopentyl, cyclo-hexyl, cyclopropyl, cyclopropylmeth L, cyclohexyl-methyl, cyclohexylethyl, or represents tetrahydro uranyl, or represents tetrahydrofuranyl- 5 302 - 8a - methyl, or represents benzyl or phenyl, which are in each case optionally nonosubs t tuted, disubstituted or tr isubst i tuted by identical or different subst i tuents, suitable substituents being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoro-methyl, tr if luoromethoxy or t r i f I uoromethy I th i o, represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, in each case straiaht-chain or branched pentyl^ hexyl, heptyl, octyl, nonyl, decyl or dodecyl, or represents allyl, in each case straight-chain or branched butenyl, pentenyl or hexenyl, propargyl, in each case straight-chain or branched butinyl, pentinyl or hexinyl, or represents straight-chain or branched halogenoalky I having 1 to 8 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine, chlorine or bromine, or represents in each case straight-chain or branched halogenoalkenyL or halogenoalk inyl having in each case 3 to 8 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 6 carbon atoms in the alkyl part, hydroxyalkyl having 1 to 6 carbon atoms and 1 to 3 hydroxyl groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxycarbonylalkenyl, alkylaminoalkyl or dialkylaminoalkyl in 302 - 9 each case having up to 4 carbon atoms in the individual aLkyl or alkenyl parts, or represents cyclopropyl, cyclopropylmethyl, cyclopropylethyl, c c lopent I , cyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmeth I, eye lohexyleth I , cyclohexenyL or cyclohexenylmethyl, which are in each case optionally monosubst i tuted, disubstituted or t r subs t i tuted by identical or different substituents, suitable substituents in each case being: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyano, irethanediyl, ethane-divl, butanedivl, butadienedivl or dichloroallvl; R furthermore represents heterocyclylmethyl, heterocyclylpropyl or heterocyclylethyl, which are optionally monosubst i tuted, disubstituted or trisub stituted in the heterocyclic part by identical or different substituents, suitable heterocycles in each case being: Z in each case represents oxygen or sulphur, and where suitable substituents in each case are: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trif luoromethy I , tr if luoromethoxy or tr f luoromethyLthio; 302 R 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 optionally straight-chain or branched benzyl, phenylethyl, pheny Ipropy I , phenylbutyl, phenylpentyl, phenyl- hexyl, phenylheptyl , pheny I cyanomethyl , phenyl- cyanoethyl, phen I c anopropy I , benzyloxy, phenyl- ethyloxy, phenoxy, benzoyl, phenyl or naphthyl, which are in each case optionally monosubst i tuted, disubst ituted or tr isubst ituted by identical or different subst tuents, suitable phenyl substi- tuents 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, trifluoromethy1 , trifluoro- ethoxy, trifluoromethylthio , trifluoromethyl- sulphinyl, trifluoromethylsulphonyl , methylsulphinyl, me thy Isulphonyl , acetyl, propionyl, methoxycar- bonyl, ethoxycarbony I , cyclohexyl or phenoxy, X represents oxygen or sulphur and Y represents oxygen or sulphur.

Very particularly preferred compounds of the formula (I) are those in which R^ represents hydrogen, methyl, ethyl, n- or i- propyl, methoxymethy I , ethoxymethy I or propoxy- meth I , represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, in each case straight-chain or branched pentyl, hexyl, heptyl, octyl, butenyl, pentenyl, hexenyl, butinyl, pentinyl or hexinyl each of which is optionally monosubst i tuted, disubst tuted or tr isubst ituted by halogen; or additionally represents cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl , cyclopropylmethyl , cyclopropyl- ethyl , cyclohexylmethyl , cyclohexylethyl Le A 25 302 - 1 1 - or cycloheptyl which are in each case optionally monosubs t i tuted, d i subs t i tuted or t r subs t i tut ed by identical or different substituents from the group comprising fluorine, chlorine, methyl, ethyl and/or cyano; and finally represents benzyl, phenylethyl or phenyl, X represents oxygen or sulphur and Y represents oxygen or sulphur.

The following substituted tr i azol inones of the general formula (I) may be mentioned individually in addition to the compounds mentioned in the preparation examples: Le A 25 302 - 12 - CH3 -C(CH3)3 CH3 -C(CH3)3 C2H5 C(CH3)3 C2H5 C(CH3)3 C2H5 C(CH3)3 A 25 302 13 - S-configuration -C(CH3)3 -C(CH3)3 -C(CH3)3 A 25 302 - 14 - H —< H CH- CH- -C-CH2-0CH3 I ?H3 "i_CH2"N CH3 A 25 302 - 15 - X Y Le A 25 302 - 16 - CH. •CH-(CH2)3-CH3 C2H5 CH- -CH-(CH2)2-CH3 C2H5 A 25 302 18 R1 CH- CH- -CH-CH2 CH, CH> ■CH- CH3 R-conf igurat ion A 25 302 - 19 - CH3 -CH CIH3 S-configuration CH3 -CH-CH2-0CH3 CH3 CH-CH3 ■CH< CH: CH3 -CH-C2H5 CH: CH3 CH3 <2 A 25 302 20 - If, for example, 1- (N-isobutylcarbamoyl ) -4-amino-3-methyl-1 ,2 ,4-triazol in-5-one is used as the starting compound, then the course of the reaction of the process (a) according to the invention can be represented by the following equation* If, for example, 4-amino-3-methyl-l ,2,4- ( 1H) -tria-zoline-5-one and t-butylisocyanate are used as starting compounds, then the course of the Taction of the process (b) according to the invention can be represented by the following equation: Le A 25 302 - 21 - If, for example, l-ethoxycarbonyl-4-amino-3-methyl- 1 ,2,4-triazolin-5-one and N,N-diethylpropane-l ,3-diamine are used as starting compounds, then the course of the reaction of the process (c) can be represented by the following equation: Formula R3 and R in each case independently of one another preferably represent hydrogen, or represent straight-chain or branched alkyl having 1 to 4 carbon atoms, or represent phenyl or benzyl.

