CA2420329C - Sulphonylaminocarbonyltriazolinones - Google Patents
Sulphonylaminocarbonyltriazolinones Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- Agronomy & Crop Science (AREA)
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- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
This invention relates to a triazolinone of the general formula (IIa) (see figure IIa) in which either (1) R1 is C1-C6-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, phenyl, C1-C4-alkoxy or C1-C4-alkoxy carbonyl) or is C3-C4-alkenyloxy and R2 is hydrogen, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represent C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents phenyl-C1-C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, and/or C1-C4-alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, trifluoromethyl, methyl C1-C4-alkoxy, fluorine-and/or chlorine- substituted C1-C3-alkoxy, C1-C4-alkylthio, fluorine- and/or chlorine-substituted C1-C3-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl and/or C1-C4-alkoxycarbonyl; or in which (2) A1 represents and Az represents OCH3 CH(CH3)2 OCH2-CH=CH2 CH3 O-CH2-CH=CH2 C2H5 O-CH2-CH=CH2 C3H7 C3H7 OCH3 OCH3 OCH3 ~ OCH3 OC2H5 The compounds of formula (IIa) are novel intermediates useful in the preparation of herbicidal sulphonylaminocarbonyltriazolinones of the general formula (I)
Description
Substituted 1,2,3-Triazol-3-ones.
The present divisional application is divided out of parent application Serial No. 2,189,698, which was itself divided out of application Serial No. 2,027,206, filed on October 10, 1990.
The invention of the parent application relates to new sulphonylaminocarbonyl-triazolinones of the formula I, to several processes for their preparation, and to their use as herbicides.
The invention of divisional application Serial No.
The present divisional application is divided out of parent application Serial No. 2,189,698, which was itself divided out of application Serial No. 2,027,206, filed on October 10, 1990.
The invention of the parent application relates to new sulphonylaminocarbonyl-triazolinones of the formula I, to several processes for their preparation, and to their use as herbicides.
The invention of divisional application Serial No.
2,189,698 relates to novel intermediates of formula IIa and processes for preparing the intermediates. Compounds of the formula IIa are useful in the preparation of compounds of formula I.
The invention of the present divisional application relates to novel intermediates of formula IIa which are structurally different than those of application Serial No. 2,189,698. The intermediates of the present divisional application are useful in the preparation of compounds of formula I, illustrated below.
It is known that certain substituted amino-carbonylimadazolinones, such as, for example, 1-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), have herbicidal properties (cf. R. Wegler, Chemie der Pflanzenschutz-and Schadlingsbekampfungsmittel [Chemistry of Plant Protection Agents and Pesticides], Vol. 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New York, 1977).
However, the action of this compound is not satisfactory in all respects. The new sulphonylaminocarbonyl-triazolinones are a subgroup of the broad class of compounds of the a general formula (T) R SOZ NH CO N N --- R
N----Rz in which R'' represents hydrogen, hydroxyl or amino, or represents an - la -opt ionally subst ituted radical f rom the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents an optionally substituted radical from the series comprising alkyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and dialkylamino, and R3 represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula (I), have now been found.
The sulphonylaminocarbonyl-triazolinones of the general formula (I) are obtained when a) triazolinones of the general formula (II) O
HN- 'N-R~
N (ll) in which R1 and R2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the general formula (III) R3 802-N C-~ (III) in which 2Q R3 has the abovementioned meanings, if appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) Z-CO-N~N-R1 (IV) ~R2 in which R' and R2 have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, axe reacted with sulphonamides of the general formula (V) R3'S~2'NH2 (V) in which R3 has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or when c) triazoli.t~ones of the general formala (II) O
1-iN~N-R1 ( I I ) ~~-----1~ 2 R
in which R1 and RZ have the abovementianed meanings are reacted with sulphonamide derivatives of the general _ formula (VI) R3-S02-NH-CO-Z (~z) i. n wh 1 ch R3 has the abovementioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, salts are formed by customary methods from ZO the compounds of the formula (T) prepared by process (a), (b) or (c).
The new sulphonylaminocarbonyl-tria2olinones of the general formula (I) and their salts are distinguished by a powerful herbicidal activity. Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than the known herbicide 1-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), which has a similar structure.
The new compounds of the present' parent application 20 are those compounds of the formula (I) in which R1 represents hydrogen, hydroxyl or amino, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-Cg-alkoxy, Cl-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is CA 02420329 2003-03-13 , optionally substituted by fluorine, chlorine and/or bromine, or represents C3-C6-cyGloalkyl which~is opt ional 1y subst ituted: by f luori.ne, - 4a -d chlorine, bromine and or.Cr-C4-alkyl, or represents phenyl-C1-C3-alkyl which ~is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C~-C4-alkyl, trifluoromethyl, Cr-C~-alkoxy and/or Lr-C4-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, C1-C~-alkoxy, fluorine- and/or chlorine-substituted Ci-C3-alkoxy, Cl-C,,-alkylthi~, fluorine- and/or chlorine-substituted C1-C3-alkyltluio, C~-C,,-alkylsul-phinyl, C,-C~-alkylsulphonyl and/or C,-C4-alkoxy-carbonyl, or represents Cr-C6-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, phenyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl., or represents C3-C4-alkenyloxy, or represents Cl-C4-alkylamino which is optionally substituted by fluorine, cyano, C1-C4-alkoxy or Cr-C4-alkoxy-car-bonyl, or represents di-(C,-Cy-alkyl)-amino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents Cr-C6-alkyl which is optionally substitut ed by fluorine, chlorine, brornine, cyano, C3-C6 cycloalkyl, C,-C,,-alkoxy or C1-C,,-alkoxy-carbonyl., or represents C3-C6-cycloal.kyl which is optionally substituted by fluorine, chlorine, bromine and/or.
Cl-C~-alkyl, or represents cyclohexenyl, or repre-sents phenyl-Cr-C3-alkyl which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, vitro, Cr-C,,-alkyl, trifluoromethyl, Cr-C4-alkoxy and/or Cl-Cy-alkoxy-carbonyls or represents phenyl which is~
34 optionally substituted by fluorine, chlorine, bromine, cyano, vitro, Cl-Cy-alkyl, trifluoromethyl.
