CA2227012A1 - Substituted aryl sulphonyl amino (thio) carbonyl triazolin(thi)ones - Google Patents
Substituted aryl sulphonyl amino (thio) carbonyl triazolin(thi)ones Download PDFInfo
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- CA2227012A1 CA2227012A1 CA 2227012 CA2227012A CA2227012A1 CA 2227012 A1 CA2227012 A1 CA 2227012A1 CA 2227012 CA2227012 CA 2227012 CA 2227012 A CA2227012 A CA 2227012A CA 2227012 A1 CA2227012 A1 CA 2227012A1
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
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- 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
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- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to novel substituted aryl sulphonyl amino (thio) carbonyl triazolin(thi)ones of formula (I) in which Ar is possibly substituted arylene or heteroarylene; Q1 is oxygen or sulphur; Q2 is oxygen or sulphur; R1 is hydrogen, hydroxy, amino, alkylidene amino or a possibly substitued radical from the series alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkyl alkyl, aryl, arylalkyl; R2 is hydrogen, hydroxy, mercapto, amino, halogen or a possibly substituted radical from the series alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylamino, alkenylamino, alkinylamino, dialkylamino, alkanoylamino, aziridino, pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cycloalkoxy, cycloalkylthio, cycloalkylamino, cycloalkyl alkyl, cycloalkyl alkoxy, cycloalkyl alkylthio, cycloalkyl alkylamino, aryl, aryloxy, arylthio, arylamino, arylalkyl, arylalkoxy, arylalkylthio, arylalkylamino, heterocyclyloxy, heterocyclylthio;
or R1 and R2 together are possibly branched alkandiyl; and R3 is possibly substituted heterocyclyl; and salts of the compounds of formula (I), process for producing the novel compounds and their use as herbicides.
or R1 and R2 together are possibly branched alkandiyl; and R3 is possibly substituted heterocyclyl; and salts of the compounds of formula (I), process for producing the novel compounds and their use as herbicides.
Description
~ CA 02227012 1998-01-14 , WO 97/03980 PCT/EP96/02932 ~, ~ b Subsliluled arvlsulphonvlamino(thio)carbonvllr;~olin(e-thi)ones The invention relates to novel substituted arylsulphonylamino(thio)carbonyltriazolin(e-thi)ones, to a plurality of processes for their prep~alion and to their use as herbicides.
It is a].ready known that certain sulphonylaminocarbonyltriazolinones have herbicidal properties (cf. EP-A 341489, EP-A 422469, EP-A 425948, EP-A 431291, EP-A
507171). However, the activity ofthese compounds is not satisfactory in every respect.
This invention, accordingly, provides the novel substituted arylsulphonylamino(thio)-- carbonyltriazolin(e-thi)ones of the general formula (I) Q' ~ (I) l O in which Ar represents respectively optionally substituted arylene or heteroarylene, Q' represents oxygen or sulphur, Q2 represents oxygen or sulphur, R' represents hydrogen, hydroxyl, amino, alkylideneamino or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, R2 represents hydrogen, hydroxyl, mercapto, amino, halogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinyl-thio, alkylamino, alkenylamino, alkinylarnino, dialkylarnino, alkanoylarnino, aziridino, pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cyclo-alkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio, cycloalkylalkylamino, aryl, aryloxy, arylthio, arylarnino, S arylalkyl, arylalkoxy, arylalkylthio, arylalkylarnino, heterocyclyloxy, hetero-cyclylthio, or R' and R2 together represent optionally branched ~lk~ne~liyl, and R3 l~,es~ optionally sub~liluled heterocyclyl, and salts of the compounds of the formula (I).
] 0 The novel substituted arylsulphonylamino(thio)carbonyl-triazolin(e-thi)ones of the general forrnula (I) are obtained when (a) triazolin(e-thi)ones of the general formula (II) H--N~N--R' (Il) N =(R2 in which IS Q', R' and R2 are each as defined above are reaicted with substituted arylsulphonyliso(thio)cyanates of the general formula (III) R3-O-CO-Ar-SO2-N=C=Q2 (III) in which WO 9'7/03980 PCT/EP96/02932 Ar, Q2 and R3 are each as defined above, if a~ l;ate in the presence of a reaction auxiliary and if a~ropliate in the presence of a diluent, or 5 (b) triazolin(e-thi)one derivatives of the general forrnula (IV) z J~--N )~ N--R1 (IV) in which Ql, Q2, R~ and R2 are each as defined above and Z represents halogen, alkoxy, aryloxy or arylalkoxy ] 0 are reacted with sulphonarnides of the general forrnula (V) R3-o-co-Ar-so2-NH2 (V) in which Ar ancl R3 are each as defined above, if app~opl;ate in the presence of an acid acceptor and if applu~l;ate in the presence of ] 5 a diluent, or (c) triazolin(e-thi)ones of the general forrnula (II) H--N N--R (Il) N =~
in which Q', R' and R2 are each as defined above S are reacted with substituted arylsulphonarnide derivatives of the general formula (VI) R3-O-CO-Ar-SO2-NH-CQ2-Z (VI) in which Ar, Q2 and R3 are each as defined above and Z represents represents halogen, alkoxy, aryloxy or arylalkoxy, 10 if a~,pluyliate in the presence of an acid acceptor and if apl)lo~l;ate in the presence of a diluent, or (d) triazolin(e-thi)ones of the general forrnula (II) H_NJ~N_R' (Il) ~N =(R2 in which Q', R' and R2 are each as defined above are reacted with substituted arylsulphonyl halides of the general formula (VII) R3-O-CO-Ar-SO2-X (VII) 5 in which Ar and R3 are each as defined above and X represents halogen and metal (thio)cyanates of the general formula (VIII) MQ2CN (VIII) 10 in whic:h Q2 is as defined above and M represents an alkali metal or an ~Ik~line earth metal equivalent, if applop,iate in the presence of a reaction auxiliary and if approl,l;ate in the presence of a di]uent, 15 and, if approp~;ate, the compounds of the formula (I) obtained by the processes (a), (b), (c) or (d) are converted into salts by customary methods.
The novel sulphonylamino(thio)carbonyl-triazolin(e-thi)ones of the general formula (I) have strong herbicidal activity.
WO 97tO3980 PCT/EP96/02932 The invention preferably provides compounds of the formula (I) in which Ar represents phenylene or naphthylene, each of which is optionally substituted by halogen, cyano, nitro, by C,-C4-alkyl, C1-C4-alkoxy, C,-C4-alkylthio, C,-C4-alkylsulphinyl, C,-C4-alkylsulphonyl, di-(CI-C4-alkyl)-arnino-sulphonyl orN-C~-C4-alkoxy-N-C,-C4-alkyl-amino-sulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represents heteroarylene of 5 or 6 ring members, at least one of which is oxygen, sulphur or nitrogen and one or two more are optionally nitrogen, which is optionally substituted by halogen, cyano, nitro, by C,-C4-alkyl or C,-C4-alkoxy (each of which is optionally 11~ substituted by fluorine andlor chlorine), Ql represents oxygen or sulphur, Q2 represents oxygen or sulphur, Rl :represents hydrogen, hydroxyl, amino, represents C2-C10-alkylideneamino, :represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-alkoxy-, Cl-C4-alkyl-carbonyl- or Cl-C4-alkoxy-carbonyl-substituted C~-C6-alkyl, represents :respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-.alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, cyano-, C,-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C,-C6-alkoxy, Cl-C6-,alkylamino or C,-C6-alkanoylamino, represents C3-C6-alkenyloxy, represents di-I(C,-C4-alkyl)-amino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- andlor C,-C4-alkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C~-C4-alkyl, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- andlor C~-C4-alkoxy-.substituted phenyl or phenyl-C,-C4-alkyl, 25 R2 :represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, :iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-,alkoxy-, C~-C4-alkyl-carbonyl- or C~-C4-alkoxy-carbonyl-substituted C~-C6-alkyl, WO 9'l/03980 PCT/EP96/02932 represents respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, le~rese~ respectively optionally fluorine-, chlorine-, cyano-, Cl-C4-alkoxy- or C,-C4-alkoxy-carbonyl-substituted Cl-C6-alkoxy, C,-C6-alkylthio, C,-C6-alkylamino or C,-C6-alkanoylamino, represents C2-C6-alkenyloxy, C2-C6-alkinyloxy, C2-C6-alkenylthio, C2-C6-alkinylthio, C2-C6-alkenylamino or C2-C6-alkinylamino, represents di-(C,-C4-alkyl)-amino, represents respectively optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C,-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C,-C4-alkyl,- C3-C6-cycloalkyl-C,-C4-alkoxy, C3-C6-cycloalkyl-CI-C4-alkylthio or C3-C6-cycloalkyl-C~-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C,-C4-alkyl-, trifluoromethyl- and/or C,-C4-alkoxy-substituted substituted phenyl, phenyl-C,-C4-alkyl, phenoxy, phenyl-C,-C4-alkoxy, phenylthio, phenyl-C,-C4-alkylthio, phenylamino or phenyl-C,-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C,-C4-alkyl-, trifluoromethyl- and/or C,-C4-alkoxy-substituted heterocyclyloxy or heterocyclylthio, the heterocyclyl component being in each case selected from the group consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, thietanyl, thienyl, tetrahydrothienyl, or R~ and R2 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and R3 represents respectively optionally halogen- or C,-C4-alkyl-substituted oxetanyl, thietanyl, furyl, tetrahydrofi~ryl, thienyl or tetrahydrothienyl.
Furthelmore, the invention preferably provides the sodium, potassium, magnesium,calcium, ammonium, Cl-C4-alkyl-ammonium, di-(C~-C4-alkyl)-ammonium, tri-(C~-C4-alkyl)-ammonium, tetra-(C,-C4-alkyl)-ammonium, tri-(C,-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C,-C2-alkyl)-benzyl-ammonium salts of compounds WO 9'7/03980 PCT/EP96J02932 of the ~formula (I) in which Ar, Ql, Q2, Rl, R2 and R3 are each as defined above by way of preference.
The invention in particular provides compounds of the formula (I) in which Ar leplesenl~ respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, S methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoro-methoxy-, trifluoromethoxy-, methylthio- or ethylthio-substituted 1,2-phenylene (ortho-phenylene), pyridine-2,3-diyl, thiophene-2,3-diyl or pyrazol-4,5-diyl, Ql represents oxygen or sulphur, Q2 represents oxygen or sulphur, 10 Rl represents hydrogen, hydroxyl, amino, represents C3-C8-alkylideneamino, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy- substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents dimethylamino or diethylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclo-hexylmethyl, or repl~sent~ respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl, R2 le~leselll~ hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, WO 9'7/03980 PCT/EP96/02932 butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s-or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenyl-amino, propinylamino, or butinylamino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl-and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-methoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclo-pentylmethylamino or cyclohexylmethylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or represellt~ respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted oxetanyloxy, furyloxy, tetrahydrofuryloxy, thienyloxy or tetrahydrothienyloxy, or R' and R2 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and R3 represents respectively optionally fluorine-, chlorine-, methyl- or ethyl-substituted oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl or tetrahydro-thienyl.
A very particularly preferred group of compounds of the formula (I) are the compounds of the i~ormula (Ia) ~ 2'NJ~--N N - R (la) in whirch Ql, Q2, R~, R2 and R3 each have the me~nine~ given above as being particularly pre-ferred.