Le A 25 302 - 22 - The hydrazones of the formula (II) were hitherto unknown* They are also subject matter of the present invention. However, they are obtained analogously to known processes (compare, for example, Acta Pol. Pharm. 3JL, 153-162 [19813 or C.A. 95: 203841j), for example when 1-unsubstituted 4-amino-triezol inones of the formula (III) n which 1 R and X have the abovement i oned meaning, are reacted with aldehydes or ketones of the formula (vil) in which 3 4 R and R have the abovement ioned meaning, if appropriate in the presence of a diluent such as, for example, dichloromethane or toluene, and if appropriate in the presence of a catalyst such as, for example, p-toluenesulphon i c acid, at temperatures between 40°C and 120°C, and the 1-unsubstituted triazol i none-hydr azones of the formula (VIII) Le A 25 302 - 23 - in which and X have the abovement ioned meaning thus obtainable are reacted in a subsequent 2nd step with iso (+-.hio) cyanates of the formula (IV) (IV) R -N=C=Y in which and Y have the abovement ioned meaning, if appropriate in the presence of a diluent such as, for example, di chloromethane or dioxane, and if appropriate in the presence of a reaction auxiliary such as, for example* triethylamine , at temperatures between 50° C and 150° C* or alternatively are reacted in a subsequent 2nd step with ( thio ) chloroformic acid esters of the formula in which R5 represents alkyl* aryl or arylalkyl and γ has the abovement ioned meaning* if appropriate* in the presence of a diluent such as for example tetrahydrofuran and* if appropriate* in the presence of a reaction auxiliary such as for example sodium hydride or potassium-t-butylate at temperatures between -20° C and +40° C and the resulting triazolinones of the ormula (X) * Le A 25 302 - 24 - in which R1 , R3, R4, R5, X and Y have the abovement oned meaning* are reacted in a subsequent 3rd step with amines of the formula (VI)» R2-NH2 (VI) in which R2 has the abovementioned meaning, if appropriate, in the presence of a diluent such as for example tetrahydrofuran and, if appropriate, in the presence of a base* such as for example sodium hydroxide or potassium hydroxide, at temperatures between 20° C and 50° C.

It is however also possible and in some cases advantageous to carry out the reaction of the 1-unsub-stituted triazolinone-hydrazones of the formula (VIII) with (thio) chloroformic acid esters of the formula (IX) and the subsequent reaction of the resulting triazoli-nones (X) with amines of the formula (VI) in one reaction step, in a so-called one-pot process (cf. example 3).

The 1-unsubs t i tuted 4-amino-tr iazol inones of the formula (III) are known or obtainable analogously to known processes (compare, for example, J . Heterocyc I .

Chem. _16, 403 C 19793 ; J.Heterocycl . Chem. V7, 1691 M9803; Europ. J. Med. Chem. 215 C 19833; Chem. Ber. 98, 3025 C 19653 or Liebigs Ann. Chem. 637, 135 C19603).

The aldehydes or ketones of the formula (VII) are generally known compounds of organic chemistry.

Le A 25 302 - 25 - The majority of the l-unsubstituted triazolinone hydrazones of the formula (VIII) are known (cf. , for example, 3. Heterocycl, Chem. 20, 77-80 [19833; 3 .

Heterocycl. Chem, 16, 403-407 [19793; Chim, Acta. Turc, 7, 269-290 [19793; J. chem. Soc , ; Perkin Trans. II, 1973. 9-11; J. org. Chem. 36, 2190-2192 [19713).

The ( thio) chloroformic acid esters of the formula (IX) are generally known compounds of organic chemistry.

Some of the triazol inones of the formula (X) mentioned as intermediates are known (cf. for example Acta. Pol. Pharm. 38, 153-162 [19813 or C.A. 95: 203841 j) .

Triazol inones of the formula (Xa) , in which R ~ represents alkyl and R^, R^ , R^ , X and Y have the abovemen ioned meaning , are not yet known.

R1"1 preferably represents straight-chain or branched alkyl with 1 to 4, in particular with 1 to 3 carbon atoms; R1"1 particularly preferably represents methyl, Le A 25 302 - 26 - R3 and R4 preferably, in each case independently of one another represent hydrogen , straight-chain or branched alkyl with 1 to 4 carbon atoms or phenyl or benzyl , R5 preferably represents straight-chain or branched alkyl with 1 to 4 carbon atoms for benzyl or phenyl, optionally mono- to tr substituted by identical or different substituents , the following being possible substituents in each case: halogen, cyano, nitro, alkyl, alkoxy or alkylthio, each of which has 1 to 4 carbon atoms and each of which is straight-chain or branched, or halogenoalkyl , halogenoalkoxy or halogenoalkyl thio , each of which has 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and each of which is straight-chain or branched; R5 represents in particular methyl, ethyl, n- or i-propyl, n- , i-, s- or t-butyl, or benzyl or phenyl, optionally mono- to disubstituted by identical or different substituents, the following being possible substituents in each case: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, trifluoro- methyl , tri f luoromethoxy or trif luoromethyl hio; X and Y in each case independently of one another represent oxygen and sulphur, preferably oxygen* The lH-triazol inones required as starting materials for carrying out the process (b) according to the invention are defined generally by the formula (III).

Le A 25 302 - 27 - In this formula (III) R1 and Z preferably represent those radicals which were already mentioned as preferred substituents in connection with the description of the compounds of the formula (I) according to the invention.

The lH-triazol inones of the formula (III) are known or can be obtained analogously to known processes (cf. for example J, Heterocycl. Chem, 16., 403 [19793; J.

Heterocycl. Chem. 17, 1691 [1980]; Europ. J, Med, Chem. 18. 215 [1983]; Chem. Ber. 98, 3025 [1965]; Liebigs Ann. Chem. 637. 135 [1960], The i so ( thio ) cyanates also required as starting materials for carrying out the process (b) according to the invention are defined generally by the formula (IV). In this formula (IV) R2 and Y preferably represent those radicals which have already been mentioned as preferred substituents in connection with the description of the compounds of the formula (I) according to the invention.

The iso ( thio ) cyanates of the formula (IV) are mostly known compounds of organic chemistry. The compounds 2,2,2-trif luoroisopropylcyanate and 2,2 ,2-trif luoro-1 , 1-di-methyl-ethylcyanate are not yet known but can however be prepared according to known methods.