Cl-C~-alkoxy, fluorine- and/or chiora.ne~-sunst~.tured C1-C3-alkoxy, Cl-C4-alkylthio, f luorine- and/or chlorine-substituted C1-C3-alkylthio, Cl-C;-alkyl-sulphinyl, C1-C~-alkylsulphonyl and/or C1-c:5-alkoxy carbonyl, or represents C1-C6-alkoxy which is option . ally substituted by fluorine, chlorine, cyano, C,-C,, alkoxy or C1-C4-alkoxy-carbonyl, or represents C1-C4-alkylamino or di-(C1-C~-alkyl)-amino, and R3 represents the group R5 , where R° and RS are identical or different and represent , hydrogen, fluorine, chlorine, bromine, iodine, vitro, CI-C6-alkyl.(which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C~-C'-alkoxycarbonyl, Cl-C~-alkylamino-carbonyl, .di-(C~-C,,-alkyl)amino-carbonyl, hydroxyl, Ci-C,-alkoxy, formyloxy, C1-C,,-alkyl-carbonyloxy, Cl-C,,-alkoxy-carbonyloxy, C1-C,-alkylamino-carbonyloxy, Cl-C4-alkylthio, C~-C,~-alkylsulphinyl, C~-C~-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl ) , or represent Cz-C6-alkenyl ( which is option-ally substituted by fluorine, chlorine, bromine, cyano, C1-C~-alkoxy-carbonyl , carboxyl or phenyl ) , or .
represent C2-C6-alkinyl (which is optionally s'ubsti-.
tuted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent - s --" C1-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-Cy-alkoxy-carbonyl, C1-C4-alkoxy, C1-C~-alkylthio, C1-C~-alkylsulphinyl or C1-C4-alkylsulphonyl ) , or represent C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C,,-alkoxy-carbonyl, C1-C4-alkylthio, Ci-C4-alkyl.sulphinyl or C1-C4-alkylsulphonyl ) , or represent C3-C6-alkenyl-oxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), or represent C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C3-alkylthio or Cl-C4-al.koxycarbonyl ) , C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the radical -S(O)p-R6 where p represents the numbers 1 or 2 and R6 represents C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C4-alkoxy-carbonyl ) , C3-C6-alkenyl ~ C3-C6-alkinyl, Ci-C4-alkoxy, Cl--C~-alkoxy-C1-C4-alkyl-amino, C1-C4-alkylamino, di- ( C,-C4-alkyl ) -amino or phenyl, or represents the radical -NHOR' where R'_ represents C1-C12-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C,-C$-alkoxy, C1-C4-alkylthio, C1-C4-alkylsul phinyl, l C,-C4-alkylsulphonyl, Cl-C4-alkyl carbonyl, C1-Cy-alkoxycarbonyl, C1-C,-alkyl amino-carbonyl or di-(C1-C4-alkyl)-amino carbonyl), or represents C3-G6-alkenyl (which is optionally substituted by fluorine, _ 7 _ _ chlorine or bromine) , C3-C6-alkinyl, C~-C6-cyclaalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substi-tuted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, C1-C4-alkoxy ar C1-C,-alkoxy-car-bonyl), or represents benzohydryl, or repre-sents phenyl (which is optionally substituted by f luorine, chlorine, nitro, cyano, C1-C,,--alkyl-, trifluoromethyl, C~-C,,-alkaxy, C~-C2-fluoroalkoxy, C1-C4-alkyl.thio, trifluoromethyl-thio or C,-C~-alkoxycarbonyl ) , R° and/or Rs furthermore represent phenyl or phenoxy, or represent C1-C~-alkylcarbonylamino, C~-C4-alkoxycarbonylamino, C1-C4~-alkylamino-carbonyl-amino, di-(C1-C4-alkyl)amino-carbonylamino, or represent the radical -CO-R8, where RB represents C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4 alkylthio, C1-C4-alkylamino, C1-Cy-alkoxyamino, C1-C4-alkoxy-C~-C4-alkyl-amino or di- ( C1-C4-alkyl ) -amino ( each of which is optionally substituted by fluorine and/or chlorine), R' and/or Rs furthermore represent tr.i.methylsilyl, thiazolinyl, C1-C,-alkylsulphonylox.y, di-(C1-C~
alkyl)-aminosulphonylamino, or represent the radical -CH=N-R9, where Rs represents Cl-C~-alkyl which is optionally substituted by fluorine, chlorine, .cyano, . carboxyl, Ci-C~-alkoxy, C1-C4-alkylthio, C1-C~
alkylsulpl~inyl or C1-(:4-alkyl sulphonyl, or represents benzyl which is optionally substi-- tuted by fluorine or chlorine, or represents C3-CB-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlor ine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, Cl-C~-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C~-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, Cl-C~-alkyl-amino, di-{Cl-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C,-alkoxy-car-bonylamino or C1-C;-alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl, furthermore R3 represents the radical -iH , where Rl° represents hydrogen or Ci-C~-alkyl, R'1 and R12 are identical or different and represent hydrogen, fluorine, chlorine, bromine, vitro, cyano, C~-C,-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C~-C~-alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl,'Cl-C,-alkoxy-carbonyl, f - ~ r dimethylaminocarbonyl, C1-C~-alkylsulphonyl or di-(C1-C,-alkyl)-aminosulphonyl;
furthermore R3 represents the radical R13 ~ R , where R'3 and R'~ are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substitut ed by fluorine and/or chlorine ) or C~-~,,-alxoxy (which is optionally substituted by fluorine and/or chlorine);
furthermore R' represents the radical ~ ~ , where . . ~N
ftib R'S and R'6 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C~-C4-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine , or represent C,-C4-alky l.thio, C1-Cy-alkylsulphinyl or C1-C4-alkylsulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represent di-(Cl-C~-alkyl)-aminosulphonyl or C1-C~-alkoxy-carbonyl or di-methylaminocarbonyl;
- to -furthermore R3 represents the radical R1~ ~ ~ ~ Rla , where ~J
R" and RlB are identical or different and represent hydrogen, fluorine, chlorine, bromine, C~-C,-alkyl (which is optionally substituted by fluorine and/or bromine), Cg-C~-alkoxy (which is optionally substi-tuted by fluorine and/or chlorine), or represent C1-C~-alkylthio, Cl-C4-alkylsulphinyl or C1-C,-alkyl-sulphonyl (each of which is optionally substituted by fluorine and/or chlorine) ~ or represent di-(C1-C4-alkyl)-aminosulphonyl;
furthermore R3 represents the radical , where ~' ~R20 Rte and RZ°.are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine) , C~-C4-alkylthio, C1-C~-ahkylsul-phinyl or Cl-C4-alkylsulphonyl (which is optional-ly substituted by fluorine. and/or chlorine), di-(C1-C4-alkyl)-amino-sulphonyl, C:l-C4-alkoxy-car-bonyl or di.methylaminocarbonyl, and.