5 The general or preferred radical definitions listed above are valid both for the end products of the formula (I) and also, in a corresponding manner, for the starting materials or intennetli~tes which are required in each case for the p~ ~dlion. These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of plef~ d compo~imds.
l O Using, for example, 2-(oxetan-3-yl-oxy-carbonyl)-phenylsulfonylisocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following scheme:
~ H--N N--OCH3 [~1~ so2 )~--N )~ N--OCH3 o o C2Hs 0~0 C2Hs ~0 ~0 15 Using, for example, 2-(thietan-3-yl-oxy-carbonyl)-benzenesulphonamide and 2-chloro-carbonyl-4-dimethylamino-5-methyl-2,4-dihydro-3H- 1 ,2,4-triazol-3-thione as starting materials, the course of the reaction in the process (b) according to the invention can be illu,trated by the following scheme:
WO 9'7/03980 PCT/EP96/02932 O~s ~cS
[~ ~ S ~Z--N )~--N N _ N(CH,)2 Using, for example, N-methoxycarbonyl-2-(2-tetrahydrofuryl-methoxy-carbonyl)-benzenesulphonamide and 5-ethoxy-4-methyl-2,4-dihydro-3H- 1 ,2,4-triazol-3-one as starting materials, the course of the reaction in the process (c) according to the 5 invention can be illustrated by the following scheme:
1~ 1 0 ~,0 0' o"
J"'~O + ~ ~ '' ~O o ~
"' - '''' SO N, N HOCH ~ ~-' " SO ~ N ~ N - CH3 ~ N ~, OCH3 OC2H5 OC2H5 Using, for exarnple, 4-ethyl-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one and 2-(3-thietanyl-oxy-carbonyl)-benzenesulphonyl chloride and potassium cyanate as starting materia,ls, the course of the reaction in the process (d) according to the invention can 10 be illustrated by the following scheme:
WO 9'7/03980 PCT/EP96/02932 ~S ~c~S
[~o H_NJ~N_C2Hs ~ KOCN ~2 NH \ =~
SC2Hs The fo~mula (II) provides a general definition of the triazolin(e-thi)ones to be used as starting materials in the processes (a), (c) and (d) according to the invention for preparing compounds of the formula (I). In the formula (II), Ql, R' and R2 each S preferably or in particular have those me~ning.C which have already been given above, in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly plefe.,cd for Q~, R' and R2.
The tri,azolin(e-thi)ones of the general formula (II) are known and/or can be prepared by processes known per se (cf. Arch. Pharm. 301 (1968), 827; loc. cit. 307 (1974), 889;
Bull. Soc. Chim. France 1962, 1365; loc. cit. 1975, 1191; Chem. Ber. 90 (1957), 909-921; loc. cit. 98 (1965), 3025-3099; loc. cit. 102 (1969), 755; J. Heterocycl. Chem. 15 (1978), 237-240; J. Indian Chem. Soc. 6 (1929), 565; Liebigs Ann. Chem. 637 (1960), 135; M~onatshefte Chemie 123 (1992), 257; Tetrahedron 32 (1976), 2347-2352; Helv.
Chim. .Acta 63 (1980), 841-859; J. Chem. Soc. C 1967, 746-751; loc. cit. 1970, 26-34;
J. Chern. Soc. Perkin I 1973, 2644; Fen Fak. Derg., Seri A (Ege Univ.) 7 (1984), 1-6 -cited in Chem. Abstracts 101:90846m; EP-A 283876; EP-A 294666; EP-A 298371;
EP-A 301946; EP-A 305844; EP-A 341489; EP-A 362633; EP-A 370293; EP-A
391187; EP-A 398096; EP-A 398097; EP-A 399294; EP-A 415196; EP-A 422469;
EP-A 425948; EP-A 431291; EP-A 477646; EP-A 502307; EP-A 503437; EP-A
505815'; EP-A 511569; EP-A 513621; DE-A 2336827; DE-A 3839206; DE-A 3916208;
DE-A :3916930; DD-P 64970; WO-A 93/04050; P.cparalion Examples).
The formula (III) provides a general definition of the substituted arylsulphonyl iso-(thio)cyanates fi~rther to be used as starting materials in the process (a) according to the invention for p.cpa hlg compounds of the formula (I). In the formula (III) Ar, Q2 and R3 each preferably or in particular have that me~ning which has already been given above, in connection with the description of the compounds of the formula (I) according to the invention, as being ple~llcd or as being particularly preferred for Ar, Q2 ancl R3.
S The slarting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. EP-A 496701, EP-A 558445).
The formula (IV) provides a general definition of the triazolin(e-thi)one derivatives to be used as starting materials in the process (b) according to the invention for ~,lep~illg the compounds of the general formula (I). In the formula (IV), Ql, Q2, Rl and R2 each 10 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I), as being preferred or as being particularly prefe.l~,d for Q~, Q2, R~ and R2; Z preferably repre-sents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
15 Some of the starting materials of the formula (IV) have not been disclosed in the literature and form part of the subject matter of commonly ~sign~d earlier patent applications.
The compounds of the general formula (IV) are obtained when triazolin(e-thi)ones of the general forrnula (II) H_N~N_R' (Il) N ~(R2 in which Q', R' and R2 are each as defined above W O 9'7/03980 PCTAEP96/02932 are reacted with carbonic acid derivatives of the general formula (IX) z-co-zl (IX) in which Z is as defined above and 5 Z1 represents halogen, alkoxy, aralkoxy or aryloxy (and has the same preferred m-o~nings as Z), if apl)lol fiate in the presence of an acid acceptor such as, for example, sodium hydroxide or potassium hydroxide, sodium t-butoxide or potassium t-butoxide, and if applol,,;ate in the presence of a diluent such as, for example, methylene chloride, 10 tetrahydrofuran or dimethoxyethane and/or water, at te~l~pc.~lu,es between 0~C and 1 OO~C.
The formula (V) provides a general definition of the sulphonamides further to be used as starting materials in the process (b) according to the invention for ~ al;llg the compolmds of the general formula (I). In the formula (V), Ar and R3 each preferably 15 or in particular have that meaning which has already been given above, in connection with the description of the compounds of the formula (I), as being plefelled or as being particularly preferred for Ar and R3.
The starting materials of the formula (V) are known and/or can be prepared by pro-cesses known per se (cf. EP-A 496701, EP-A 558445).
20 The formula (VI) provides a general definition of the substituted arylsulphonamide derivatives to be used as starting materials in the process (c) according to the invention for plepal;llg the compounds of the formula (I). In the formula (VI), Ar, Q2 and R3 each preferably or in particular have that meaning which has already been given above, in connection with the description of the compounds of the formula (I), as being W O 9'7/03980 PCTAEP96/02932 pler~.l, d or as being particularly p~c~-~cd for Ar, Q2 and R3; Z preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
The st~rting materials of the formula (VI) are known ancl/or can be prepared by 5 processes known per se.
The folmula (VII) provides a general definition of the substituted arylsulphonyl halides to be used as starting materials in the process (d) according to the invention for pre-paring the compounds of the formula (I). In the formula (VII), Ar and R3 each pre-ferably or in particular have that me~ning which has already been given above, in 10 connection with the description of the compounds of the formula (I), as being preferred or as being particularly preferred for Ar and R3; X preferably represents fluorine, chlorine or bromine, in particular chlorine.
The starting m~tt~ri~l~ of the formula (VII) are known and/or can be prepaled byprocesses known per se (cf. EP-A 496701, EP-A 558445).
The processes (a), (b), (c) and (d) according to the-invention for the prep~lion of the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene; 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, for example acetonitrile and propionitrile; amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexam~ thylphosphoric triamide.
WO 9'T103980 PCT/EP96/02932 As reaction auxiliaries and/or as acid acceptors in the processes (a), (b), (c) and (d) according to the invention it is possible to employ all acid-binding agents which can customarily be used for such reactions. Preference is given to alkali metal hydroxides, for example sodium hydroxide and potassium hydroxide, ~Ik~lin~ earth metal 5 hydroxides, for example calcium hydroxide, alkali metal carbonates and alkoxides, such as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropyl-amine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4--ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1 ,4-diazabicyclo-[2,2,2]-octane (DABCO).
The reaction te~ dlules in the processes (a), (b), (c) and (d) according to the invention can be varied within a relatively wide range. The reactions are in general carried out at telll~ res of between -20~C and +150~C, preferably at temperatures bet~,veen 0~C and +100~C.
The processes (a), (b), (c) and (d) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
20 For calrying out processes (a), (b), (c) and (d) according to the invention, the starting materials required in each case are in general employed in approximately equimolar quantities. However, it is also possible to use one of the components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a 25 number of hours at the particular telllpeldlur~ required. Work-up in the processes (a), (b), (c) and (d) according to the invention is in each case carried out by customary methods (cf. the Plel)~dlion Examples).
Salts of the compounds of the general formula (I) according to the invention can be WO 9'7/03980 PCT/EP96/02932 ,lepaled if desired. Such salts are obtained in a simple manner by customary methods of fornning salts, for example by dissolving or dispersing a compound of the formula (I) in an applopl;ate solvent, for example methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding an applop~iate base. The salts can then - if desired after 5 prolonged stirring - be isolated by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers 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 not wanted.
Whether the substances according to the invention act as total or selective herbicides ] 0 depencls essentially on the amount used.
The active compounds according to the invention can be used, for example, in connec:tion with the following plants:
Dicotvledonous weeds of the ~enera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemi~, Galinsoga, Chenopodium, Urtica, Senecio, Alll;~lllhus, Portulaca, 15 Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsiurn, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lin~eTni~ Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the ~enera: Gossypiurn, Glycine, Beta, Daucus, Phaseolus, Pisum. Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, 20 Lactuca, Cucumis and Cucurbita.
Monocot~ledonous weeds of the ~enera: Echinochloa, Setaria, Panicum, Digitaria, Phleurn, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and 25 Apera.
Monocotvledonous crops of the ~enera: Oryza, Zea, Triticum, Hordeum, Avena, W O 97/03980 PCT~EP96/02932 Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no wayrestricted to these genera, but also extends in the same manner to other plants.
The co:mpounds are suitable, depending on the concentration, for the total control of 5 weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree pl~nting~. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, decorative tree pl~ntings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit 10 pl~nting~ and hopfields, in lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in mono-cotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
15 The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These i'ormulations are produced in a known manner, for example by mixing the active 20 compol,mds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If water is used as extender, it is also possible to use for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated 25 aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum WO 9'7/03980 PCT/EP96/02932 fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers ;md esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
5 Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, 10 - marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty a]cohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl 15 sulphates, arylsulphonates as well as protein hydrolysates; suitable di~e,sa~ are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and 20 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, titaniurn oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, m~ne~nese, boron, 25 copper. cobalt, molybdenum and zinc.
The fo]mulations in general comprise between 0.1 and 95 per cent by weight of active compolmd, preferably between 0.5 and 90%.
W O 9'7/03980 PCT~EP96102932 For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, ready-l:o-use formulations or tank mixes being possible.
Possibile components for the mixtures are known herbicides, for example anilides, such 5 as diflufenican and propanil; arylcarboxylic acids, such as dichiloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D,2,4-DB,2,4-DP, fluroxy-pyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl;
azinones, such as chloridazon and norflurazon; carb~m~tes, such as chlol~lol)ha~10 desmedipham, phenme-liph~m and plol)halll; chloroacet~nili-les, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachilor and propachlor; dinitro-anilines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen;
ureas, such as chilorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz-] S thiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim andtralkoxydim; imi-l~7.nlinones, such as imazethapyr, im~7~methabenz, imazapyr and imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as mc fenacet; sulphonyl-ureas, such as amidosulphuron, bensulphuron-methyl, chilorin;luron-ethyl, chlorsulphuron, cinosulphuron, metsulphuron-methyl, nicosulphuron, 20 primisulphuron, pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron and kibenuron-methyl; thiocarb~m~tes, such as butylate, cycloate, .~ tc~ EPTC, esprocarb, molinate, prosulphocarb, thiobencarb and triallate; triazines, such as atrazine, cyanaz;ine, ~im~7ine, simetryne, terbukyne and terbutylazine; triazinones, such as hexazi:none, metamikon and metribuzin; others, such as aminotriazole, benfuresate, 25 bentazone, cinmethylin, clomazone, clopyralid, defenzoquat, dithiopyr, ethofumesate, fluoroc,hiloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nukients and agents which improve soil 30 structure, are also possible.
WO 9 ,'/03980 PCT/EP96/02932 The acl:ive compounds can be used as such, in the form of their formulations or in the use folms prepal~,d thelcrlom 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.