Iso(thio)cyanates can be obtained, for example, when corresponding amines are reacted with phosgene, if appropriate* in the presence of a base such as, for example, tr iethylamine (compare e . g . DE-0S , 804 , 802 , DE-OS 2,512,514, 0S-P 3,584,028, US-P 2,706,753, US-P 3,311,654, JA 50/29,599, Synthesis 1985, page 682 or J. Am, Chem. Soc. 77, 1901-1902 (1955)), The t iazol inones required as starting materials for carrying out the process (c) according to the invention are defined generally by the formula (V). In this formula (V), R1 , X and Y preferably represent those radicals which have already been mentioned as preferred substituents in connection with the description of the Le A 25 302 - 28 - compounds of the formula (I) according to the inven-tion.

R5 preferably represent straight-chain or branched alkyl with 1 to carbon atoms or benzyl or phenyl, optionally mono- to trisubstituted by identical or different substituents , the following being possible substituents in each case*, halogen* cyano, nitro* alkyl* alkoxy or alkylthio, each of which has 1 to 4 carbon atoms and each of which is straight-chain or branched, or halogenoalkyl , halogenoalkoxy or halogenoalkylthio * each of which has 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and each of which is straight-chain or branched; R5 represents in particular methyl* ethyl* n- or i-propyl* n-, i-, s- or t-butyl or benzyl or phenyl* optionally mono- to dieubstituted by identical or different substituents* possible substituents in each case being: fluorine* chlorine* bromine* cyano* nitro* methyl* ethyl* n- or i-propyl, n- , i-, s- or t-butyl * methoxy* ethoxy* n- or i-propoxy, methyl hio, trifluoro- methyl* trif luoromethoxy or trif luoromethyl thio .

Some of the triazolinones of the formula (V) are known (cf. for example J. Heterocycl, Chem. 17_, 1691-1696 [1980]).

Triazolinones of the formula (Va) Le A 25 302 - 29 - in which R1"1 represents alkyl, preferably straight-chain or branched alkyl with 1 to 4, in particular with 1 to 3 carbon atoms, and particularly preferably methyl and R5, X and Y have the abovement ioned meaning, are not yet known.

They are obtained analogously to the preparation of the known compounds of the formula (V), by reacting lH-triazol inones of the formula (Ilia) H in which R ~ and X have the abovement ioned meaning, with ( thio) chloroformi c acid esters of the formula (IX) , R°-0-C-Cl (IX) II Y in which 5 and Y have the abovement ioned meaning, if appropriate in the presence of a diluent such as for example tetrahydrofuran and if appropriate in the presence of a reaction auxiliary such ae for example Le A 25 302 - 30 - potassium-t-butylate or sodium hydride at temperatures between -20° C and +40° C (cf, also the preparation examples).

The lH-triazolinones of the formula (Ilia) are known or can be obtained analogously to Known processes (cf. for example J. Heterocycl. Chem. 16., 403 [19793; J. Heterocycl. Chem. 17, 1691 [19803; Europ. J. med.

Chem. 18, 215 [1983]; Chem. Ber. 98, 3025 [1965]; Liebigs Ann. Chem. 637. 135 [I960]).

All inorganic and organic acids customarily utilizable for hydrazone cleavage are suitable as acids for carrying out the process (a) according to the invention. Inorganic mineral acids such as hydrochloric acid, sulphuric acid or phosphoric acid are preferably used.

All customary organic or inorganic solvents are suitable as diluents for carrying out the process (a) according to the invention. Polar organic solvents miscible with water, in particular alcohols, such as methanol, ethanol, propanol or butanol, their mixtures with water or pure water are preferably used as diluents.

The reaction temperatures can be varied within a relatively wide range in carrying out the process (a) according to the invention. In general, the reaction is carried out at temperatures between 20°C and 150°C, preferably at temperatures between 50°C and 120°C.

The process (a) accordingto the invention is customarily carried out at atmospheric pressure or under reduced pressure. If the process is carried out under reduced pressure, then suitable pressure ranges are between 20 and 400 mbar, preferably between 100 and 200 mbar.

For carrying out the process (a) according to the invention, 1 to 50 moles, preferably 1 to 20 moles, of acid are generally employed per mole of hydrazone of the formula (II). To achieve this, the hydrazone of the I.e A 25 302 - 31 - formula (II) is dissolved in a suitable amount of diluent, then the necessary amount of acid is added and the mixture is slowly concentrated under reduced pressure over several hours.

In a particular embodiment it is also possible to carry out the process (a) according to the invention and the preparation of the precursors of the formula (II) necessary for said process in one reaction step, in a so-called one-pot process.

For this purpose it is possible to select the tria-zolinones of the formula (X) as starting compounds and to react them successively, in a one-pot process, with amines of the formula (VI) and then with acid according to process (a) according to the invention (in this connection cf. also the preparation examples), or alternatively, to select the triazoline hydrazones of the formula (VIII) as starting compounds and to react them successively, in a one-pot process with ( thio ) chloro-formic acid esters of the formula (IX), then with amines of the formula (VI) and then with acid according to process (a) according to the invention, Inert organic solvents can be used as dilents for carrying out process (b) according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as for example benzine, benzene, toluene, xylene, chloro-benzene, petroleum ether, hexane, cyclohexane, dichloro-methane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, nitriles, such as Le A 25 302 - 32 - acetonitrile or propionitri le * amides* such as dimethyl-formamide, dimethyl acetamide* N-methyl formamide * N-methylpyrrol idone or hexamethylphosphor i c acid triamide or esters, such as ethyl acetate.

The process (b) according to the invention is optionally carried out in the presence of a suitable reaction auxiliary. All customary inorganic or organic bases can be used as reaction auxiliaries. They include for example tertiary amines* such as triethylamine , N,N-dimethylani 1 ine , N,N-diethylbenzylamine , N,N-dimethyl-cyclohexylamine or dibutyl tin dilaureate, pyridine, Ν,Ν-dimethylaminopyridine* diazabicyclooctane (DABCO)* diazabicyclononene (DBN) and diazabicycloundecane (DBU) , When carrying out the process (b) according to the invention the reaction temperatures can be varied within a relatively large range. In general temperatures between 0° C and 150° C, and preferably temperatures between 20° C and 100° C are used.

In general 1.0 to 2.0 mols* preferably 1.0 to 1.5 mols of iso ( thio ) cyanate of the formula (IV) and, where appropriate* 0.001 to 2.0 mols* preferably 0.001 to 1.0 mol of reaction auxiliaries are used per mol of lH-triazol inone of the formula (III)* for carrying out process (b) according to the invention.