A represents oxygen, sulphur or the group N-Z', _ 11 where - Z' represents hydrogen, Cl-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by f luorine, chlorine, bromine or vitro ) , C1-C4-alkylcarbonyl, C1-C,-alkoxy-carbonyl or di-(C,-C~-alkyl)-aminocarbonyl;
furthermore R3 represents the radical .~~R22 r where 1 , R21 and R22 are identical or different and represent hydrogen, C1-Cy-alkyl, halogen, Ci-Ca-alkoxy-carbonyl, Ci-C~-alkoxy or C1-C4-halogenoalkoxy, Y1 represents sulphur or the group N-R23, where Rz3 represents hydrogen or C1-Cu-alkyl g furthermore R3 represents the radical ( , where tJ~N
~24 R
R24 represents hydrogen, C,-C~-alkyl, benzyl, quinolinyl or phenyl, RZS represents hydrogen, halogen, cyano, vitro, C1-C~-alkyl (which is optionally substituted by fluorine and/or chlorine); Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or Cl-C4-alkoxy-carbonyl, and Rz6 represents hydrogen, halogen or C1-C4-alky l furthermore R3 represents one of the groups listed below, \ ~ ~ N'_Ca~9 ' N ~
~S S ~'OCHZCP3 '~ 1 \ o The invention furthermore preferably relates to the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkylammonium, di-(Cl-C~-alkyl)-ammonium, tri-(Cl-C4-alkyl)-ammonium, C5- or C~-cycloalkyl-ammonium and di-(Cl-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which Rl, R2 and R3 have the meanings mentioned above as being preferred.
In particular, the invention of the parent application relates to compounds of the formula (I) in which R1 represents hydrogen, or represents C1-C~-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, methoxy or ethoxy, or represents allyl, or represents C3-C6-cycloalkyl, or repre-sents phenyl, or represents.benzyl, or represents C1-C3-alkoxy, or represents C1-C3-alkylamino, or represents di-(C1-C2-alkyl)-amino, R2 represents hydrogen, or represents Ci-C"-alkyl which is optionally substituted by fluorine and/or chlor ine or by methoxy or ethoxy, or represents C3 cycloalkyl, or represents phenyl, or represents C1-C3-alkoxy, or represents C1-C3-alkylamino, or represents di-(C1-C2-alkyl)-amino, and R3 represents the group , R~ , where R4 represents fluorine, chlorine, bromine,, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C1-C3-alkylthio, C~-C3-alkylsulphinyl, C1-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylamino-sulphonyl, phenyl, phenoxy or C1-C3-alkoxy-~car-bonyl, and Rs represents hydrogen, fluorine, chlorine or bromine;
furthermore R9 represents the radical _~1~~ , where R'° represents hydrogen, ' , R11 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and R~'2 represents hydrogen, furthermore R~ represents the radical ~J
RO-C S ' IJ
O
where R represents Cl-C4-alkyl, or represents the radical O
I I
RO-C
I ,IN
N
~3 where R represents C1-C4-alkyl.
Examples of the compounds are listed in Table 1 below -- cf. also the Preparation Examples.
R3-S02-N!-~-CO-H~N-~i (I) R
Table 1: Examples of the compounds of the formula (I) R1 R2 ~3 F
H
H
CH2-CH=CHI C2HS
OCH3 C3H7 ~H2_ O-CH2-CH=CH2 S COOCH3 C2H5 C9H9_n - is -Table 1 - cont~.nuation CH3 C3H?
S02N(CH3)2 C3H~
GH3 CzHS C 1_~
~/
Br CHI
~~COOCH3 OC3H~ CH3 'NI~N~
CH3 C3H7 S~COO.CH3 N(CH3)2 CHZ ~H2_ - Table 1 - continuation NH-CH3 ~H
COOCZHS
CH3 C3Hy r/
F~CHO
OCZHS
F
CH~~ CH2~ /
CHZ C3H' ~/
~ .N~
C3H~ ~N
COOCH~
CH~O
CH3 C2H5 ~ SAN-C4H9 Table 1 - continuation ,~ CONtCH312 CH3 CqH9 CON(CHal2 CH3 C3H~ i C3H~ /~
CH3 C3H~-n C3H7-n Tabs _ continuation CF'3 CH3 C4H~ HZ' CH3 ~ v H2_ Cl C2H5 / H2, CFA
CN
CH3 CH(CH3)2 H
~~~COOCZHS
N, ~. ~
Table 1~- continuation ~COOC2H5 N N
OCH3 CaHS ~N
i COOCH(CH3)2 ca CH3 CH3 ..' ! CF3 r ~N--C H 3 C 1.
CON(CH372 CH3 CH3 H3C' N
CH3 CH(CH3)2 H2 Table 1 - continuation R1 R2 ~3 Br OCH2-C~-i=CH2 C2H5 CH3 ~CH3 S02-N., OCH3 C2Hg /
Br CH3 CH(CH3~2 CH3 CHZ-CH=C~2 SO~CH3 SCH(CH3)2 F
F
.~~ CON(CH3)2 CH2-CH=CH2 H
s Table 1 - continuation Ri R2 H3 OCHFZ
CH2-GH=CN2 CH3 r CH2-CH=CHZ G~HS ~N'N
C2Hg S OOCH3 CH3 C3H' ~~__~ H 2 _ Si(CH3)3 i I CON(CH3)~
C2~i5 C~
Table 1 - continuation f~ 1 R2 N3 CON<CH3)2 C2H$ C4H9 S
CH3 C3H? , NHS CH2-CF3 'O
C 2H 5 NwN/'r.