5 The acl:ive compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essçnti.~lly on the nature of the desired effect. In general, the amounts used are between 10 g and 10 kg of active compound per hectare of soil surface, preferably between 10 50 g and 5 kg per ha.
The pll~p~dlion and use of the active compounds according to the invention can be seen from the examples that follow.
WO 9'7/03980 PCT/EP96/02932 Preparation Examples:
Example 1 ~O
O~J .
[~SO~_ N )~--N N ~ CH3 (Process (d)) A mixlure of 2.3 g (8 mmol) of tetrahydrofur-3-yl 2-chlorosulphonylbenzoate, 1.2 g (8 mmol) of 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 1.0 g (8 mmol) of sodium cyanate and 100 ml of acetonitrile is heated under reflux with stirring for about 15 hours. The mixture is then concentrated using water pump vacuum, the residue is shaken with methylene chloride and aqueous hydrochloric acid (pH 1), and the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.
0.7 g (20% of theory) of 4-methyl-5-methylthio-2-[2-(tetrahydro-fur-3-yl-oxycarbonyl)-phenyl sulphonyl-aminocarbonyl]-2,4-dihydro-3H- 1 ,2,4-triazol-3-one of melting point 1 60~C is obtained.
WO 9'7/03980 PCT/EP96/02932 Example 2 r~
o~
SO~--N ~--N N_CH3 C2Hs (Process (d)) A mixture of 2.8 g (10 mmol) of oxetan-3-yl 2-chlorosulphonyl-benzoate, 1.3 g (10 mnnol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 1.3 g (20 mmol) of sodiurn cyanate and 50 ml of acetonitrile is heated under reflux for 90 mimltes The mixture is subsequently concentrated using water pump vacuum and the residue is stirred with methylene chloride and IN hydrochloric acid. The organic phase is then dried ~vith sodium sulphate and filtered. The filkate is concenkated~ the residue is digested ~vith isoplopal1ol and the resulting crystalline product is isolated by filtration with suction.
1.7 g l~41% of theory) of 5-ethyl-4-methyl-2-[2-(oxetan-3-yl-oxycarbonyl)-phenyl-sulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 137~C
are obtained.
By the methods of Examples 1 and 2 and according to the general description of the p~ lion processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) and the compounds of the formula (Ia) listed in Table I below.
WO 9'7/03980 PCT/EP96/02932 ~,SO2 ~ N )~ N--R (la) Table :i: Examples of compounds of the formula (Ia) Ex Q Q2 R' R2 R3 Melting No point (~C) 3 O O CH3 ~C2Hs ~ 127 4 O O CH3 n-c3H7 ~1~
O O CH3 i-C3H, ~G~
6 O ~ CH3 OCH3 ~G~
7 O O CH3 ~C2Hs ~GO 148 8 O ~ CH3 OC3H7-n ~G~
REPLACEMENT SHEET (RULE 26) WO 97/03980 PCT/EP96tO2932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 9 0 0 CH3 OC3H,~ o 0 ~ CH3 OC4Hg-n ~co 11 0 ~ CH3 OC4H9-i ~o 12 O ~ CH3 OC4Hg-s ~cO
13 O ~ CH3 OC6Hs ~~
14 O ~ CH3 O-cH2-cH=cH2 ~~
O ~ CH3 SCH3 ~JO 123 16 O ~ CH3 SC2Hs ~1~
REPLACEMENT SHEET (RULE 26) W O 9'7/03980 PCTAEP96/02932 Table 1: (continued) Ex. Q~ Q2 Rl R2 R3 Melting No. point (~C) 17 0 ~ CH3 SC3H~-n ~CI~
18 0 ~ CH3 SC3H7-i ~G~
19 0 ~ CH3 S-CH2-CH=CH2 ~C1~
O ~ CH3 S ~ ~~
21 0 ~ CH3 SCH2CH2F ~G~
22 0 ~ CH3 SCH2CHF2 ~1~
23 0 ~ CH3 SCH2CF3 ~C~~
24 0 ~ CH3 N(CH3)2 ~0 O O CH, SCH2F ~ o REPLACEMENT SHEET (RULE 26) W 0 9'7/03980 PCTtEP96tO2932 Table l:(continued) Ex Q' Q2 R~ R2 R3 point (~C) 26 0 ~ CH3 SCH2Cl ~G~
27 0 ~ CH3 SCH2CH2Cl ~G~
28 0 ~ CH3 Cl ~G~
29 0 ~ CH3 Br ~G~
0 0 CH3 CH3 ~0 31 0 ~ CH3 C4Hg-n ~CI~
32 0 0 CH3 ~ ~G~
33 0 0 CH3 CH=CH-CH3 ~G~
34 0 0 CH3 CH2OC2Hs ~J~
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table :I: (continued) Ex. Q' Q2 R' R2 R3 Melting No. (poocn)t O O CH3 CH2-CH=CH2 ~G~
36 O ~ CH3 CH20CH3 ~1~
37 O O CH3 OCH2CF3 ~1~
38 O ~ CH3 OcH2cHF2 ~CI~
39 O O CH3 OcH2cF2cHF2 ~C~~
O O CH3 ~ ~o 41 O ~ CH3 OCH2CH2OCH3 ~C1~
42 S ~ CH3 OC2H5 CI~
REPLACEMENT SHEET (RULE 26) WO 97/03980 PCTtEP96/02932 Table 1: (continued) Ex. Ql Q2 Rl R2 R3 Melting No. point (~C) 43 O S CH3 OC2H5 ~cO
44 S S CH3 OC2H5 ~O
O O C2Hs OC2H5 46 O ~ C2Hs C2H5 ~O
47 O O C2Hs n-c3H7 ~G~
48 O ~ C2H5 i-C3H7 ~G~
49 O O C2Hs OCH3 ~CI~
O O C2H5 OC2H5 ~Jo 51 O ~ C2H5 OC3H7-n ~1~
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table :1: (continued) Ex. Q' Q2 Rl R2 R3 Melting No. point ( C) 52 O ~ C2H5 OC3H7-i ~C~~
53 O O C2Hs OC4H9-n ~C~
54 O O C2Hs OC4H9-i ~o O O C2Hs OC4H9-s ~LI~
56 O ~ C2H5 OC6H5 ~O
57 O O C2Hs O-cH2-cH=cH2 ~C~~
58 O ~ C2H5 SCH3 ~O
59 O O C2Hs SC2Hs ~GO
O ~ C2H5 SC3H,-n ~O
REPLACEMENT SHEET (RULE 26) Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 61 O ~ C2H5 SC3H7-i ~o 62 O ~ C2H5 S-cH2-cH=cH2 ~C1~
63 O ~ C2H5 S ~ ~G~
64 O ~ C2H5 SCH2CH2F ~CI~
O ~ C2H5 SCH2CHF2 ~~
66 O ~ C2H5 SCH2CF3 ~CI~
67 O ~ C2H5 N(CH3)2 ~Jo 68 O ~ C2H5 SCH2F ~G~
69 O ~ C2H5 SCH2Cl ~G~
REPLACEMENT SHEET (RULE 26) . WO 97103980 PCT/EP96102932 Table 1: (continued) Ex Q' Q2 R' R2 R3 Melting No point (~C) O O C2H5 SCH2CH2CI ~G~
71 O ~ C2H5 Cl ~cO
72 O ~ C2H5 Br ~G~
73 O O C2Hs CH3 ~G~
74 O O C2Hs C4Hg-n ~Go O O C2H5 f ~ ~G~
76 O ~ C2H5 CH=CH-CH3 ~C1~
77 O O C2Hs CH2OC2Hs ~G~
78 O O C2H, CHz-cH=cH2 ~C~~
REPLACEMENT SHEET (RULE 26) Table 1: (continued) Ex Q' Q2 R' R2 R3 Melting No point (~C) 79 O O C2Hs CH20CH3 ~Go O ~ C2H5 OCH2CF3 ~G~
81 O ~ C2H5 OCH2CHF2 ~~
82 O ~ C2H5 OcH2cF2cHF2 ~G~
83 O o C2H5 ~ ~G~
84 O ~ C2H5 OCH2CH20CH3 ~G~
S ~ C2H5 OC2H5 ~CJ~
86 O S C2H5 OC2H5 ~O
87 O O ~ ~ OC2H5 ~O
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Exo Ql Q2 Rl R2 R3 pomt (~C) 88 O O ~ C2Hs ~L~
89 O O ~ n-C3H7 ~c~o 0 0 ~ i-C3H7 ~CI~
91 0 0 ~ OCH3 ~G~
92 O O ~ OC2H5 ~cO
93 O O ~, OC3H7-n ~C~~
94 O O ~ 0~3H7-i ~1~
O O ~,~ OC4Hg-n ~C~~
96 O O ~ OC4H9-i ~o REPLACEMENT SHEET (RULE 26) W O 9,7/03980 PCT~EP96/02932 Table ]: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 97 O O OC4H9-s o 99 o O O-cH2-cH=cH2 ~
~ ,G .
101 0 o SC2H5 0 102 O O SC3H7-n O
~ )~
103 O O SC3H7-i O
~ ,G
104 O O ~ S-CH2-CH=CH2 ~C1~
105 O O ~ ~ ~ ~ o REPLACEMENT SHEET (RULE 26) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 106 O O ~ SCH2CH2F ~O
107 O O ~ SCH2CHF2 ~O
108 O O ~ SCH2CF3 ~Jo 109 0 0 ~ N(CH3)2 ~~
11 0 0 0 ~ SCH2F ~G~
111 0 0 ~ SCH2C1 ~G~
112 O O ~ SCH2CH2C1 ~o 113 O O ~ Cl ~C1~
1 14 O O ~ Br ~C~o REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 1 15 O O ~ CH3 ~Co 1 16 O O ~ C4Hg-n ~o 117 O O ~ ~ ~C~o 1 18 O O ~ ~ CH=CH-CH3~Co 119 0 0 ~ CH2OC2Hs ~G~
120 O ~ ~ CH2-cH=cH2 ~G~
121 O O ~ CH20CH3 ~G~
122 O O OCH2CF3 r~
REPLACEMENT SHEET (RULE 26) Table 1: (contim~ed) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 123 O O ~ OcH2cHF2 ~CI~
124 O O ~ OcH2cF2cHF2 ~C~~
125 ~ ~ ~ O~
126 O O ~ OCH2CH2OCH3 ~O
127 S O ~ ~C2Hs ~GO
128 O S ~ OC2H5 ~c~O
129 O O OCH3 OC2H5 ~
130 O O OCH3 C2Hs ~G~
131 O O OCH3 n-C3H7 ~O
REPLACEMENT SHEET (RULE 26) WO Sl7/03980 PCT/EP96/02932 Table 1: (col-tinllec~) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 132 O O OCH3 i-C3H, ~C~
133 O O OCH3 OCH3 ~c~o 134 O O OCH3 OC2H5 ~cO
135 O O OCH3 OC3H7-n ~C~~
136 O O OCH3 OC3H7-i ~C~~
137 O O OCH3 OC4Hg-n ~c~o 138 O O OCH3 OC4H9-i ~G~
139 O ~ OCH3 OC4Hg-s ~G~
140 O O OCH3 OC6H5 ~O
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Ex. Ql Q2 R' R2 R3 Melting No. point (~C) 141 O O OCH3 O-cH2-cH=cH2 ~G~
142 O O OCH3 SCH3 ~G~
143 O O OCH3 S~2H5 ~O
144 O O OCH3 SC3H7-n ~O
145 O O OCH3 SC3H7-i ~O
146 O ~ OCH3 S-cH2-cH=cH2 ~G~
147 O O OCH3 ~ S ~ ~1 148 O O OCH3 SCH2CH2F ~o REPLACEMENT SHEET (RULE 26) - W O 9'l/03980 PCTAEP96102932 Table:l:(continued) Ex Q' Q2 R' R2 R3 pomt (~C) 149 O ~ OCH2 SCH2CHF2 p ~
150 O O OCH3 SCH2CF3 ~O
151 0 0 OCH3 N(CH3)2 ~C~
152 O ~ OCH3 SCH2F ~o 153 O O OCH3 SCH2CI ~c~o 154 O O OCH3 SCH2CH2CI ~o 155 O O OCH3 Cl po 156 O O OCH3 Br po 157 O O OCH3 CH3 ~CI~
REPLACEMENT SHEET (RULE 26) WO 97/03980 PCTtEP96tO2932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 No.