The reaction* the working up and the isolation of the reaction products are carried out according to generally auxiliary methods.

Inert organic solvents can be used as diluents for carrying out the process (c) according to the invention.

Le A 25 302 - 33 - These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as for example benzine, benzene, toluene, xylene, chloro-benzene, petroleum ether, hexane, cyclohexane, dichloro-methane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, nitriles, such as acetonitrile or propioni tri le , amides, such as dimethyl formamide, dimethyl acetamide, N-methylformanilide, N-methylpyrrol idone or hexamethylphosphoric acid triamide or esters, such as ethyl acetate, or sulphoxides, such as dimethyl sulphoxide.

The process (c) according to the invention can optionally be carried out in the presence of a suitable reaction auxiliary. All customary inorganic or organic bases are suitable as reaction auxiliaries. They include for example alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or sodium hydrogencarbonate , and tertiary amines, such as triethylamine , Ν,Ν-dimethylaniline, pyridine, N,N-dimethylaminopyridine , diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabxcycloundecane (DBU).

When carrying out the process (c) according to the invention the reaction temperatures can be varied within a relatively large range. In general temperatures between 0° C and 120° C and preferably temperatures between 20° C and 50° C are used.

In general 1.0 to 5.0 mols, preferably 1.0 to 2.5 mols of amine of the formula (VI) and optionally 1.0 Le A 25 302 - 34 - to 2.0 mols, preferably 1.0 to 1.2 mole of reaction auxiliaries are used per mol of triazolinone of the formula (V), for carrying out the process (c) according to the invention.

The reaction* the working-up and the isolation of the reaction products are carried out according tp generally customary methods.

In a particular embodiment it is also possible to carry out the process (c) according to the invention and the preparation of the precursors of the formula (V) necessary for said process in one reaction step, in a so-called one-pot process. ΙΗ-Triazol inones of the formula (III) are used as starting materials and they are reacted successively in a one-pot process first with (thio)chloroformic acid esters of the formula (IX) and then with amines of the formula (VI) according to process (c) according to the invention.

A further method of obtaining compounds of the formula (I) according to the invention comprises reacting oxadiazol nones of the formula (XI), in which R1 , R2 and Y have the abovementioned meaning, with hydrazine hydrate in the presence of a suitable Le A 25 302 - 35 - diluent such as for example methanol or ethanol at temperatures between 20° C and 100° C and thermally cyclising the resulting carbazidic acid derivatives of the formula (XII) (XII) in which R1 , R^ and Y have the abovement ioned meaning, in the presence of a suitable diluent such as for example toluene, chlorobenzene or dichlorobenzene , at temperatures between 80° C and 200° C.

Oxadiazol inones of the formula (XI) are known (cf, for example FR 14 15 605 or C.A. 64: P5105g and NL 6 510 645 or C.A, 6j>: P2274d-f) or can be obtained by generally Known processes, for example by reacting the corresponding 4H-oxadiazol inones with iso{ thio ) cyanates of the formula (IV) by a procedure analogous to that used for carrying out the process (b) according to the invention or to that used for synthesising the precursors of the formula (II).

Le A 25 302 - 36 - The purification of the final products of the formula (I) is carried out with the aid of customary processes, for example by column chromatography or by rec rys tal I i zat ion . The characterization is carried out with the aid of the melting point or with the aid of the proton nuclear magnetic resonance spectrum in the case of non-crystal I izable compounds.

The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Cheno-podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea and Mercurialis.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopers con, Arachis, Brassica, Lac-tuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Bra-chiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agro- Le A 25 302 - 37 - pyron, Cynodon, Monochoria, F imbr istyl is, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: 0ryz a , Zea , Trit -cum, Hordeum, Avena, Secale, Sorghum-, Panicum, Saccharum, Ananas, 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 manner to other plants.

The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

In this way the active compounds according to the invention can be used with particularly good effect for combating monocotyledon and dicotyledon weeds, in particular in dicotyledon cultures, such as for example sugarbeet.

In particular, the outstanding activity against mercury (Mercurial is), a problem weed which is difficult to control, is worthy of mention.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wett-able powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances .

Le A 25 302 38 - These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is 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 aliphatic hydrocarbons, such as chlorobenzenes, chloroethyl-enes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum frac-tions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethyl ormamide and dimethylsulphox ide, as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmoril-lonite or diatomaceous earth, and ground synthetic miner-als, such as highly disperse silicic acid, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks 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 poly-oxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, ar Isulphonates as well Le A 25 302 as albumin hydrolysat ion products; as dispersing agents there are suitable: for example I i gn i n-sulph i te waste liquors and methylcellulose.

Adhesives such as carboxymethylcel lulose and natural and synthetic polymers in the form of powders, granules or latices, 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 dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixes being poss ible.

Herbicides which are suitable for the mixtures are known herbicides such as, for example, 1-amino-6-ethylth o-3-(2,2-dimethylpropyt )-1,3,5-tr azine-2,4( 1H, 3H)-dione or N-(2-benzoth i azoly )-N,N'-di methyl urea for combating weeds in cereals; 4-amino-3-methy l-6-phenyl-1,2,4-tr iazin-5(4H)-one for combating weeds in sugarbeet and 4-amino-6-( 1 , 1-dimethy let hy I )-3-methy 11 h io-1,2,4-t r iaz in-5(4H)-one for combating weeds in soya beans.