OCH3 CH(CH3)2 / H2~
. i CF'3 CHI H
Table 1 - continuation Ri R2 ~3 CHI, C3H~ f OCH3 C3H? \ 1) O .
O
SOZCH~
Bc OCHF'2 CHZ-CH~GH2 CH2-O-CH3 Table 1 - continuation Rt R2 R3 OCH2CH~-C1 N(CH 3~. N(CH 3~
If, for example, 2-6-difluoraphenyl isocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (a) can be outlined by the following equation:
O
H.N~N~OGH3 _. N=C~O + !
N
P
SOZ NH-CO~ ~ ~OCH3 N N
N
~C 1H
2s If, for example, 2-methylthio-benzenesulphonamide and 2-chlorocarbonyl-4-dimethylamino-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (b) can be outlined by the following equation:
SCH3 ~
r Cl-CO~N~N~N(CH3)2 _ \ , S02-NHZ + N -HCl H
SCHg O
\~/ SOZ-NH-CO~N~N~N(CH3~
N--H
If, for example, N-methoxycarbonyl-2-methoxy-benzenesul-phonamide and 5-diethylamino-4-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (c) can be outlined by the following equation:
OCH3 () + H.N~N..CHFa \ ~ SOz~~ ~~~ ~ I
N(C~,Hs~
O
-H c \ / ~°2~~ co,N~..,N'CHF2 N rt(C2H~)a .
'Formula (II) provides a general definition of the triazo-linones to be used as starting substances in processes (a) and (c) for the preparation of compounds of the formula (I).
In formula (II), R1 and R2 preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the - compounds of the formula (I) as being preferred, or f part icularly preferred, far R1 and Rz .
Examples of the starting substances of the formula (II) are listed in Table 2 below.
O
~~~~R1 N (II) Table 2: Examples of the starting substances of the formula (II) H H
C3H~ H
Table 2 - continuation CH(CH3)2 ~
CqH9 ' H
CH2CH(CH~)2 H
C(CH3)3 H C~HS
H CgH~
H cHccNs)2 H C~H9 H CH~CH(CH3)2 H CICH3)3 CHF'2 H
H ' CH20CH3 H CH20CZH~
Table 2 - continuation CHa GZHS
CH3 C~H~
CH3 CHtCH3)2 CH3 C~~9 CH3 CH2C~i t CH3 ) 2 CH3 C(C~~~3 CZHS C~3 , C3H7 CH3.
CH(CH3)2 C~3 CH2CHtCH3)2 CH3 C3H7 C3H~
CFZCHFZ CH
,, v . . ..:,,i i Table 2 , continuation C2H5 C'~Hg C6H5 t:H3 /t:H 2 _C~CH CH3 cH3 ~ ~G~cH
CHI
GH3 NtCH~)~
C2H~ N(CH~) ~, CzHS
C3H~
C~H~
_ 31 -<~ Table 2 - continuation .
~2H5 C3H~
CH3 NHCH~
NHCH~ CH3 NHCH~ C~H' N(CH3)2 CHI
N(CH3)2 C2H5 N(CH3)2 C3H7 a , Table 2 continua~tiox~
.. R~ ~~
OCN3 C~l~
OCH3 C~H~
OCZHS CHI
~C2H5 G2H~
..:.~
CH2'O-C~1-i5 N(CH~>~, O-C3H7 C3H?
O-CH2-CH=CH2 CH~-O-CHZ-CH=CH2 C~HS
O-CH~-CH=CH2 C3H7 O-CHI-~H-CH2-Br C~H7 ;
Hr Table 2 - continuation OC H.3 OCH
OCH3 CHx OCH3 NtCN3)2 O-CH2-COOCH3 C3H~
NtCH3)2 NtCH~)2 NtCH3)2 OC2HS Cgkl7 Table 2 - continuation .. R1 NH-CH3 . C~2-p-CHI
.__L.~ CN2_O_CH3 CH3 Ctl2-p-CH3 - ~5 -', The starting substances of the formula (II) are known w and/or can be prepared by processes known per se (cf.
Chem. Ber. 90 (1957) 909-921 loc.cit. 98 (1965), 3025 3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra hedron 32 (1976), 237-2352; Hely. Chim. Acta 63 (1980), 841-859; J. Chem. Soc. C 196?, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11.1988;
DE-P 3,916,20?/LeA 26,849 dated 18.05.1989;
DE-P 3,916,208/LeA 26,850 dated 18.05.1989;.7. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated 24.05.1989).
For example, the triazoli.nones of the formula (II) are obtained when «) oxadiazolinones of the general formula (V)T) ~N~ t Y I I ) N~R2 in which R2 has the abovementioned meaning are reacted with amino compounds of the general formula (VIII) HZN-Ri (VIII) in which R' has the abovementioned meaning, at temperatures between 20°C and 120°C and, if appropriate, in the presence of a diluent, such as, - for example, water, and the hydrazine derivatives formed by this process, q~ t~~ general formula (IX) H~ ~.CO-N~-R~
H
(IX) .-Nw in which Rl and R2 have the abovementioned meanings, are isolated by customary methods (cf. the Preparation Examples) and - or if appropriate even without intermediate isolation - the compounds of the formula (IX) are condensed at temperatures between 20°C and 120°C and, if appropriate, in the presence of a basic condensation auxiliary, such as, for example, sodium hydroxide, and, if appropriate, in the presence of a diluent, such as, for example, water, to give the compounds of the formula (II) (cf. EP-A 301,946, DE-OS (German Published Specification) 3,743,493/LeA 25,759 and the Preparation Examples ), or when p) amino compounds of the general formula (VIII) H2N'RI (YIII) in which Rl has the abovementioned meaning, are reacted with carbonic acid derivatives, such as, for example, Biphenyl carbonate, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of the general formula (X) ~ Rp~ 30 in which R2 has the abovementioned meaning and R represents lower alkyl, at temperature between 0°C and 150°C and, if appropriate, in the presence of a diluent, such as, for example, ethylene chloride (cf. DE-P
3,920,270/LeA 26,937 dated 21.06.1989, DE-P 3,928,662/LeA
27,137 dated 30.08.1989, and the Preparation Examples).