158 O O OCH3 C4H9-n ~c~o 159 O O OCH3 ~,~ ~CI~
160 O O OCH3 CH=CH-CH3 ~G~
161 O O OCH3 CH2OC2Hs ~C~~
162 O O OCH3 CH2-cH=cH2 ~G~
163 O O OCH3 CH2OCH3 ~O
164 O O OCH3 OCH2CF3 ~C~~
165 O ~ OCH3 OCH2CHF2 ~~
166 O O OCH3 OCH2CF2CHF2 ~c~
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table l: (continued) Ex. Q' Q2 R' R2 R3 No.
167 O O OCH3 ~, ~O
168 O ~ OCH3 OCH2CH2- O
OCH3 ~C
169 S O OCH3 OC2H5 ~CI~
170 O S OCH3 OC2Hs ~C1~
171 O ~ OC2H5 OC2H5 ~
J' 172 O ~ OC2H5 C2H5 CI~
173 O ~ OC2H5 n-C3H, ~O
174 O ~ OC2H5 i-C3H, ~cO
175 O ~ OC2H5 OCH3 ~c~o WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 No.
176 O ~ OC2H5 OC2H5 ~CJ~
177 O ~ OC2H5 OC3H,-n ~cO
178 O ~ OC2H5 OC3H,-i ~CI~
179 O ~ OC2H5 SCH3 ~c~O
180 O ~ OC2H5 SC2Hs ~C~~
181 O ~ OC2H5 N(CH3)2 ~G~
182 O ~ OC2H5 SCH2F ~o 183 O ~ OC2H5 SCH2CI ~CI~
184 O ~ OC2H5 SCH2CH2CI ~G~
~ CA 02227012 1998-01-14 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 185 O O OC2E~5 Cl ~G~
186 0 ~ OC2H5 Br ~0 187 0 ~ OC2H5 CH3 ~CJ~
188 0 ~ OC2H5 f ~ ~CI~
189 0 ~ OC2H5 CH=CH-CH3 ~o 190 0 ~ OC2H5 CH2OC2Hs ~~
191 0 ~ OC2H5 CH2-CH=CH2 ~G~
192 0 ~ OC2H5 CH20CH3 ~C~
193 0 0 N(CH3)2 C2Hs ~GO
WO 9'1/03980 PCT/EP96/02932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point ( C) 194 O O N(CH3)2 n-C3H, ~C~~
195 O O N(CH3)2 CH3 ~CI~
196 O O N(CH3)2 OCH3 ~C~
197 O O N(cH3)2 OC2Hs ~Cl~
198 O O N(CH3)2 OC3H,-n ~CI~
199 0 0 N(CH3)2 SCH3 ~O
200 O ~ CH3 C2H5 ~CI~ 159 By the methods of Examples 1 and 2, it was also possible to prepare the following compolmds:
REPLACEMENT SHEET (RULE 26) Examlple 201 ~0 OJ~
_~H~N~N_cH, Melting point: 146~C
Example 202 ~0 [~2--NH~ N J'' N--CH3 CH3 N =( MeltinlJ point: 1 58~C
REPLACEMENT SHEET (RULE 26) - WO 9'1/03980 PCT/EP96/02932 Startinp materials of the formula (VII):
Example (VII-1) ~bo At -lO"C, a solution of 3.4 g of pyridine in 20 ml of methylene chloride is added dropwi ,e with stirring to a mixture of 9.46 g (39 mmol) of 2-chlorosulphonyl-benzoyl chloride, 3.5 g (39 mmol) of 3-hydroxymethyl-tetrahydrofuran and 100 ml of methylene chloride, and the reaction mixture is then stirred at 20~C for about 6 hours.
The mixture is subsequently concentrated using water pump vacuum, the residue isshaken with methylene chloride and aqueous hydrochloric acid (pH 1), and the organic phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully distillecl off from the filtrate using water pump vacuum.
8.2 g (72.5% of theory) of tetrahydrofur-3-yl 2-chlorosulphonyl-benzoate are obtained as an oily residue which can be used directly as such for further reactions.
Example (VII-2) o~lo Step 1 A mixl[ure of 68.3 g (0.20 mol) of bis-(2-chlorocarbonyl-phenyl) disulphide, 29.6 g (0.40 mol) of 3-hydroxy-oxetane, 42.5 g (0.42 mol) of triethylamine and 500 ml of methyllene chloride is stirred at 20~C for 15 hours. 200 ml of lN hydrochloric acid are then added and the organic phase is separated off, washed with water, dried with5 sodiwn sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
48.6 g (58% of theory) of bis-[2-(oxetan-3-yl-oxycarbonyl)-phenyl] ~ phide of meltin~ point 143~C are obtained.
10 Step 2 At -5~C to 0~C, 11.2 g of chlorine are introduced over a period of about 15 minutes into a mixture of 10.5 g (25 mmol) of bis-[2-(oxetan-3-yl-oxycarbonyl)-phenyl]
disulphide, 12.9 g of sodium acetate and 100 ml of 50% strength aqueous acetic acid.
The reaction IllixLule is stirred at 0~C for a further 15 minutes and then admixed with 15 150 ml of methylene chloride. The methylene chloride phase is then separated off, washed with ice-water, dried with sodium sulphate and filtered. The filtrate is concen-trated using water pump vacuum and the residue is purified twice by silica gel column chromatography (first run with methylene chloride, second run with ethyl acetate).
10.4 g (75% of theory) of oxetan-3-yl 2-chlorosulphonyl-benzoate are obtained as a 20 yellowish oil.
'H NMR (CDCl3, TMS, ~): 4.9 (m, 2H), 5.0 (m, 2H), 5.8 (m, lH), 7.8 (m, 3H), 8.2 (m, lH) ppm.
WO 97/03980 PCTtEP96tO2932 Use examples:
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 active compound plcpa~dtion, 1 part by weight of active com-pound 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. After about 24 hours, the soil is 10 watered with the p,cpaldlion of active compound. It is advantageous to keep the amount of water per unit area constant. The concentration of the active compound in the ~lcl,~dlion is immaterial, only the amount of active compound applied per unit area matters.
After tllree weeks, the degree of damage to the plants is rated in % damage by com-15 parison with the development of the untreated control.
The fi~ures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, the compounds of the formula (I) according to the invention show strong 20 activity against weeds (cf. Table A).
WO 9'7/03980 PCT/EP96/02932 Example B
Post-ernergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable active compound plep~lion, 1 part by weight of active com-pound is mixed with the stated amount of solvent, the stated amount of emlllcifier 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 10 desired per unit area. The concentration of the spray liquor is chosen so that the particu]ar 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 by com-parison with the development of the untreated control.
The figures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, the compounds of the formula (I) according to the invention show strong activity against weeds (cf. Table B).
WO 9'7l03980 PCTIEP96/02932 Table A: Pre-emergence test/greenhouse Active com- Applic- Maize Alope- Cype- Seta- Amaran- Sina-pound ation rate curus rus ria thuspis (according to (g/ha) Preparation Ex.) (7) 250 10 80 - 70 100 (201) 250 - 80 95 80 70 100 (202) 250 0 80 1 00 70 - 70 10 Table :B: Post-emergence test/greenhouse Active com- Application Maize Alopecurus Avena fatua Sinapis pound rate (according to (glha) Plep~lion Ex.) (201) 250 10 80 80 100
It is a].ready known that certain sulphonylaminocarbonyltriazolinones have herbicidal properties (cf. EP-A 341489, EP-A 422469, EP-A 425948, EP-A 431291, EP-A
507171). However, the activity ofthese compounds is not satisfactory in every respect.
This invention, accordingly, provides the novel substituted arylsulphonylamino(thio)-- carbonyltriazolin(e-thi)ones of the general formula (I) Q' ~ (I) l O in which Ar represents respectively optionally substituted arylene or heteroarylene, Q' represents oxygen or sulphur, Q2 represents oxygen or sulphur, R' represents hydrogen, hydroxyl, amino, alkylideneamino or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, R2 represents hydrogen, hydroxyl, mercapto, amino, halogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinyl-thio, alkylamino, alkenylamino, alkinylarnino, dialkylarnino, alkanoylarnino, aziridino, pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cyclo-alkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio, cycloalkylalkylamino, aryl, aryloxy, arylthio, arylarnino, S arylalkyl, arylalkoxy, arylalkylthio, arylalkylarnino, heterocyclyloxy, hetero-cyclylthio, or R' and R2 together represent optionally branched ~lk~ne~liyl, and R3 l~,es~ optionally sub~liluled heterocyclyl, and salts of the compounds of the formula (I).
] 0 The novel substituted arylsulphonylamino(thio)carbonyl-triazolin(e-thi)ones of the general forrnula (I) are obtained when (a) triazolin(e-thi)ones of the general formula (II) H--N~N--R' (Il) N =(R2 in which IS Q', R' and R2 are each as defined above are reaicted with substituted arylsulphonyliso(thio)cyanates of the general formula (III) R3-O-CO-Ar-SO2-N=C=Q2 (III) in which WO 9'7/03980 PCT/EP96/02932 Ar, Q2 and R3 are each as defined above, if a~ l;ate in the presence of a reaction auxiliary and if a~ropliate in the presence of a diluent, or 5 (b) triazolin(e-thi)one derivatives of the general forrnula (IV) z J~--N )~ N--R1 (IV) in which Ql, Q2, R~ and R2 are each as defined above and Z represents halogen, alkoxy, aryloxy or arylalkoxy ] 0 are reacted with sulphonarnides of the general forrnula (V) R3-o-co-Ar-so2-NH2 (V) in which Ar ancl R3 are each as defined above, if app~opl;ate in the presence of an acid acceptor and if applu~l;ate in the presence of ] 5 a diluent, or (c) triazolin(e-thi)ones of the general forrnula (II) H--N N--R (Il) N =~
in which Q', R' and R2 are each as defined above S are reacted with substituted arylsulphonarnide derivatives of the general formula (VI) R3-O-CO-Ar-SO2-NH-CQ2-Z (VI) in which Ar, Q2 and R3 are each as defined above and Z represents represents halogen, alkoxy, aryloxy or arylalkoxy, 10 if a~,pluyliate in the presence of an acid acceptor and if apl)lo~l;ate in the presence of a diluent, or (d) triazolin(e-thi)ones of the general forrnula (II) H_NJ~N_R' (Il) ~N =(R2 in which Q', R' and R2 are each as defined above are reacted with substituted arylsulphonyl halides of the general formula (VII) R3-O-CO-Ar-SO2-X (VII) 5 in which Ar and R3 are each as defined above and X represents halogen and metal (thio)cyanates of the general formula (VIII) MQ2CN (VIII) 10 in whic:h Q2 is as defined above and M represents an alkali metal or an ~Ik~line earth metal equivalent, if applop,iate in the presence of a reaction auxiliary and if approl,l;ate in the presence of a di]uent, 15 and, if approp~;ate, the compounds of the formula (I) obtained by the processes (a), (b), (c) or (d) are converted into salts by customary methods.
The novel sulphonylamino(thio)carbonyl-triazolin(e-thi)ones of the general formula (I) have strong herbicidal activity.