Mixtures with 5-(2-chloro-4-tr if luoromethyl-phenoxy )-2-n i t ro-benzo c acid; chloroacety l-N-(methoxymethy I )-2,6-diethylanil de; methyl-6,6-dimethyl-2,4-dioxo-3-C 1-(2-propeny loxyam no)-butyl idene]-cyclohexanecarboxylate; Le A 25 302 - 40 - methyl-5-(2,4-dichlorophenoxy)-2-n trobenzoate; 5-ami no-4-ch loro-2-pheny I -2, 3-d i hydro-3-oxy-py r idaz i ne ; ethyl 2-•CC(4-chloro-6-methoxy-2-pyrimidinyl)-aniinocarbonyl3-aminosulphonyl>-benzoate; exo-1-methyl-4-(1-methylethyl)-2-<2-methylphenyl-methoxy )-7-o ab icyc lo(2,2, 1 )-heptane; ethyl 2--CC(4-chloro-6-metho y-2-pyridin l )-aminocarbonyl]-aminosulphonyl>-benzoate; 3,6-dichloro-2-pyridinecarboxy-lic acid; N,S-diethyl-N-cyclohexyl-thiolcarbamate; 3-(methoxycarbonylaminophenyl)-N-phenyl carbamate; 2-C4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl or its ethyl ester; 4-ami no-6-t-buty I -3-et hy 11 hio-1,2,4-triazin-5(4H)-one; 2--C4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy>-propano c acid, its methyl or its ethyl ester; trimethylsilylraethyL 2-C4-(3,5-d chloropyrid-2-yloxy)-phenoxy]-propionate; 5-(2-chloro-4-tr if luoromethylphen-oxy)-N-methylsulphonyl-2-nitrobenzamide; 2-{-4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]-phenoxy>-propanoic acid or its ethyl ester; methyl 2-C4-(2,4-dichlorophenoxy)-phenoxy]-propionate; 2-C5-methyl-5-<1-methylethyl )-4-oxo-2-imidazol in-2-yl.l-3-quinoline-carboxylic acid; 1-isobutylaminocarbonyl-2-imidazol tdin-one; 3-cyc lohexyl-5,6-tr methy lene-urac i I ; N-methyl-2-( 1,3-benzoth azol-2- loxy)-acetan l de; 2-chloro-N-(?2,6-dimethylphenyl)-N-[( lH)-pyrazol-1- I -methyl ]-acet am tde ; 2-ethyl-6-methy l-N-( 1-methyl-2-methoxyeth I )-chloroacet-an lide; S-iethoxycarbonylaminophenyD-N-iS'-methyl-phen D-carbamate; 2- 1-(ethoxamino)-butylidene]-5-(2-ethylth opropyl)-1,3-cyclohexadione; N,N-diisoproyl-S-(2,3,3-trichloroallyl)-thiolcarbamate or 2,6-dinitro-4-trif luoromethyl-N,N-dipropylaniline are also possible.

Surprisingly some mixtures also show synergistic action.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the Le A 25 302 - 41 - form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, preferably between 0.05 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 CH3)2 (process a) 20 ml of concentrated hydrochloric acid are added to 11.1 g (0.04 mol) of 1-(N-isobutylcarbamoyl )-4-iso-propyl ideneimino-3-methyl-1,2,4-triazol in-5-one in 100 ml of ethanol and the solution is concentrated at 60°C and about 200 fflbar in the course of 5 hours on a rotary evaporator. The residue is brought to crystallization by trituration with ethanol /diethyl ether (1:1) and dried in air. 4.3 g (50% of theory) of 4-amino-1-(N-isobuty l-carbamoyl)-3-methyl-triazol in-5-one of melting point Le A 25 302 - 42 - 183° C are obtained* Example 2 ( 3.6 g (0.036 mol) of t-butyl isocyanate and 0.05 g to 0.1 g of diazabicycloundecene (DBU) are added to 3.42 g (0.03 mol) of 4-amino-3-methyl-l ,2,4-(lH)-triazol in-5-one in 80 ml of absolute acetonitri le , the mixture is stirred for 2 hours at 20° C, concentrated in vacuo and the residue taken up in dichloromethane. the solution is washed with water, dried over sodium sulphate and concentrated in vacuo and the residue is crystallised by trituration with diethyl ether. 5,0 g (78.3% of theory) of 4-amino-l-(N-t-butyl-carbamoyl )-3-methyl-l ,2 ,4-triazol in-5-one of a melting point of 132° C are obtained.

Example 3 one-pot variant) Le A 25 302 - 43 - 4.2 g (0.03 mol) of (2 ,2-dichlorocyclopropyl ) -methylamine are added to 8.2 g (0.03 mol) of 4-isopropyl ideneimino-3-roethyl-l-phenoxycarbonyl-l ,2 ,4-triazol in-5-one in 50 ml of absolute tetrahydrofuran , the mixture is then stirred for 12 hours at 20° C, concentrated in vacuo and the residue taken up in 100 ml of ethanol, 3 ml of concentrated hydrochlorid acid are added to the solution which is stirred for 3 to 4 hours at 60° C and 200 mbar. For the working up the mixture is concentrated in vacuo, the residue is taken up in dichloromethane and the solution is washed three times with a saturated aqueous sodium hydrogen carbonate solution, dried over sodium sulphate and concentrated in vacuo. The residue is crystallised in vacuo. The residue is crystallised out by trituration with diethyl ether . 4,4 g (52% of theory) of 4-amino-l-[N-(2,2-dichlorocyclopropylmethyl ) -carbamoyl 3-3-methyl-l ,2,4-triazol in-5-one of a melting point of 149° C are obtained.

Example 4 CH3 (process c) Le A 25 302 - 44 - 8.9 g (0.088 mol) of 1 , 1 -dimethylbutylamine are added to 3.2 g (0.0137 mol) of -amino-3-methyl - 1 -phenoxycarbonyl - 1 , 2 ,4-tr iazol in-5-one in a mixture of 25 ml of tetrahydrofuran and 10 ml of dioxane, the mixture is heated to reflux temperature for 24 hours, concentrated in vacuo and the residue taken up in dichloromethane, the solution is washed with 2% sodium hydroxide solution and water, dried over sodium sulphate, the solvent removed in vacuo and the residue crystallised by trituration with diethyl ether. 1.9 g (61% of theory) of 4-amino- 1- CN- ( 1 , 1 -di -methylbutyl ) -carbamoyl ]-3-methyl-l ,2 ,4-tr iazol in-5 -one of a melting point of 110° C are obtained.