Some of the compounds of formula II are novel.
According to one aspect of the invention of the divisional application Serial No. 2,189,698, there is provided a triazolinone of the general formula (IIa) HN N~ (IIa) N
A
in which either (1) A1 represents di-(C1-C4-alkyl)-amino and A2 represents hydrogen, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, Cl-C4 alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents C1-C~-alkoxy;
or in which ( 2 ) A1 represents and A2 represents OCIi3 CH3 OCH 3 ~(~ 3)2 OGH2C6Iis CH3 OG2Hs C~.H~
OCH 3 C,~.H9 a OC~H~ C3H~.
OCHZ-CHCH2 ~3 O-CHZ-CHCH2 ~-2H5 O-CH2-CH-CH-Hr C~.H~
Br ~3 ~3 O-CH~_COOCH 3 C3H7 C3H~
CH(CH 3)~
C~~
H
- 39a -NHz OCH3 o CzHs -CHZCH=CHz CH3 CH3 -CHzOCH3 -CHZOC2Hs ~ -N ( CH3 ) z .
According to one aspect of the present divisional invention, there is provided a triazolinone of the formula HN N~ (IIa) I
N Rz wherein R1 is Cl-C6-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, phenyl, Cl-C4-alkoxy or C1-C4-alkoxycarbonyl) or is C3-C4-alkenyloxy and Rz is hydrogen, or represents Cl-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy or Cl-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents phenyl-C1-C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or Cl-C4-alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, methyl, C1-C4-alkoxy, fluorine- and/or chlorine-substituted - 39b -C1-C3-alkoxy, C1-C4-alkylthio, fluorine- and/or chlorine-substituted C1-C3-alkylthio, C1-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-alkoxy-carbonyl.
According to another aspect of the present divisional invention, there is provided a triazolinone as described herein, wherein R'' is methoxy, ethoxy, propoxy or isopropoxy, and RZ is hydrogen, C2-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl.
According to still another aspect of the present divisional invention, there is provided a triazolinone as described herein, selected from the group consisting of those wherein - 39c -R1 represents and Rz represents OCH3 CzHs OCH3 C3H~
OCZHS
CzHs OCH3 CH ( CH3 ) z OCzHs C3H~
OC3H~ C3H~
O-CHz-CH=CHz CH3 O-CHz-CH=CHz Calls O-CHz-CH=CHz C3H~
0- C H 2 -C H-C H z-B r C3H~
Br H
CHz O-CHz_COOCH3 C3H~
The new triazolinones of the formula (IIa) are obtained either when oxadiazolinones of the general formula (VIIa) - 3 9d -N 0 (VIIa) N-Az in which A2 has the abovementioned meaning, are reacted with amino compounds of the general formula (VIIIa) H2N A1 (VIIIa) in which A1 has the abovementioned meaning, analogously to the process described above under (a), or when amino compounds of the general formula (VIIIa) HzN A1 (VIIIa) are reacted with carbonic acid derivatives, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of - 39e -the general formula (Xa) tR0)3C-A2 (Xa) in which A2 and R have the aboyementio~ed meanings, analogouslx to tile process described above under (,e) (also see the Preparation Examples).
In the general formula (IIa), Al preferably represents C1-C5-alkyl, C3-CS-alkenyl or C3-C6-cycloalkyl, or represents Cl-C6-alkoxy ' which is optionally substituted by fluorine, chlo-rine, bromine, cyano, Cl-C4-alkoxy or Cl-C4-alk-oxy-carbonyl, in particular methyl, ethyl, allyl, .cyclopropyl, methoxy, ethoxy, propoxy or isoprop-oxy;,or represents di-(Cl-C4-alkyl)-amino, in par-ticular dimethylamino or diethylamino, and A2 preferabhy represents hydrogen, or represents C~-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, C1-C~-alkyl-carbonyl or C~-C~-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C~-alkyl, or represents phenyl-C1-C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or Cl-C~-alkoxycarbonyl, or represents phenyl which is optionallx substituted by fluorine, chlor-ine, bromine, cyano, vitro, C1-C4-alkyl, trifluoro-methyl, Cl-Cw-alkoxy, fluorine- and/or chlorine-substituted C1-C3-alkoxy, C1-C~-alkylthio, fluorine-and/or chlorine-substituted C1-C3-alkylthio, Cl-C4-alkylsulphinyl, C1-C,,-alkylsulphonyl and/or C1-C~-- 40 _ alkoxy-carbonyl, or represents C1-C4-alkoxy, in particular hydrogen, C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl, or represents methoxy or ethoxy, provided that both Al and A2 do not simultaneously represent C1-C6-alkyl.
The compounds of the formulae (VII), (VIIa);
(VTII), (VIIIa) and (X) or (Xa) which are to be used as starting substances for the preparation of the triaxolinones of the formulae (II) or (IIa) are known (cf. Helv. Chim. Acta 55(1972), 1174; EP-A 301,946; DE-OS (German Published Specification) 3,743,493).
Formula (III) provides a general definition of the sulphonyl isocyanates further to be used as starting substances in process (a) for the preparation of compounds of the formula (I).
In formula ( IIT ) , R3 preferably, or in part icular, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
Examples of the starting substances of the formula (III) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-,. 2-propylthio-, 2-methyl-sulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-.
2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl, 2-propoxycarbonyl- and 2-isopropoxy-carbonyl-phenylsulphonyl isocyanate, 2-fluoro-, 2-chloro-, 2-difluoramethoxy-, 2-trifluorometh-2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl isocyanate, 2-methoxy-carbonyl-3-thienyl-sulphonyl isocyanate, 4-methoxycarbonyl-and 4-ethoxycarbonyl-1-methylpyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of the formula (III) are known and/or can be prepared by processes known per se (cf.