WO 97tO3980 PCT/EP96/02932 The invention preferably provides compounds of the formula (I) in which Ar represents phenylene or naphthylene, each of which is optionally substituted by halogen, cyano, nitro, by C,-C4-alkyl, C1-C4-alkoxy, C,-C4-alkylthio, C,-C4-alkylsulphinyl, C,-C4-alkylsulphonyl, di-(CI-C4-alkyl)-arnino-sulphonyl orN-C~-C4-alkoxy-N-C,-C4-alkyl-amino-sulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represents heteroarylene of 5 or 6 ring members, at least one of which is oxygen, sulphur or nitrogen and one or two more are optionally nitrogen, which is optionally substituted by halogen, cyano, nitro, by C,-C4-alkyl or C,-C4-alkoxy (each of which is optionally 11~ substituted by fluorine andlor chlorine), Ql represents oxygen or sulphur, Q2 represents oxygen or sulphur, Rl :represents hydrogen, hydroxyl, amino, represents C2-C10-alkylideneamino, :represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-alkoxy-, Cl-C4-alkyl-carbonyl- or Cl-C4-alkoxy-carbonyl-substituted C~-C6-alkyl, represents :respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-.alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, cyano-, C,-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C,-C6-alkoxy, Cl-C6-,alkylamino or C,-C6-alkanoylamino, represents C3-C6-alkenyloxy, represents di-I(C,-C4-alkyl)-amino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- andlor C,-C4-alkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C~-C4-alkyl, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- andlor C~-C4-alkoxy-.substituted phenyl or phenyl-C,-C4-alkyl, 25 R2 :represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, :iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-,alkoxy-, C~-C4-alkyl-carbonyl- or C~-C4-alkoxy-carbonyl-substituted C~-C6-alkyl, WO 9'l/03980 PCT/EP96/02932 represents respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, le~rese~ respectively optionally fluorine-, chlorine-, cyano-, Cl-C4-alkoxy- or C,-C4-alkoxy-carbonyl-substituted Cl-C6-alkoxy, C,-C6-alkylthio, C,-C6-alkylamino or C,-C6-alkanoylamino, represents C2-C6-alkenyloxy, C2-C6-alkinyloxy, C2-C6-alkenylthio, C2-C6-alkinylthio, C2-C6-alkenylamino or C2-C6-alkinylamino, represents di-(C,-C4-alkyl)-amino, represents respectively optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C,-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C,-C4-alkyl,- C3-C6-cycloalkyl-C,-C4-alkoxy, C3-C6-cycloalkyl-CI-C4-alkylthio or C3-C6-cycloalkyl-C~-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C,-C4-alkyl-, trifluoromethyl- and/or C,-C4-alkoxy-substituted substituted phenyl, phenyl-C,-C4-alkyl, phenoxy, phenyl-C,-C4-alkoxy, phenylthio, phenyl-C,-C4-alkylthio, phenylamino or phenyl-C,-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C,-C4-alkyl-, trifluoromethyl- and/or C,-C4-alkoxy-substituted heterocyclyloxy or heterocyclylthio, the heterocyclyl component being in each case selected from the group consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, thietanyl, thienyl, tetrahydrothienyl, or R~ and R2 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and R3 represents respectively optionally halogen- or C,-C4-alkyl-substituted oxetanyl, thietanyl, furyl, tetrahydrofi~ryl, thienyl or tetrahydrothienyl.
Furthelmore, the invention preferably provides the sodium, potassium, magnesium,calcium, ammonium, Cl-C4-alkyl-ammonium, di-(C~-C4-alkyl)-ammonium, tri-(C~-C4-alkyl)-ammonium, tetra-(C,-C4-alkyl)-ammonium, tri-(C,-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C,-C2-alkyl)-benzyl-ammonium salts of compounds WO 9'7/03980 PCT/EP96J02932 of the ~formula (I) in which Ar, Ql, Q2, Rl, R2 and R3 are each as defined above by way of preference.
The invention in particular provides compounds of the formula (I) in which Ar leplesenl~ respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, S methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoro-methoxy-, trifluoromethoxy-, methylthio- or ethylthio-substituted 1,2-phenylene (ortho-phenylene), pyridine-2,3-diyl, thiophene-2,3-diyl or pyrazol-4,5-diyl, Ql represents oxygen or sulphur, Q2 represents oxygen or sulphur, 10 Rl represents hydrogen, hydroxyl, amino, represents C3-C8-alkylideneamino, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy- substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents dimethylamino or diethylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclo-hexylmethyl, or repl~sent~ respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl, R2 le~leselll~ hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, WO 9'7/03980 PCT/EP96/02932 butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s-or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenyl-amino, propinylamino, or butinylamino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl-and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-methoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclo-pentylmethylamino or cyclohexylmethylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or represellt~ respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted oxetanyloxy, furyloxy, tetrahydrofuryloxy, thienyloxy or tetrahydrothienyloxy, or R' and R2 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and R3 represents respectively optionally fluorine-, chlorine-, methyl- or ethyl-substituted oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl or tetrahydro-thienyl.
A very particularly preferred group of compounds of the formula (I) are the compounds of the i~ormula (Ia) ~ 2'NJ~--N N - R (la) in whirch Ql, Q2, R~, R2 and R3 each have the me~nine~ given above as being particularly pre-ferred.
5 The general or preferred radical definitions listed above are valid both for the end products of the formula (I) and also, in a corresponding manner, for the starting materials or intennetli~tes which are required in each case for the p~ ~dlion. These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of plef~ d compo~imds.
l O Using, for example, 2-(oxetan-3-yl-oxy-carbonyl)-phenylsulfonylisocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following scheme:
~ H--N N--OCH3 [~1~ so2 )~--N )~ N--OCH3 o o C2Hs 0~0 C2Hs ~0 ~0 15 Using, for example, 2-(thietan-3-yl-oxy-carbonyl)-benzenesulphonamide and 2-chloro-carbonyl-4-dimethylamino-5-methyl-2,4-dihydro-3H- 1 ,2,4-triazol-3-thione as starting materials, the course of the reaction in the process (b) according to the invention can be illu,trated by the following scheme:
WO 9'7/03980 PCT/EP96/02932 O~s ~cS
[~ ~ S ~Z--N )~--N N _ N(CH,)2 Using, for example, N-methoxycarbonyl-2-(2-tetrahydrofuryl-methoxy-carbonyl)-benzenesulphonamide and 5-ethoxy-4-methyl-2,4-dihydro-3H- 1 ,2,4-triazol-3-one as starting materials, the course of the reaction in the process (c) according to the 5 invention can be illustrated by the following scheme:
1~ 1 0 ~,0 0' o"
J"'~O + ~ ~ '' ~O o ~
"' - '''' SO N, N HOCH ~ ~-' " SO ~ N ~ N - CH3 ~ N ~, OCH3 OC2H5 OC2H5 Using, for exarnple, 4-ethyl-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one and 2-(3-thietanyl-oxy-carbonyl)-benzenesulphonyl chloride and potassium cyanate as starting materia,ls, the course of the reaction in the process (d) according to the invention can 10 be illustrated by the following scheme:
WO 9'7/03980 PCT/EP96/02932 ~S ~c~S
[~o H_NJ~N_C2Hs ~ KOCN ~2 NH \ =~
SC2Hs The fo~mula (II) provides a general definition of the triazolin(e-thi)ones to be used as starting materials in the processes (a), (c) and (d) according to the invention for preparing compounds of the formula (I). In the formula (II), Ql, R' and R2 each S preferably or in particular have those me~ning.C which have already been given above, in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly plefe.,cd for Q~, R' and R2.
The tri,azolin(e-thi)ones of the general formula (II) are known and/or can be prepared by processes known per se (cf. Arch. Pharm. 301 (1968), 827; loc. cit. 307 (1974), 889;
Bull. Soc. Chim. France 1962, 1365; loc. cit. 1975, 1191; Chem. Ber. 90 (1957), 909-921; loc. cit. 98 (1965), 3025-3099; loc. cit. 102 (1969), 755; J. Heterocycl. Chem. 15 (1978), 237-240; J. Indian Chem. Soc. 6 (1929), 565; Liebigs Ann. Chem. 637 (1960), 135; M~onatshefte Chemie 123 (1992), 257; Tetrahedron 32 (1976), 2347-2352; Helv.
Chim. .Acta 63 (1980), 841-859; J. Chem. Soc. C 1967, 746-751; loc. cit. 1970, 26-34;
J. Chern. Soc. Perkin I 1973, 2644; Fen Fak. Derg., Seri A (Ege Univ.) 7 (1984), 1-6 -cited in Chem. Abstracts 101:90846m; EP-A 283876; EP-A 294666; EP-A 298371;
EP-A 301946; EP-A 305844; EP-A 341489; EP-A 362633; EP-A 370293; EP-A
391187; EP-A 398096; EP-A 398097; EP-A 399294; EP-A 415196; EP-A 422469;
EP-A 425948; EP-A 431291; EP-A 477646; EP-A 502307; EP-A 503437; EP-A
505815'; EP-A 511569; EP-A 513621; DE-A 2336827; DE-A 3839206; DE-A 3916208;
DE-A :3916930; DD-P 64970; WO-A 93/04050; P.cparalion Examples).
The formula (III) provides a general definition of the substituted arylsulphonyl iso-(thio)cyanates fi~rther to be used as starting materials in the process (a) according to the invention for p.cpa hlg compounds of the formula (I). In the formula (III) Ar, Q2 and R3 each preferably or in particular have that me~ning which has already been given above, in connection with the description of the compounds of the formula (I) according to the invention, as being ple~llcd or as being particularly preferred for Ar, Q2 ancl R3.
S The slarting materials of the formula (III) are known and/or can be prepared by processes known per se (cf. EP-A 496701, EP-A 558445).
The formula (IV) provides a general definition of the triazolin(e-thi)one derivatives to be used as starting materials in the process (b) according to the invention for ~,lep~illg the compounds of the general formula (I). In the formula (IV), Ql, Q2, Rl and R2 each 10 preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I), as being preferred or as being particularly prefe.l~,d for Q~, Q2, R~ and R2; Z preferably repre-sents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
15 Some of the starting materials of the formula (IV) have not been disclosed in the literature and form part of the subject matter of commonly ~sign~d earlier patent applications.
The compounds of the general formula (IV) are obtained when triazolin(e-thi)ones of the general forrnula (II) H_N~N_R' (Il) N ~(R2 in which Q', R' and R2 are each as defined above W O 9'7/03980 PCTAEP96/02932 are reacted with carbonic acid derivatives of the general formula (IX) z-co-zl (IX) in which Z is as defined above and 5 Z1 represents halogen, alkoxy, aralkoxy or aryloxy (and has the same preferred m-o~nings as Z), if apl)lol fiate in the presence of an acid acceptor such as, for example, sodium hydroxide or potassium hydroxide, sodium t-butoxide or potassium t-butoxide, and if applol,,;ate in the presence of a diluent such as, for example, methylene chloride, 10 tetrahydrofuran or dimethoxyethane and/or water, at te~l~pc.~lu,es between 0~C and 1 OO~C.
The formula (V) provides a general definition of the sulphonamides further to be used as starting materials in the process (b) according to the invention for ~ al;llg the compolmds of the general formula (I). In the formula (V), Ar and R3 each preferably 15 or in particular have that meaning which has already been given above, in connection with the description of the compounds of the formula (I), as being plefelled or as being particularly preferred for Ar and R3.
The starting materials of the formula (V) are known and/or can be prepared by pro-cesses known per se (cf. EP-A 496701, EP-A 558445).
20 The formula (VI) provides a general definition of the substituted arylsulphonamide derivatives to be used as starting materials in the process (c) according to the invention for plepal;llg the compounds of the formula (I). In the formula (VI), Ar, Q2 and R3 each preferably or in particular have that meaning which has already been given above, in connection with the description of the compounds of the formula (I), as being W O 9'7/03980 PCTAEP96/02932 pler~.l, d or as being particularly p~c~-~cd for Ar, Q2 and R3; Z preferably represents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
The st~rting materials of the formula (VI) are known ancl/or can be prepared by 5 processes known per se.