The following substituted triazol inones of the general formula (I) are obtained in a corresponding manner and according to the general instructions for the preparation: Le A 25 302 - 45 - Table 1 Example physical No. X Y properties CH3 -CH(CH3)2 0 0 mp. 63° C 10 CH3 -(CH2)5-CH2C1 1H-NMR*) 1,45 (m,4H) 11 -CH-C2H5 0 0 1H-NMR* ) 0,95 (t,CH3) CH3 Le A 25 302 - 46 - Table 1 (continuation) Exam le physical No. X Y proper- tiee 13 CH3 -CH(C2H5)2 0 0 mp.l03°C 14 CH3 -CH-CH(CH3)2 0 0 mp,103°C CH-, 17 CH- ■CH2~C~CH 0 0 mp,106°C (decomp . ) CH, 18 CH- CH-(CH2) 0 0 n|° 1.5496 CH- I 20 CH- ■c CH- S 0 mp.lOO0 C I CH3 Le A 25 302 - 47 - Table 1 (continuation) Exam le physical No. X Y properties 21 (CH2)5-CH2C1 mp.131° C CH- 23 ■C-CH2C1 0 0 mp.ll8°C 24 CH¾ -CH -CH=CH2 mp. 92° C 0 II 25 CH- CH2-C-0C mp.l27° C CH2C1 I 2 26 CH- 0 0 ng2 1.5055 I 3 CH2C1 CH- 27 CH, -C-CHCl- 0 0 mp.l76°C CH- Le A 25 302 - 48 - Table 1 (continuation) Example physical No. X Y properties CH: 28 C2H5 -CH2-C-CH3 0 0 1H H--NMR *) . 4,4i 7,95 CH: CH2F I 2 29 CH- -C-CH- 0 0 mp.l33°C CH2F CH2F I 2 30 C2H5 -C-CH- 0 0 mp.30-40° C i ¾ CH->F CH3 32 CH: -C-C2H5 0 0 mp. 99° C CH, -CH-(CH2)3-CH(CH3)2 0 0 !H-NMR* I 4,40; CH3 7,61 Le A. 25 302 - 49 - Table 1 (continuation) Example physical No. R1 R2 X Y properies 35 -CH. mp.l98°C 36 CH3 ~(CH2)3"CH3 0 0 mp.108- 109 °C 37 CH3 CH3 0 0 mp.168- 170 °C 38 CH3 -(CH2)2-CH3 0 0 mp.134- 136 °C CH I 3 39 CH, -CH C-CH3 0 0 mp.l49°C I I CH3 CH I 3 40 CH3 -C-CF 0 0 mp.149- I 151 °C CH3 Le A 25 302 - 50 - Table 1 (continuation) Exam le physical No. properies 41 CHo —( 0 0 mp.93- 3 1 94 °C 42 CH3 -CH2-CH2-CN 0 0 mp.175- 178 °C 43 CH3 -CH2-CH-(CH2)3-CH3 0 0 mp.91- j 92° C C2H5 CH- 44 C2H5 ■?-C2H5 mp.102 103 °C CH- CH3 45 CH- -C-CH2-F 0 0 mp.178 CH3 Le A 25 302 - 51 - Table 1 (continuation) Example physical No* X Y properties 49 CH- -CH 0 0 1H-NMR* 5 I 0.35-0.6; CH3 0.93 CH- 51 CH- ■C-CH -N 0 0 mp.211 °C (hydro¬ CH- chloride ) 53 CHg -C H5 o 0 nip.185 °C CH? I ci 55 CH- •C-CH*C< 0 0 mp.135 °C I CI CH3 Le A 25 302 - 52 - Table 1 (continuation) Examp e physical No. propert es CH, 57 CH3 -C-CSCH 0 0 mp.U9 °C CH, 58 CH, ■CH-CH2-C1 0 0 mp.136 °C 59 -C-CH?-C-CH 0 0 mp.122 °C CH3 CH3 60 CH, -CH-CF 0 0 mp.141 °C 3 I CH, I 61 CH, -C-CN 0 0 mp.176 °C 3 I CH, 62 CH3 -CH-(CH2)4-CH3 0 0 rap.67 CH, 63 CH3 -CH-CH2-0CH3 0 0 mp.120 CH- Le A 25 302 - 53 - Table 1 (continuation) Example physical No. x y properties 64 CH3 -(CH2)2-0CH3 0 0 mp.114 ) 66 CH3 -(CH2)3-CH3 0 S inp.147 69 CH, -CH- 0 S mp .212 71 -CH—CH-Cl 0 0 mp.114 °C I I CH3 CH3 CI 72 -CH-CH*C< 0 0 n§° 1.5328 I CI CH,C1 73 CH, -CH< 0 0 mp.120 °C CH=CH2 Le A 2S 302 54 Table 1 (continuation) Exam e physical No. X Y properies CH2C1 75 CH, -CH< and 0 0 mp.158 °C CH2C1 ■CH-CH?C1 Cl (3:1) 76 CH3 -CH-CH2C1 0 0 mp.147 °C C2H5 77 CH3 -CH-CH2-NN 0 0 nf>2 1.4995 (hydro¬ CH- chloride ) CH- 78 CH3 -C-(CH2)3-CH3 0 0 nge 1.4891 CH3 79 -CH3 -CH-(CH2)5-CH3 n8° 1.4920 CH: CH? I 3 80 CH3 -CH-CH2-C-CH3 0 0 mp.140 °C CH CH Preparation of the starting compounds Example II-1 12 g (0.12 mo I) of isobutyl isocyanate are added dropwise at 20°C with stirring to 6 g (0.04 mol) of 4-isopropyl idene im no-3-met l-1H-tr azol in-5-one and 4 g (0.04 mol) of t r i ethyl am i ne in 20 ml of dioxane and the mixture is stirred for 3 hours at 100°C after completion of the addition. For working up, the reaction mixture is concentrated in vacuo, the residue is taken up in 100 ml of dichloromethane, and the solution is washed repeatedly with 100 ml of water in each case, dried over sodium sulphate and freed from solvent in vacuo. 11.2 g (100% of theory) of 1-(N-isobutylcarbam-oyl)-4-isopropyl idene imino-3-meth 1-1 ,2,4-t r azol in-5-one are obtained as an oil.

H-NMR (C0C13): * * 0.85 (d, 6H) ppm.