US-P 4,127,405, 4,169,719,'4,371,391;.EF-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (a) for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Suitable diluents in this context are virtually ail inert organic solvents. These preferably include aliphatic and aromatic, optionally haiogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such. as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetra-methylene sulphone and hexamethylphosphoric triamide.
In process (a), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 150°C, preferably at temperatures between 10°C and 80°C.
Process (a) 1s generally carried out under atmospheric pressure.
For carrying out process (a), between 1 and 3 moles, preferably between 1 and 2 moles, of sulphonyl isocyanate of the formula (:III) are generally employed per mole of triazolinone of the formula (II).
The reactants can be combined in any desired seguence. The reaction mixture is stirred until the reaction is complete. and concentrated, and the crude product which remains in the residue is crystallized using a suitable solvent, such as, for example, diethyl ether. The product of the formula (T) which has been obtained in crystalline form is isolated by filtration with suction.
Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting substances in process (b) for the preparation of compounds of the formula (I).
In formula (IU), R1 and R2, preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula ( T ) as being preferred, or particularly preferred; for R1 and R2, and Z preferably represents chlorine, Cl-C4-alkoxy, benzylaxy or phenoxy, in particular methoxy or - 43a -- phenoxy.
Examples of the starting substances of the formula (IV) which are possible are the compounds of the formula (IV) to be prepared from the compounds of the formula (II) listed in Table 2 Wand phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or Biphenyl carbonate.
The starting substances of the formula (IV) are known and/or can be prepared by processes known per se (cf. EP-A 283,876; EP-A 294,666; EP-A 298,371.
The triazolinone derivatives of the formula (IV) are obtained for example When ~.riazolinanes of the general formula (II) NN~N~R1 tII>
I RZ
in which R1 and R2 have the abovementioned meanings, are reacted with carbonic said derivatives of the general formula (XIj z-co-z~
in which Z has the abovementioned meaning and _ 44 _ Z1 represents a leaving croup, such as chlorine, methoxy, benzyloxy or phenoxy, at temperatures between -20°C and -+-100°C, if appropriate in the~presence of a diluent, such as, for example, tetrahydrofuran, and, if appropriate, in the presence of an acid acceptor, such as, for example, sodium hydride or potassium tent-butylate (cf. the Preparation Examples).
Formula (V) provides a general definition of the sulphonamides further to be used as starting substances in process (b) for the preparation of compounds of the formula (T). .
In formula ( V ) , R3 preferably, or in part icular, has the meaning which has already been mentioned above in connection with the description of .the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
examples of the starting substances of the formula (V) which may be mentioned are:
2-fluoro-, ~2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, ZO 2-t rif luoromethyi- , 2-dif luoro-methoxy- , 2-t rif luoromethoxy- , 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylamino-sulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-isopropoxy-carbonyl-benzenesulphonamide, 2-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyJ.-and 2-ethaxycarbonyl-phenylmethanesulphanamide, 2-methoxy-carbonyl-3-thiaphenesu7_phonamide, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-sulphonamide.
The sulphonamides of the formula (V) are known and/or can be prepared by processes known per se (cf. US-P
4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (b) for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Suj.table diluents in this context are virtually all inert organic solvents, for example those which have been indicated above in the case of process (a).
Acid acceptors which can be employed in process (b) are all acid-binding agents which can customarily be used for reactions of this type. The following are preferably suitable: alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate, potassium carbonate, sodium tert-butylate and potassium tert-butylate, furthermore aliphatic, aromatic or heteracyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1-5-diazabicyclo-(4.3.0]-non-5-ene (DBN), 1-8-diazabicyclo-[5.4.U)-undec-7-ene (DHU) and 1,4-diazabicyclo-[2,2,2]-octane (DABCO).
When carrying out process (b), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C.
In general, process (b) is carried out under atmospheric pressure: However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process (b), the specifically required starting substances are generally.employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess. In general, the reactions are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in~process (b) is carried out in each case by customary methods.
The triazolinones of the formula (II) which are to be used as starting substances in process (c) for the preparation of compounds of the formula (I) have already been described as starting substances for process (a).
formula (VI) provides a general definition of the sulphonamide derivatives further to be used as starting substances in process (c) for the preparation of compounds of the formula (I).
In formula (VI), R3 and Z preferably, or in particular, have those meanings which have already been ment ioned above in connect ion with 'the descript ion of the _ 47 compounds of the formula (I) or (IV) as being preferred, or particularly preferred, for R3 and Z.
Process (c) is preferably carried out using diluents. Suitable diluents in this context are the same organic solvents as have been mentioned above in connection with the description of process (a).
If appropriate, process (c) is carried out in the presence of an acid acceptor. Suitable acid-binding agents in this context are the same as have been mentioned above in connection with the description of process (b).
When carrying out process (c) the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C.
In general, process (c) is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
for carrying out process (c), the specifically required starting substances are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess.. In general, the reactions' are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in process (c) is carried out in each case by customary methods.
To convert tlne compounds of the formula ( :I ) into salts, they are stirred with suitable salt formers, such as, for example, sodium hydroxide, sodium methylate, sodium ethylate, potassium hydroxide, potassium methylate or potassium ethylate, ammonia, isopropylamine, dibutylamine or triethylamine, using suitable diluents, such as, for example, water, methanol or ethanol. The salts can be isolated as crystalline products - then if appropriate after concentrating the mixture.
The active compounds can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense; there are to be understood all plants which grow in locations where they are undesired. Whether the substances act as total or selective herbicides depends essentially on the amount used.
The active compounds can be used, for example; in connection. with the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,. Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Tpornoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus; Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, );mex, Datura, Viola, Galeopsis; Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the genera~ Gossypium, Glycine, Heta, Daucus, Phaseolus, Pj.sum, Solanum, Linum, Ipoznaea, Vicia, Nicoti_aIla, Lyropersleon, Arachis, E3rassica, Lar_tuca, Cucumis and Cucurbita.