The folmula (VII) provides a general definition of the substituted arylsulphonyl halides to be used as starting materials in the process (d) according to the invention for pre-paring the compounds of the formula (I). In the formula (VII), Ar and R3 each pre-ferably or in particular have that me~ning which has already been given above, in 10 connection with the description of the compounds of the formula (I), as being preferred or as being particularly preferred for Ar and R3; X preferably represents fluorine, chlorine or bromine, in particular chlorine.
The starting m~tt~ri~l~ of the formula (VII) are known and/or can be prepaled byprocesses known per se (cf. EP-A 496701, EP-A 558445).
The processes (a), (b), (c) and (d) according to the-invention for the prep~lion of the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene; 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, for example acetonitrile and propionitrile; amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexam~ thylphosphoric triamide.
WO 9'T103980 PCT/EP96/02932 As reaction auxiliaries and/or as acid acceptors in the processes (a), (b), (c) and (d) according to the invention it is possible to employ all acid-binding agents which can customarily be used for such reactions. Preference is given to alkali metal hydroxides, for example sodium hydroxide and potassium hydroxide, ~Ik~lin~ earth metal 5 hydroxides, for example calcium hydroxide, alkali metal carbonates and alkoxides, such as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropyl-amine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4--ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1 ,4-diazabicyclo-[2,2,2]-octane (DABCO).
The reaction te~ dlules in the processes (a), (b), (c) and (d) according to the invention can be varied within a relatively wide range. The reactions are in general carried out at telll~ res of between -20~C and +150~C, preferably at temperatures bet~,veen 0~C and +100~C.
The processes (a), (b), (c) and (d) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
20 For calrying out processes (a), (b), (c) and (d) according to the invention, the starting materials required in each case are in general employed in approximately equimolar quantities. However, it is also possible to use one of the components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a 25 number of hours at the particular telllpeldlur~ required. Work-up in the processes (a), (b), (c) and (d) according to the invention is in each case carried out by customary methods (cf. the Plel)~dlion Examples).
Salts of the compounds of the general formula (I) according to the invention can be WO 9'7/03980 PCT/EP96/02932 ,lepaled if desired. Such salts are obtained in a simple manner by customary methods of fornning salts, for example by dissolving or dispersing a compound of the formula (I) in an applopl;ate solvent, for example methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding an applop~iate base. The salts can then - if desired after 5 prolonged stirring - be isolated by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers 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 not wanted.
Whether the substances according to the invention act as total or selective herbicides ] 0 depencls essentially on the amount used.
The active compounds according to the invention can be used, for example, in connec:tion with the following plants:
Dicotvledonous weeds of the ~enera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemi~, Galinsoga, Chenopodium, Urtica, Senecio, Alll;~lllhus, Portulaca, 15 Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsiurn, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lin~eTni~ Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the ~enera: Gossypiurn, Glycine, Beta, Daucus, Phaseolus, Pisum. Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, 20 Lactuca, Cucumis and Cucurbita.
Monocot~ledonous weeds of the ~enera: Echinochloa, Setaria, Panicum, Digitaria, Phleurn, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and 25 Apera.
Monocotvledonous crops of the ~enera: Oryza, Zea, Triticum, Hordeum, Avena, W O 97/03980 PCT~EP96/02932 Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no wayrestricted to these genera, but also extends in the same manner to other plants.
The co:mpounds are suitable, depending on the concentration, for the total control of 5 weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree pl~nting~. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, decorative tree pl~ntings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit 10 pl~nting~ and hopfields, in lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in mono-cotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
15 The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These i'ormulations are produced in a known manner, for example by mixing the active 20 compol,mds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If water is used as extender, it is also possible to use for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated 25 aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum WO 9'7/03980 PCT/EP96/02932 fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers ;md esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
5 Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, 10 - marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty a]cohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl 15 sulphates, arylsulphonates as well as protein hydrolysates; suitable di~e,sa~ are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and 20 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, titaniurn oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, m~ne~nese, boron, 25 copper. cobalt, molybdenum and zinc.
The fo]mulations in general comprise between 0.1 and 95 per cent by weight of active compolmd, preferably between 0.5 and 90%.
W O 9'7/03980 PCT~EP96102932 For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, ready-l:o-use formulations or tank mixes being possible.
Possibile components for the mixtures are known herbicides, for example anilides, such 5 as diflufenican and propanil; arylcarboxylic acids, such as dichiloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D,2,4-DB,2,4-DP, fluroxy-pyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl;
azinones, such as chloridazon and norflurazon; carb~m~tes, such as chlol~lol)ha~10 desmedipham, phenme-liph~m and plol)halll; chloroacet~nili-les, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachilor and propachlor; dinitro-anilines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen;
ureas, such as chilorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz-] S thiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim andtralkoxydim; imi-l~7.nlinones, such as imazethapyr, im~7~methabenz, imazapyr and imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as mc fenacet; sulphonyl-ureas, such as amidosulphuron, bensulphuron-methyl, chilorin;luron-ethyl, chlorsulphuron, cinosulphuron, metsulphuron-methyl, nicosulphuron, 20 primisulphuron, pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron and kibenuron-methyl; thiocarb~m~tes, such as butylate, cycloate, .~ tc~ EPTC, esprocarb, molinate, prosulphocarb, thiobencarb and triallate; triazines, such as atrazine, cyanaz;ine, ~im~7ine, simetryne, terbukyne and terbutylazine; triazinones, such as hexazi:none, metamikon and metribuzin; others, such as aminotriazole, benfuresate, 25 bentazone, cinmethylin, clomazone, clopyralid, defenzoquat, dithiopyr, ethofumesate, fluoroc,hiloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nukients and agents which improve soil 30 structure, are also possible.
WO 9 ,'/03980 PCT/EP96/02932 The acl:ive compounds can be used as such, in the form of their formulations or in the use folms prepal~,d thelcrlom 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.
5 The acl:ive compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essçnti.~lly on the nature of the desired effect. In general, the amounts used are between 10 g and 10 kg of active compound per hectare of soil surface, preferably between 10 50 g and 5 kg per ha.
The pll~p~dlion and use of the active compounds according to the invention can be seen from the examples that follow.
WO 9'7/03980 PCT/EP96/02932 Preparation Examples:
Example 1 ~O
O~J .
[~SO~_ N )~--N N ~ CH3 (Process (d)) A mixlure of 2.3 g (8 mmol) of tetrahydrofur-3-yl 2-chlorosulphonylbenzoate, 1.2 g (8 mmol) of 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 1.0 g (8 mmol) of sodium cyanate and 100 ml of acetonitrile is heated under reflux with stirring for about 15 hours. The mixture is then concentrated using water pump vacuum, the residue is shaken with methylene chloride and aqueous hydrochloric acid (pH 1), and the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the crystalline product is isolated by filtration with suction.
0.7 g (20% of theory) of 4-methyl-5-methylthio-2-[2-(tetrahydro-fur-3-yl-oxycarbonyl)-phenyl sulphonyl-aminocarbonyl]-2,4-dihydro-3H- 1 ,2,4-triazol-3-one of melting point 1 60~C is obtained.
WO 9'7/03980 PCT/EP96/02932 Example 2 r~
o~
SO~--N ~--N N_CH3 C2Hs (Process (d)) A mixture of 2.8 g (10 mmol) of oxetan-3-yl 2-chlorosulphonyl-benzoate, 1.3 g (10 mnnol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 1.3 g (20 mmol) of sodiurn cyanate and 50 ml of acetonitrile is heated under reflux for 90 mimltes The mixture is subsequently concentrated using water pump vacuum and the residue is stirred with methylene chloride and IN hydrochloric acid. The organic phase is then dried ~vith sodium sulphate and filtered. The filkate is concenkated~ the residue is digested ~vith isoplopal1ol and the resulting crystalline product is isolated by filtration with suction.
1.7 g l~41% of theory) of 5-ethyl-4-methyl-2-[2-(oxetan-3-yl-oxycarbonyl)-phenyl-sulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 137~C
are obtained.
By the methods of Examples 1 and 2 and according to the general description of the p~ lion processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) and the compounds of the formula (Ia) listed in Table I below.
WO 9'7/03980 PCT/EP96/02932 ~,SO2 ~ N )~ N--R (la) Table :i: Examples of compounds of the formula (Ia) Ex Q Q2 R' R2 R3 Melting No point (~C) 3 O O CH3 ~C2Hs ~ 127 4 O O CH3 n-c3H7 ~1~
O O CH3 i-C3H, ~G~
6 O ~ CH3 OCH3 ~G~
7 O O CH3 ~C2Hs ~GO 148 8 O ~ CH3 OC3H7-n ~G~
REPLACEMENT SHEET (RULE 26) WO 97/03980 PCT/EP96tO2932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 9 0 0 CH3 OC3H,~ o 0 ~ CH3 OC4Hg-n ~co 11 0 ~ CH3 OC4H9-i ~o 12 O ~ CH3 OC4Hg-s ~cO
13 O ~ CH3 OC6Hs ~~
14 O ~ CH3 O-cH2-cH=cH2 ~~
O ~ CH3 SCH3 ~JO 123 16 O ~ CH3 SC2Hs ~1~
REPLACEMENT SHEET (RULE 26) W O 9'7/03980 PCTAEP96/02932 Table 1: (continued) Ex. Q~ Q2 Rl R2 R3 Melting No. point (~C) 17 0 ~ CH3 SC3H~-n ~CI~
18 0 ~ CH3 SC3H7-i ~G~
19 0 ~ CH3 S-CH2-CH=CH2 ~C1~
O ~ CH3 S ~ ~~
21 0 ~ CH3 SCH2CH2F ~G~
22 0 ~ CH3 SCH2CHF2 ~1~
23 0 ~ CH3 SCH2CF3 ~C~~
24 0 ~ CH3 N(CH3)2 ~0 O O CH, SCH2F ~ o REPLACEMENT SHEET (RULE 26) W 0 9'7/03980 PCTtEP96tO2932 Table l:(continued) Ex Q' Q2 R~ R2 R3 point (~C) 26 0 ~ CH3 SCH2Cl ~G~
27 0 ~ CH3 SCH2CH2Cl ~G~
28 0 ~ CH3 Cl ~G~
29 0 ~ CH3 Br ~G~
0 0 CH3 CH3 ~0 31 0 ~ CH3 C4Hg-n ~CI~
32 0 0 CH3 ~ ~G~
33 0 0 CH3 CH=CH-CH3 ~G~
34 0 0 CH3 CH2OC2Hs ~J~
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table :I: (continued) Ex. Q' Q2 R' R2 R3 Melting No. (poocn)t O O CH3 CH2-CH=CH2 ~G~
36 O ~ CH3 CH20CH3 ~1~
37 O O CH3 OCH2CF3 ~1~
38 O ~ CH3 OcH2cHF2 ~CI~
39 O O CH3 OcH2cF2cHF2 ~C~~
O O CH3 ~ ~o 41 O ~ CH3 OCH2CH2OCH3 ~C1~
42 S ~ CH3 OC2H5 CI~
REPLACEMENT SHEET (RULE 26) WO 97/03980 PCTtEP96/02932 Table 1: (continued) Ex. Ql Q2 Rl R2 R3 Melting No. point (~C) 43 O S CH3 OC2H5 ~cO
44 S S CH3 OC2H5 ~O
O O C2Hs OC2H5 46 O ~ C2Hs C2H5 ~O
47 O O C2Hs n-c3H7 ~G~
48 O ~ C2H5 i-C3H7 ~G~
49 O O C2Hs OCH3 ~CI~
O O C2H5 OC2H5 ~Jo 51 O ~ C2H5 OC3H7-n ~1~
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table :1: (continued) Ex. Q' Q2 Rl R2 R3 Melting No. point ( C) 52 O ~ C2H5 OC3H7-i ~C~~
53 O O C2Hs OC4H9-n ~C~
54 O O C2Hs OC4H9-i ~o O O C2Hs OC4H9-s ~LI~
56 O ~ C2H5 OC6H5 ~O
57 O O C2Hs O-cH2-cH=cH2 ~C~~
58 O ~ C2H5 SCH3 ~O
59 O O C2Hs SC2Hs ~GO
O ~ C2H5 SC3H,-n ~O
REPLACEMENT SHEET (RULE 26) Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 61 O ~ C2H5 SC3H7-i ~o 62 O ~ C2H5 S-cH2-cH=cH2 ~C1~
63 O ~ C2H5 S ~ ~G~
64 O ~ C2H5 SCH2CH2F ~CI~
O ~ C2H5 SCH2CHF2 ~~
66 O ~ C2H5 SCH2CF3 ~CI~
67 O ~ C2H5 N(CH3)2 ~Jo 68 O ~ C2H5 SCH2F ~G~
69 O ~ C2H5 SCH2Cl ~G~
REPLACEMENT SHEET (RULE 26) . WO 97103980 PCT/EP96102932 Table 1: (continued) Ex Q' Q2 R' R2 R3 Melting No point (~C) O O C2H5 SCH2CH2CI ~G~
71 O ~ C2H5 Cl ~cO
72 O ~ C2H5 Br ~G~
73 O O C2Hs CH3 ~G~
74 O O C2Hs C4Hg-n ~Go O O C2H5 f ~ ~G~
76 O ~ C2H5 CH=CH-CH3 ~C1~
77 O O C2Hs CH2OC2Hs ~G~
78 O O C2H, CHz-cH=cH2 ~C~~
REPLACEMENT SHEET (RULE 26) Table 1: (continued) Ex Q' Q2 R' R2 R3 Melting No point (~C) 79 O O C2Hs CH20CH3 ~Go O ~ C2H5 OCH2CF3 ~G~
81 O ~ C2H5 OCH2CHF2 ~~
82 O ~ C2H5 OcH2cF2cHF2 ~G~
83 O o C2H5 ~ ~G~
84 O ~ C2H5 OCH2CH20CH3 ~G~
S ~ C2H5 OC2H5 ~CJ~
86 O S C2H5 OC2H5 ~O
87 O O ~ ~ OC2H5 ~O
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Exo Ql Q2 Rl R2 R3 pomt (~C) 88 O O ~ C2Hs ~L~
89 O O ~ n-C3H7 ~c~o 0 0 ~ i-C3H7 ~CI~
91 0 0 ~ OCH3 ~G~
92 O O ~ OC2H5 ~cO
93 O O ~, OC3H7-n ~C~~
94 O O ~ 0~3H7-i ~1~
O O ~,~ OC4Hg-n ~C~~
96 O O ~ OC4H9-i ~o REPLACEMENT SHEET (RULE 26) W O 9,7/03980 PCT~EP96/02932 Table ]: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 97 O O OC4H9-s o 99 o O O-cH2-cH=cH2 ~
~ ,G .