The following initial products of the general formula (II) La A 25 302 - 63 - are obtained in a corresponding manner and according to the general instructions for the preparation: Le A 25 302 - 64 - Table 2 physical Exam le R2 =C X y properNo: ties II-2 CH3 -<3> =C(CH3)2 0 0 11-3 CH3 —^ =CH-CH(CH3)2 0 0 3,9 II-4 CH3 -CH-C2H5 =C(CH3)2 0 0 CH3 II-5 CH3 -CH(CH3)2 =C(CH3)2 0 0 II-6 CH3 -CH(C2H5)2 =C(CH3)2 0 0 II-9 CH3 -C-CH =C(CH3)2 0 0 mp, 88° C CH-a 2"5 Le A 25 302 - 65 - Table 2 (continuation) ^RJ physical Example R1 R2 •■C X Y proper-No: ^R4 ties 11-12 CH3 -CH2-C00C2H5 =C(CH3)2 0 0 mp.l08°C 11-13 CH3 -CH2-CH=CH2 =C(CH3)2 0 0 rop. 86° C I CH3 -CH2-C-CH3 =C(CH3)2 0 0 mp.121- I 122° C CH3 Le A 25 302 - 66 - Exaroo1 e 111 - 1 11.4 g (0.1 mol) of 4-amino-3-methyl-lH-l ,2,4-tria-zolin-5-one (compare Europ. J.Med .Chem, : Chim, Ther. 18. 215-220 [1983]) and 0.1 g of p-toluenesulphonic acid in 100 ml (79.06 gi 1.36 mol) of acetone are stirred at 70° C for 40 hours, and the mixture is then concentrated in vacuo. 15.4 g (100X of theory) of 4- sopropy1 idene-imino-3-methyl-lH-l , 2 ,4-triazol in-5-one of melting point 140-144° C are obtained.

Example V- 1 2*7 g (0.024 mol) of potassium-t-butylate are added to 2.3 g (0.02 mol) of 4-amino-3-methyl-l ,2,4-(lH)-tria-zolin-5-one in 25 ml of absolute tetrahydrofuran , the mixture is stirred for 1 hour at 20° C, 3.1 g (0,02 mol) of phenyl chloroformate are then added dropwise with stirring, the mixture is stirred for 12 hours at room temperature, than the pH is adjusted to 5 with glacial Le A 25 302 - 67 - acetic acid, the mixture is concentrated in vacuo, the residue is taken up in chloroform, and the solution is washed with water, dried over sodium sulphate, concentrated in vacuo and the residue crystallised by trituration with ether. 1.1 g (23.5% of theory) of 4-amino-3-methyl-l-phenoxycarbonyl-1 ,2,4-triazolin-5-one of a melting point of 175° C are obtained.

Example X- 1 13.4 g (0.12 mol) of potassium- t-butylate are first added at room temperature to 15.4 g (0*1 mol) of 4-isopropyl ideneimino-3-methyl-l ,2 ,4- ( 1H) -triazol in-5-one in 100 ml of absolute tetrahydrofuran , the mixture is stirred for one hour at room temperature, 15.5 g (0.1 mol) of phenyl chloroformate are then added and the mixture is stirred for a further 12 hours at 20° C.

For the working up the mixture is acidified with glacial acetic acid and concentrated in vacuo, the residue is taken up in chloroform and the solution is washed with water, dried over sodium sulphate, concentrated once again in vacuo and the residue recrystallised from acetone.

Le A 25 302 - 68 - 10 g (36.5¾ of theory) of 4- i sopropyl idene imino-3-methyl - 1 -phenoxycarbonyl - 1 , 2 ,4- triazol in-5-one of a melting point of 162° C are obtained.

Example X-2 1.5 g (0.05 mol) of sodium hydride are added at 20° C to 7.7 g (0.05 mol) of 4-isopropylideneimino-3-methyl-1 ,2,4- ( 1H ) - tr iazol in-5-one in 50 ml of absolute tetrahydrofuran , the mixture is stirred for one hour at room temperature and then 5,4 g (0.05 mol) of ethyl chloroformate are added dropwise with stirring and when the addition has ended the mixture is stirred at 20° C for a further 12 hours.

For the working up the mixture is acidified with glacial acetic acid and concentrated in vacuo, the residue is taken up in dichloromethane and the solution is washed with water, dried over sodium sulphate, concentrated once again in vacuo and the residue recrystal-lised from isopropanol. 5.0 g (44% of theory) of l-ethoxycarbonyl-4-iso-propyl ideneimino-3-methyl-l ,2,4-triazolin-5-one of a melting point of 91° C are obtained.

Le A 25 302 - 69 - Use Examples: The compounds shown below were employed as the comparison substances in the following use examples: 4-Amino-3-methy1-6 -phenyl- 1 ,2 ,4-triazin-5-one (known from DE-OS (German Published Specification) 2,364,474, Example 1-22) N-Isobutyl-2-oxoimidazolidine-l-carboxamide (known from R. Wegler "Chemie der Pf lanzenschutz- und Schadl ingsbe-kampfungsmittel" Vol. 5, page 219 (1977)), Le A 25 302 - 70 - Example A Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active 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.

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 X ■ no action (like untreated control) 100 % = total destruction.

In this test, for example, the compounds according to the preparation examples 2, 14, 23, 32, 41, 45, 48 and 57 show a remarkedly better herbicidal activity against weeds and a remarkedly better selectivity in useful plants, such as, for example , sugar beets, than the comparison substance (B).

Le A 25 302 - 71 - Table A - Pre-emergence-Test / greenhouse Amount employed Active compound kg/ha Sugar beets Alopecurus Amaranthus Datura Sinapis St (B) 2000 30 70 0 40 80 (known) ( 2) 2000 0 90 100 100 100 (14) 2000 0 80 100 100 100 (23) 2000 0 90 100 100 100 (32) 2000 0 95 100 100 100 (41) 2000 0 80 100 80 100 (45) 2000 - 80 100 100 100 (48) 2000 0 80 100 95 90 (57) 2000 0 80 100 100 100 Example B Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active com-pound, 1 part by weight of active compound 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 2,000 I 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, for example, the compounds according to Examples 1 and 48, and 1, 2, 3, 14, 23, 32, 41, 45, 48, 57 and 78 show a distinctly better herbicidal action than the comparison substance (A) and (B) ,respectively in combating mono- and dicotelydon weeds.