Monacotyledon weeds of the Genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Branchiaria, Lolium, Bramus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactylactenium, Agrastis, Alopecurus and Apera.
Monocot~edon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However,-the use of-the active compounds is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks,~and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields,. in lawns, turf, meadows and pastures, and for the selective cornbating of weeds in annual cultures.
The compounds of the formula (I) are suitable for combating monocotyledon and dicotyledon weeds both 'in the pre-emergence and the post-emergence method. They are - markedly more effective than, for example, isocarbamide.
To a certain extent, the compounds also Shaw a fungicidal action, far example against powdery mildews and against apple scab, and also against Pyricularia oryzae on rice.
The active campounds ca.n be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-act ive agents, that is emulsifying agents and/or dispersing agents and/or forming agents.
In the case of the use of water. as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions; mineral and vegetable oils, alcohols, such as ~ CA 02420329 2003-03-13 butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dixnethyl sulphoxide, as well as water.
As solid carriers there ~:re suitable: 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 highly disperse silica, alumina and silicates, as solid carriers fox granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as Well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives 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, as well as natural phospholipids, such as cephalir~s and lecithins, and synthetic phospholipids, can be used in the formulations.
Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs, and metal phthalocyanine dyestuffs, and trace nutrients such as salts of ion, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds, the active compounds as such' or in-the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3~(2,2-dimethylpropy'1)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURONj for combating weeds in cereals 4-amino-3-methyl-6-phenyl-1,2,4-t_riazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino=6-(l,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIHUZIN) for combating weeds in soya beans= furthermore also mixtures with 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butric acid (2,4-DH); 2,4-dichlorophenoxypropionic acid (2,4-DP); 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid (ACIFLUORFEN);
2-chloro-2',6'-diethyl-N-methoxy-methyl-- 53a -acetanilide (ALACHLOR); 2-chloro-4-ethylamino-6-iso-propylamino-1,3,5-triazine (ATRAZINE); methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]carbonyl]-amino]-sulphonyl]-methyl]-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitro-benzoate (BTFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)-acetamide (BUTACHLOR); ethyl 2-{[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHT.ORIMURON);2-chloro-N-i[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-phenyl)-urea(CHLORTOLURON); 2-chlaro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine(CYANAZINE);2,6-dichlo-robenzonitrile(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propianic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxazolidin-3-one (DIMET~iAZONE); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(9H)-one (ETHIOZIN); 2-~4-[6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanaic acid, its methyl ester or its ethyl ester (FENOXAPROP);
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); N,N-dimethyl-N'-(3-trifluoromethyl.phenyl)-urea {FLUOMETURON); 1-methyl-3-phenyl-5-(3-triflnoromethylphenyl)-4-pyridone (FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-mett~ylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)~5-oxo-0 1H-imidazol-2-yl]-9(5)-methylbenzoate (IMAZAMETHABENZ);
- 2-(4,5-dihydro-9-methyl-9-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid (IMAZ,APYR); 2-[5-methyl 5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinoli_n carboxylic acid (TMAZAQUIN); 2-[4,5-dihydro-4-methyl-4 isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETIiAPYR); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-iso-propylphenyl)-urea (ISOPROTURON); (2-methyl-4-chloro-phenoxy)-acetic acid {MCPA); (9-chloro-2-methylphenoxy)-propionic acid (MCPP); N-methyl-2-(1,3-benzothiazol-2--yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-di_methyl-phenyl)-N-[(1H)-pyrazol-1-yl-methyl]-acetamide (METAZACHLOR); 2-ethyl-6-methyl-N-(1-methyl- 2-metho-xyethyl)-chloroacetanilide (METOLACHLOR); 2-.{[j((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic aicd or its methyl ester (METSULFURON}; 1-(3-trifluoromethyl-phenyl)-4-methyl-amino-5-chloro-6-pyridazone (NORFLURAZON); N-(1-ethyl-propyl)-3_,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
0-{6-chloro-3-phenyl-pyridazin-9-yl) S-octyl thio-carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETH'YL); 2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); methyl 2-~[(4,6-dimethyl-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl]-benzoate (SULFOMETURON); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate {THIAMETURON); S-(2,3,3-trichloroallyl)-N,N-diisopropylthiocarbamate (TRI-ALLATE), 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN). Surprisingly, some mixtures also show a synergistic effect.
Mixtures with other known active compounds, such as fungicides, 1I18eCtiCideS, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds can he applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 15 kg of active compound per hectare of soil surface, preferably between 0.05 and 10 kg per ha.
The preparation and use of the active compounds can be seen from the following examples.
a Prega~ation~Xamples:
- Examgle 1 (A ,j--S02-NH-CO~N~N
(Process (a)) 3.0 g (17.95 mmol) of 4-cyclopentyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 60 ml of acetonitrile, and 6.9 g (28.6 mmol) of 2-methoxycarbonyl-phenylsulphonyl isocyanate~ dissolved in 20 ml of aceto-nitrile, are added to this solution with stirring. The reaction mixture is stirred for 6 hours at 20°C and then concentrated. The residue which remains is stirred with diethyl ether, and the product Which has been obtained in crystalline form is isolated by filtration with suction.
This gives 6.6 g (90 % of theory) of 4-cyclo pentyl-5-methyl-2-(2-methoxycarbonyl-phenylsulphonyl aminocarbonyl)-2,4-dihydro-3~.-~,2i4-triazol-3-one of melting point 146°C.
- 5? -Example 2 CI
_ O
S02 NH-CO~N"~N~CH3 N---~
'C H
2 l (Process (b)) 1.8 g (11.8 mmol) of 1,8-diazabicyclo-[5,4,0]-under-7-ene (DBU) are added to a stirred mixture of 3.0 g (y2.1 mmol) of 5-ethyl-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.5 g (12.2 mmol) of 2-chloro-6-methyl-benzenesulphonamide and 60 ml of acetonitrile. The reaction mixture is stirred for 2 hours at 20°C, then poured into about twice the volume of ice-water, and a pH of about 2 is established by dropwise addition of concentrated hydrochloric acid. The product which has been obtained during this process in crystalline form is isolated by f. l It rat ion with suet ion .