101 0 o SC2H5 0 102 O O SC3H7-n O
~ )~
103 O O SC3H7-i O
~ ,G
104 O O ~ S-CH2-CH=CH2 ~C1~
105 O O ~ ~ ~ ~ o REPLACEMENT SHEET (RULE 26) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 106 O O ~ SCH2CH2F ~O
107 O O ~ SCH2CHF2 ~O
108 O O ~ SCH2CF3 ~Jo 109 0 0 ~ N(CH3)2 ~~
11 0 0 0 ~ SCH2F ~G~
111 0 0 ~ SCH2C1 ~G~
112 O O ~ SCH2CH2C1 ~o 113 O O ~ Cl ~C1~
1 14 O O ~ Br ~C~o REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 1 15 O O ~ CH3 ~Co 1 16 O O ~ C4Hg-n ~o 117 O O ~ ~ ~C~o 1 18 O O ~ ~ CH=CH-CH3~Co 119 0 0 ~ CH2OC2Hs ~G~
120 O ~ ~ CH2-cH=cH2 ~G~
121 O O ~ CH20CH3 ~G~
122 O O OCH2CF3 r~
REPLACEMENT SHEET (RULE 26) Table 1: (contim~ed) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 123 O O ~ OcH2cHF2 ~CI~
124 O O ~ OcH2cF2cHF2 ~C~~
125 ~ ~ ~ O~
126 O O ~ OCH2CH2OCH3 ~O
127 S O ~ ~C2Hs ~GO
128 O S ~ OC2H5 ~c~O
129 O O OCH3 OC2H5 ~
130 O O OCH3 C2Hs ~G~
131 O O OCH3 n-C3H7 ~O
REPLACEMENT SHEET (RULE 26) WO Sl7/03980 PCT/EP96/02932 Table 1: (col-tinllec~) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 132 O O OCH3 i-C3H, ~C~
133 O O OCH3 OCH3 ~c~o 134 O O OCH3 OC2H5 ~cO
135 O O OCH3 OC3H7-n ~C~~
136 O O OCH3 OC3H7-i ~C~~
137 O O OCH3 OC4Hg-n ~c~o 138 O O OCH3 OC4H9-i ~G~
139 O ~ OCH3 OC4Hg-s ~G~
140 O O OCH3 OC6H5 ~O
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Ex. Ql Q2 R' R2 R3 Melting No. point (~C) 141 O O OCH3 O-cH2-cH=cH2 ~G~
142 O O OCH3 SCH3 ~G~
143 O O OCH3 S~2H5 ~O
144 O O OCH3 SC3H7-n ~O
145 O O OCH3 SC3H7-i ~O
146 O ~ OCH3 S-cH2-cH=cH2 ~G~
147 O O OCH3 ~ S ~ ~1 148 O O OCH3 SCH2CH2F ~o REPLACEMENT SHEET (RULE 26) - W O 9'l/03980 PCTAEP96102932 Table:l:(continued) Ex Q' Q2 R' R2 R3 pomt (~C) 149 O ~ OCH2 SCH2CHF2 p ~
150 O O OCH3 SCH2CF3 ~O
151 0 0 OCH3 N(CH3)2 ~C~
152 O ~ OCH3 SCH2F ~o 153 O O OCH3 SCH2CI ~c~o 154 O O OCH3 SCH2CH2CI ~o 155 O O OCH3 Cl po 156 O O OCH3 Br po 157 O O OCH3 CH3 ~CI~
REPLACEMENT SHEET (RULE 26) WO 97/03980 PCTtEP96tO2932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 No.
158 O O OCH3 C4H9-n ~c~o 159 O O OCH3 ~,~ ~CI~
160 O O OCH3 CH=CH-CH3 ~G~
161 O O OCH3 CH2OC2Hs ~C~~
162 O O OCH3 CH2-cH=cH2 ~G~
163 O O OCH3 CH2OCH3 ~O
164 O O OCH3 OCH2CF3 ~C~~
165 O ~ OCH3 OCH2CHF2 ~~
166 O O OCH3 OCH2CF2CHF2 ~c~
REPLACEMENT SHEET (RULE 26) WO 9'7/03980 PCT/EP96/02932 Table l: (continued) Ex. Q' Q2 R' R2 R3 No.
167 O O OCH3 ~, ~O
168 O ~ OCH3 OCH2CH2- O
OCH3 ~C
169 S O OCH3 OC2H5 ~CI~
170 O S OCH3 OC2Hs ~C1~
171 O ~ OC2H5 OC2H5 ~
J' 172 O ~ OC2H5 C2H5 CI~
173 O ~ OC2H5 n-C3H, ~O
174 O ~ OC2H5 i-C3H, ~cO
175 O ~ OC2H5 OCH3 ~c~o WO 9'7/03980 PCT/EP96/02932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 No.
176 O ~ OC2H5 OC2H5 ~CJ~
177 O ~ OC2H5 OC3H,-n ~cO
178 O ~ OC2H5 OC3H,-i ~CI~
179 O ~ OC2H5 SCH3 ~c~O
180 O ~ OC2H5 SC2Hs ~C~~
181 O ~ OC2H5 N(CH3)2 ~G~
182 O ~ OC2H5 SCH2F ~o 183 O ~ OC2H5 SCH2CI ~CI~
184 O ~ OC2H5 SCH2CH2CI ~G~
~ CA 02227012 1998-01-14 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point (~C) 185 O O OC2E~5 Cl ~G~
186 0 ~ OC2H5 Br ~0 187 0 ~ OC2H5 CH3 ~CJ~
188 0 ~ OC2H5 f ~ ~CI~
189 0 ~ OC2H5 CH=CH-CH3 ~o 190 0 ~ OC2H5 CH2OC2Hs ~~
191 0 ~ OC2H5 CH2-CH=CH2 ~G~
192 0 ~ OC2H5 CH20CH3 ~C~
193 0 0 N(CH3)2 C2Hs ~GO
WO 9'1/03980 PCT/EP96/02932 Table 1: (continued) Ex. Q' Q2 R' R2 R3 Melting No. point ( C) 194 O O N(CH3)2 n-C3H, ~C~~
195 O O N(CH3)2 CH3 ~CI~
196 O O N(CH3)2 OCH3 ~C~
197 O O N(cH3)2 OC2Hs ~Cl~
198 O O N(CH3)2 OC3H,-n ~CI~
199 0 0 N(CH3)2 SCH3 ~O
200 O ~ CH3 C2H5 ~CI~ 159 By the methods of Examples 1 and 2, it was also possible to prepare the following compolmds:
REPLACEMENT SHEET (RULE 26) Examlple 201 ~0 OJ~
_~H~N~N_cH, Melting point: 146~C
Example 202 ~0 [~2--NH~ N J'' N--CH3 CH3 N =( MeltinlJ point: 1 58~C
REPLACEMENT SHEET (RULE 26) - WO 9'1/03980 PCT/EP96/02932 Startinp materials of the formula (VII):
Example (VII-1) ~bo At -lO"C, a solution of 3.4 g of pyridine in 20 ml of methylene chloride is added dropwi ,e with stirring to a mixture of 9.46 g (39 mmol) of 2-chlorosulphonyl-benzoyl chloride, 3.5 g (39 mmol) of 3-hydroxymethyl-tetrahydrofuran and 100 ml of methylene chloride, and the reaction mixture is then stirred at 20~C for about 6 hours.
The mixture is subsequently concentrated using water pump vacuum, the residue isshaken with methylene chloride and aqueous hydrochloric acid (pH 1), and the organic phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully distillecl off from the filtrate using water pump vacuum.
8.2 g (72.5% of theory) of tetrahydrofur-3-yl 2-chlorosulphonyl-benzoate are obtained as an oily residue which can be used directly as such for further reactions.
Example (VII-2) o~lo Step 1 A mixl[ure of 68.3 g (0.20 mol) of bis-(2-chlorocarbonyl-phenyl) disulphide, 29.6 g (0.40 mol) of 3-hydroxy-oxetane, 42.5 g (0.42 mol) of triethylamine and 500 ml of methyllene chloride is stirred at 20~C for 15 hours. 200 ml of lN hydrochloric acid are then added and the organic phase is separated off, washed with water, dried with5 sodiwn sulphate and filtered. The filtrate is concentrated using water pump vacuum, the residue is digested with diethyl ether and the resulting crystalline product is isolated by filtration with suction.
48.6 g (58% of theory) of bis-[2-(oxetan-3-yl-oxycarbonyl)-phenyl] ~ phide of meltin~ point 143~C are obtained.
10 Step 2 At -5~C to 0~C, 11.2 g of chlorine are introduced over a period of about 15 minutes into a mixture of 10.5 g (25 mmol) of bis-[2-(oxetan-3-yl-oxycarbonyl)-phenyl]
disulphide, 12.9 g of sodium acetate and 100 ml of 50% strength aqueous acetic acid.
The reaction IllixLule is stirred at 0~C for a further 15 minutes and then admixed with 15 150 ml of methylene chloride. The methylene chloride phase is then separated off, washed with ice-water, dried with sodium sulphate and filtered. The filtrate is concen-trated using water pump vacuum and the residue is purified twice by silica gel column chromatography (first run with methylene chloride, second run with ethyl acetate).
10.4 g (75% of theory) of oxetan-3-yl 2-chlorosulphonyl-benzoate are obtained as a 20 yellowish oil.