Le A 25 302 - 72 - Table B-2: : Post-emergence-Test / greenhouse Active Amount compound employed Sugar beets AmaranLhus Chenopodium Datura kg/ha (B) 2000 50 20 70 30 (known) ( 2) 2000 0 100 100 100 (14) 2000 0 90 100 100 (23) 2000 0 100 100 100 (32) 2000 10 100 100 100 (41 ) 2000 0 100 100 100 (45) 2000 10 100 100 100 (48) 2000 0 90 95 100 (57) 2000 10 100 100 100 (78) 2000 10 100 100 100 - 73 - 86668/2

Claims

1. Substituted triazolinones of the formula (I) in which R1 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, alkoxyalkyl, cycloalkyl, cycloalkylalkyl, tetrahydrofuranyl, tetrahydrofuranylalkyl, or represents benzyl or phenyl, which are in each case optionally monosubstituted, disubstituted or trisubstituted by identical or different substituents, selected from: flourine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, R2 represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, halogenoalkinyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkenyl, alkyl- aminoalkyl, dialkylaminoalkyl, or represents cycloalkyl having 11 carbon atoms, or represents cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl in each case having 3 to 8 carbon atoms in the cycloalkyl or cycloalkenyl part and where appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl part, and which are in each case optionally monosubstituted or polysubstituted by identical or different substituents selected from halogen, cyano and also in - 74 - 86668/2 each case straight-chain or branched alkyl or halogenoalkyl in each case having 1 to 4 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms or represents straight-chain or branched halogenoalkenyl having up to 4 carbon atoms and 1 to 5 halogen atoms or in each case bivalent bonded alkanediyl or alkenediyl in each case having up to 4 carbon atoms; furthermore, R2 represents heterocyclylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part and 1 to 9 carbon atoms and also 1 to 3 hetero atoms - in particular nitrogen, oxygen and/or sulphur - in the heterocyclic part, and which is optionally monosub- stiruted or polysubstituted in the heterocyclic part by identical or different substituents selected from halogen, cyano, nitro, and also in each case straight-chain or branched alkyl, alkoxy, alkylthio halogenoalkyl, halogenoalkoxy, halogenoalkylthio or alkoxycarbonyl in each case having 1 to 5 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms; furthermore, R2 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, or R2 represents optionally \ straight-chain or branched benzyl, phenylethyl, phenylpropyl, , phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenylcyano- methyl, phenylcyanoethyl, phenylcyanopropyl, benzyloxy, phenyl- ethyloxy, phenoxy, benzoyl, phenyl or naphthyl, which are in each case optionally monosubstituted, disubstituted or trisubstituted on the phenyl ring by identical or different substituents selected from flourine, chlorine, bromine, hydroxyl, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, methylsulphinyl, - 75 - 86668/2 methylsulphonyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, cyclohexyl or phenoxy, or represents alkoxy, alkenyloxy or alkinyloxy, X represents oxygen or sulphur and Y represents oxygen or sulphur.

2. Substituted triazolinones of the formula (I) according to Claim which R1 represents hydrogen, or 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 the individual alkyl parts, or represents cycloalkyl or cycloalkylalkyl in each case having 3 to 7 carbon atoms in the cycloalkyl part and where appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl part, or represents tetrahydrofuranyl, or represents tetrahydrofuranylalkyl optionally having 1 to 4 carbon atoms in the straight-chain or branched alkyl part, or represents benzyl or phenyl, which are in each case optionally monosubstituted, disubstituted or trisubstituted by identical or different substituents, selected from: flourine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, R2 represents hydrogen, or represents in each case straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 8 - 76 - 86668/2 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 or halogenoalkinyl in each case having 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, hydroxyalkyl having 1 to 8 carbon atoms and 1 to 6 hydroxyl groups, alkoxyalkyl, alkoxycarbonylalkyl or alkoxy-carbonylalkenyl in each case having up to 6 carbon atoms in the individual alkyl or alkenyl parts, alkylaminoalkyl or dialkylamino-alkyl in each case having 1 to 6 carbon atoms in the individual alkyl parts, cycloalkyl having 11 carbon atoms, or represents cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl in each case having 3 to 8 carbon atoms in the cycloalkyl or cycloalkenyl part and where appropriate 1 to 6 carbon atoms in the straight-chain or branched alkyl part, and which are in each case optionally monosubstituted or poly substituted by identical or different substituents selected from halogen, cyano and also in each case straight-chain or branched alkyl or halogenoalkyl in each case having 1 to 4 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms or represents straight-chain or branched halogenoalkenyl having up to 4 carbon atoms and 1 to 5 halogen atoms or in each case bivalent bonded alkanediyl or alkenediyl in each case having up to 4 carbon atoms; furthermore, R2 represents heterocyclylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part and 1 to 9 carbon atoms and also 1 to 3 hetero atoms - in particular nitrogen, oxygen and/or sulphur - in the heterocyclic part, and which is optionally monosubstituted or polysubstituted in the heterocyclic part by identical or different substituents selected from halogen, cyano, nitro, and also in each case straight-chain or branched alkyl, alkoxy, - 77 - 86668/2 alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio or alkoxycarbonyl in each case having 1 to 5 carbon atoms and where appropriate 1 to 9 identical or different halogen atoms; furthermore, R2 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, or R2 furthermore represents heterocyclylmethyl, heterocyclylpropyl or heterocyclylethyl, which are optionally monosubstituted, disubstituted or trisubstituted in the heterocyclic part by identical or different substituents.the heterocycles in each case being selected from where Z in each case represents oxygen or sulphur, and where the optional substituents in each case are: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoro- methylthio; X represents oxygen or sulphur; and Y represents oxygen or sulphur. - 78 - 86668/2

3. Process for the preparation of substituted triazolinones of the formula (I) in which R1, R2, X and Y have the same meaning as in Claim 1, characterized in that (a) hydrazones of the 10 in which , R , X and Y have the abovemen t i oned meaning and and independently of one another in each case represent hydrogen, alkyl, aralkyl or aryl, are reacted with an acid, if appropriate in the presence of a diluent, or in that b) lH-triazol inones of the formula (III), 20 H 25 in which and X have the above mentioned meaning are reacted with i so ( thio ) cyanates of the formula (IV), 30 R2-N=C=Y (IV) - 79 - 86668/3 triazolinones of the formula (V) Y 0-Rb i n wh i c h R , X and Y have the above mentioned meaning and R5 represents alkyl, aryl or arylalkyl, are reacted with amines of the formula (VI), R2-NH2 (VI) in which R has the above mentioned meaning, * if appropriate, in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary.

4. Herbicidal compositions characterized in that they contain an effective amount of at least one substituted triazolinone of the formula (I) according to Claims 1 to 2.

5. Process for combatting weeds, characterized in that substituted triazolinones of the formula (I) according to Claim 1 or 2 are allowed to act on the weeds and/or their environment.

6. Process for the preparation of herbicidal compositions characterized in that effective amounts of substituted triazolinones of the formula (I) according to Claims 1 or 2 are mixed with extenders and/or surface-active substances. For the Applicants,