'H NMR (CDCl3, TMS, ~): 4.9 (m, 2H), 5.0 (m, 2H), 5.8 (m, lH), 7.8 (m, 3H), 8.2 (m, lH) ppm.
WO 97/03980 PCTtEP96tO2932 Use examples:
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 active compound plcpa~dtion, 1 part by weight of active com-pound 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. After about 24 hours, the soil is 10 watered with the p,cpaldlion of active compound. It is advantageous to keep the amount of water per unit area constant. The concentration of the active compound in the ~lcl,~dlion is immaterial, only the amount of active compound applied per unit area matters.
After tllree weeks, the degree of damage to the plants is rated in % damage by com-15 parison with the development of the untreated control.
The fi~ures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, the compounds of the formula (I) according to the invention show strong 20 activity against weeds (cf. Table A).
WO 9'7/03980 PCT/EP96/02932 Example B
Post-ernergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable active compound plep~lion, 1 part by weight of active com-pound is mixed with the stated amount of solvent, the stated amount of emlllcifier 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 10 desired per unit area. The concentration of the spray liquor is chosen so that the particu]ar 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 by com-parison with the development of the untreated control.
The figures denote:
0% = no effect (like untreated control) 100% = total destruction In this test, the compounds of the formula (I) according to the invention show strong activity against weeds (cf. Table B).
WO 9'7l03980 PCTIEP96/02932 Table A: Pre-emergence test/greenhouse Active com- Applic- Maize Alope- Cype- Seta- Amaran- Sina-pound ation rate curus rus ria thuspis (according to (g/ha) Preparation Ex.) (7) 250 10 80 - 70 100 (201) 250 - 80 95 80 70 100 (202) 250 0 80 1 00 70 - 70 10 Table :B: Post-emergence test/greenhouse Active com- Application Maize Alopecurus Avena fatua Sinapis pound rate (according to (glha) Plep~lion Ex.) (201) 250 10 80 80 100
Claims (9)
1. Substituted arysulphonylamino(thio)carbonyltriazolin(e-thi)ones of the general formula (I) in which Ar represents respectively optionally substituted arylene or heteroarylene, Q1 represents oxygen or sulphur, Q2 represents oxygen or sulphur, R1 represents hydrogen, hydroxyl, amino, alkylideneamino or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, R2 represents hydrogen, hydroxyl, mercapto, amino, halogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenyl-thio, alkinylthio, alkylamino, alkenylamino, alkinylamino, dialkylamino, alkanoylamino, aziridino, pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkyl-alkyl, cycloalkylalkoxy, cycloalkylalkylthio, cycloalkylalkylamino, aryl, aryloxy, arylthio, arylamino, arylalkyl, arylalkoxy, arylalkylthio, arylalkyl-amino, heterocyclyloxy, heterocyclylthio, or R1 and R2 together represent optionally branched alkanediyl, and R3 represents optionally substituted heterocyclyl, and salts of the compounds of the formula (I).
2. Compounds of the formula (I) according to Claim 1, characterized in that in them Ar represents phenylene or naphthylene, each of which is optionally substituted by halogen, cyano, nitro, by C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, di-(C1-C4-alkyl)-amino-sulphonyl or N-C1-C4-alkoxy-N-C1-C4-alkyl-amino-sulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represents heteroarylene of 5 or 6 ring members, at least one of which is oxygen, sulphur or nitrogen and one or two more are optionally nitrogen, which is optionally substituted by halogen, cyano, nitro, by C1-C4-alkyl or C1-C4-alkoxy (each of which is optionally substituted by fluorine and/or chlorine), Q1 represents oxygen or sulphur, Q2 represents oxygen or sulphur, R1 represents hydrogen, hydroxyl, amino, represents C2-C10-alkylideneamino, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylamino or C1-C6-alkanoylamino, represents C3-C6-alkenyloxy, represents di-(C1-C4-alkyl)-amino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted phenyl or phenyl-C1-C4-alkyl, R2 represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, represents respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or C1-C6-alkanoylamino, represents C2-C6-alkenyloxy, C2-C6-alkinyloxy, C2-C6-alkenylthio, C2-C6-alkinylthio, C2-C6-alkenylamino or C2-C6-alkinylamino, represents di-(C1-C4-alkyl)-amino, represents respectively optionally methyl-and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, represents respectively optionally fluorine-, chlorine-, bromine-, cyano-and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-C1-C4-alkylthio or C3-C6-cycloalkyl-C1-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or phenyl-C1-C4-alkylamino, or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted heterocyclyloxy or heterocyclylthio, the heterocyclyl component being in each case selected from the group consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, thietanyl, thienyl, tetrahydrothienyl, or R1 and R2 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and R3 represents respectively optionally halogen- or C1-C4-alkyl-substituted oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl or tetrahydrothienyl, and the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I).
3. Compounds of the formula (I) according to Claim 1, characterized in that in them Ar represents respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio- or ethylthio-substituted 1,2-phenylene (ortho-phenylene), pyridine-2,3-diyl, thiophene-2,3-diyl or pyrazol-4,5-diyl, Q1 represents oxygen or sulphur, Q2 represents oxygen or sulphur, R1 represents hydrogen, hydroxyl, amino, represents C3-C8-alkylideneamino, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n-or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents dimethylamino or diethylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclo-butylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl R2 represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propinyl or butinyl, represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethyl-thio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, butenylthio, propinyl-thio, butinylthio, propenylamino, butenylamino, propinylamino, or butinyl-amino, represents dimethylamino, diethylamino or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyl-oxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-methoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethyl-thio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethyl-amino, cyclopentylmethylamino or cyclohexylmethylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or represents respectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted oxetanyloxy, furyloxy, tetrahydrofuryloxy, thienyloxy or tetrahydrothienyloxy, or R1 and R2 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and R3 represents respectively optionally fluorine-, chlorine-, methyl- or ethyl-substituted oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl or tetrahydro-thienyl.
4. Compounds of the formula (Ia) in which Q1, Q2, R1, R2 and R3 are each as defined in Claim 3.
5. Process for preparing compounds of the formula (I) according to Claim 1, characterized in that (a) triazolin(e-thi)ones of the general formula (II) in which Q1, R1 and R2 are each as defined in Claim 1 are reacted with substituted arylsulphonyliso(thio)cyanates of the general formula (III) R3-O-CO-Ar-SO2-N=C=Q2 (III) in which Ar, Q2 and R3 are each as defined in Claim 1, if appropriate in the presence of a reaction auxiliary and if appropriate in thepresence of a diluent, or (b) triazolin(e-thi)one derivatives of the general formula (IV) in which Q1, Q2, R1 and R2 are each as defined above and Z represents halogen, alkoxy, aryloxy or arylalkoxy are reacted with sulphonamides of the general formula (V) R3-O-CO-Ar-SO2-NH2 (V) in which Ar and R3 are each as defined above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or (c) triazolin(e-thi)ones of the general formula (II) in which Q1, R1 and R2 are each as defined above are reacted with substituted arylsulphonamide derivatives of the general formula(VI) R3-O-CO-Ar-SO2-NH-CQ2-Z (VI) in which Ar, Q2 and R3 are each as defined above and Z represents represents halogen, alkoxy, aryloxy or arylalkoxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or (d) triazolin(e-thi)ones of the general formula (II) in which Q1, R1 and R2 are each as defined above are reacted with substituted arylsulphonyl halides of the general formula (VII) R3-O-CO-Ar-SO2-X (VII) in which Ar and R3 are each as defined above and X represents halogen and metal (thio)cyanates of the general formula (VIII) MQ2CN (VIII) in which Q2 is as defined above and M represents an alkali metal or an alkaline earth metal equivalent, if appropriate in the presence of a reaction auxiliary and if appropriate in thepresence of a diluent, and, if appropriate, the compounds of the formula (I) obtained by the processes (a), (b), (c) or (d) are converted into salts by customary methods.
6. Herbicides, characterized in that they comprise at least one compound of the formula (I) of a salt thereof according to Claim 1.
7. Use of compounds of the general formula (I) or salts thereof according to Claim 1 for controlling undesirable vegetation.
8. Method for controlling weeds, characterized in that compounds of the general formula (I) or salts thereof according to Claim 1 are allowed to act on the weeds or their habitat.
9. Process for preparing herbicides, characterized in that compounds of the general formula (I) or salts thereof according to Claim 1 are mixed with extenders and/or surfactants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19525974.2 | 1995-07-17 | ||
| DE1995125974 DE19525974A1 (en) | 1995-07-17 | 1995-07-17 | Substituted arylsulfonylamino (thio) carbonyltriazolin (thi) one |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2227012A1 true CA2227012A1 (en) | 1997-02-06 |
Family
ID=7767020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2227012 Abandoned CA2227012A1 (en) | 1995-07-17 | 1996-07-04 | Substituted aryl sulphonyl amino (thio) carbonyl triazolin(thi)ones |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0840734A1 (en) |
| JP (1) | JPH11509219A (en) |
| CN (1) | CN1195347A (en) |
| AU (1) | AU6518896A (en) |
| CA (1) | CA2227012A1 (en) |
| DE (1) | DE19525974A1 (en) |
| WO (1) | WO1997003980A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19933260A1 (en) * | 1999-07-15 | 2001-01-18 | Bayer Ag | Substituted thien-3-yl-sulfonylamino (thio) carbonyl-triazolin (thi) one |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3815765A1 (en) * | 1988-05-09 | 1989-11-23 | Bayer Ag | 2-SULFONYLAMINOCARBONYL-2,4-DIHYDRO-3H-1,2,4-TRIAZOL-3-ONE, INCLUDING 4,5-CONDENSED, BICYCLIC DERIVATIVES, METHODS AND NEW INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND USE THEREOF AS ARE |
| DE3934081A1 (en) * | 1989-10-12 | 1991-04-18 | Bayer Ag | SULFONYLAMINOCARBONYLTRIAZOLINONE |
| DE3936623A1 (en) * | 1989-11-03 | 1991-05-08 | Bayer Ag | SULFONYLAMINOCARBONYLTRIAZOLINONE WITH SUBSTITUTES TIED ABOVE SULFUR |
| DE3936622A1 (en) * | 1989-11-03 | 1991-05-08 | Bayer Ag | HALOGENED SULFONYLAMINOCARBONYLTRIAZOLINONE |
| DE4131842A1 (en) * | 1991-09-25 | 1993-04-01 | Bayer Ag | SULFONYLAMINOCARBONYLTRIAZOLINONE WITH TWO OXYGEN SUBSTITUTES |
| DE4110795A1 (en) * | 1991-04-04 | 1992-10-08 | Bayer Ag | SULFONYLAMINOCARBONYLTRIAZOLINONE WITH OXYGEN SUBSTITUTES |
| DE4435547A1 (en) * | 1994-10-05 | 1996-04-11 | Bayer Ag | Sulfonylaminocarbonyltriazolinone with substituents bonded via oxygen and sulfur |
-
1995
- 1995-07-17 DE DE1995125974 patent/DE19525974A1/en not_active Withdrawn
-
1996
- 1996-07-04 CA CA 2227012 patent/CA2227012A1/en not_active Abandoned
- 1996-07-04 EP EP96924877A patent/EP0840734A1/en not_active Withdrawn
- 1996-07-04 AU AU65188/96A patent/AU6518896A/en not_active Withdrawn
- 1996-07-04 JP JP9506228A patent/JPH11509219A/en active Pending
- 1996-07-04 CN CN 96196762 patent/CN1195347A/en active Pending
- 1996-07-04 WO PCT/EP1996/002932 patent/WO1997003980A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11509219A (en) | 1999-08-17 |
| AU6518896A (en) | 1997-02-18 |
| WO1997003980A1 (en) | 1997-02-06 |
| CN1195347A (en) | 1998-10-07 |
| DE19525974A1 (en) | 1997-01-23 |
| EP0840734A1 (en) | 1998-05-13 |
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