This gives 3.2 g 973.5 $ of theory) of 5-ethyl-4-methyl-2.-(2-chloro-6-methyl-phenylsulphonyl-aminocarbonyl) 2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 176°C.
For example the compounds of the formula (I) listed in Table 3 below can also be prepared analogously to Examples 1 and 2 and following the general instructions of the preparation processes R3-S02-NH-CO~N~N~1 (I) ~R2 Table 3~ Preparation Examples of the compounds of the formula (1y (w. - melting point):
p, Ex . R1 R2 R3 No.
3 CbNS CH3 158 ocHF2 OCNFZ
c~.._r OCHF'2 6 CH3 C3H~ ~ 143 7 C2H5 C2H5 ~ 139 _ 59 _ r Table 3: continuation -EX. R1 R2 R9 m.p. ( "C) No.
CI
The invention of the present divisional application relates to novel intermediates of formula IIa which are structurally different than those of application Serial No. 2,189,698. The intermediates of the present divisional application are useful in the preparation of compounds of formula I, illustrated below.
It is known that certain substituted amino-carbonylimadazolinones, such as, for example, 1-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), have herbicidal properties (cf. R. Wegler, Chemie der Pflanzenschutz-and Schadlingsbekampfungsmittel [Chemistry of Plant Protection Agents and Pesticides], Vol. 5, p. 219, Springer-Verlag, Berlin-Heidelberg-New York, 1977).
However, the action of this compound is not satisfactory in all respects. The new sulphonylaminocarbonyl-triazolinones are a subgroup of the broad class of compounds of the a general formula (T) R SOZ NH CO N N --- R
N----Rz in which R'' represents hydrogen, hydroxyl or amino, or represents an - la -opt ionally subst ituted radical f rom the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, alkoxy, alkenyloxy, alkylamino and dialkylamino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents an optionally substituted radical from the series comprising alkyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, alkoxy, alkylamino and dialkylamino, and R3 represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, as well as salts of compounds of the formula (I), have now been found.
The sulphonylaminocarbonyl-triazolinones of the general formula (I) are obtained when a) triazolinones of the general formula (II) O
HN- 'N-R~
N (ll) in which R1 and R2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the general formula (III) R3 802-N C-~ (III) in which 2Q R3 has the abovementioned meanings, if appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) Z-CO-N~N-R1 (IV) ~R2 in which R' and R2 have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, axe reacted with sulphonamides of the general formula (V) R3'S~2'NH2 (V) in which R3 has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or when c) triazoli.t~ones of the general formala (II) O
1-iN~N-R1 ( I I ) ~~-----1~ 2 R
in which R1 and RZ have the abovementianed meanings are reacted with sulphonamide derivatives of the general _ formula (VI) R3-S02-NH-CO-Z (~z) i. n wh 1 ch R3 has the abovementioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and, if appropriate, salts are formed by customary methods from ZO the compounds of the formula (T) prepared by process (a), (b) or (c).
The new sulphonylaminocarbonyl-tria2olinones of the general formula (I) and their salts are distinguished by a powerful herbicidal activity. Surprisingly, the new compounds of the formula (I) show a considerably better herbicidal action than the known herbicide 1-isobutyl-aminocarbonyl-2-imidazolidinone (isocarbamide), which has a similar structure.
The new compounds of the present' parent application 20 are those compounds of the formula (I) in which R1 represents hydrogen, hydroxyl or amino, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-Cg-alkoxy, Cl-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is CA 02420329 2003-03-13 , optionally substituted by fluorine, chlorine and/or bromine, or represents C3-C6-cyGloalkyl which~is opt ional 1y subst ituted: by f luori.ne, - 4a -d chlorine, bromine and or.Cr-C4-alkyl, or represents phenyl-C1-C3-alkyl which ~is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C~-C4-alkyl, trifluoromethyl, Cr-C~-alkoxy and/or Lr-C4-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, C1-C~-alkoxy, fluorine- and/or chlorine-substituted Ci-C3-alkoxy, Cl-C,,-alkylthi~, fluorine- and/or chlorine-substituted C1-C3-alkyltluio, C~-C,,-alkylsul-phinyl, C,-C~-alkylsulphonyl and/or C,-C4-alkoxy-carbonyl, or represents Cr-C6-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, phenyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl., or represents C3-C4-alkenyloxy, or represents Cl-C4-alkylamino which is optionally substituted by fluorine, cyano, C1-C4-alkoxy or Cr-C4-alkoxy-car-bonyl, or represents di-(C,-Cy-alkyl)-amino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents Cr-C6-alkyl which is optionally substitut ed by fluorine, chlorine, brornine, cyano, C3-C6 cycloalkyl, C,-C,,-alkoxy or C1-C,,-alkoxy-carbonyl., or represents C3-C6-cycloal.kyl which is optionally substituted by fluorine, chlorine, bromine and/or.
Cl-C~-alkyl, or represents cyclohexenyl, or repre-sents phenyl-Cr-C3-alkyl which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, vitro, Cr-C,,-alkyl, trifluoromethyl, Cr-C4-alkoxy and/or Cl-Cy-alkoxy-carbonyls or represents phenyl which is~
34 optionally substituted by fluorine, chlorine, bromine, cyano, vitro, Cl-Cy-alkyl, trifluoromethyl.
Cl-C~-alkoxy, fluorine- and/or chiora.ne~-sunst~.tured C1-C3-alkoxy, Cl-C4-alkylthio, f luorine- and/or chlorine-substituted C1-C3-alkylthio, Cl-C;-alkyl-sulphinyl, C1-C~-alkylsulphonyl and/or C1-c:5-alkoxy carbonyl, or represents C1-C6-alkoxy which is option . ally substituted by fluorine, chlorine, cyano, C,-C,, alkoxy or C1-C4-alkoxy-carbonyl, or represents C1-C4-alkylamino or di-(C1-C~-alkyl)-amino, and R3 represents the group R5 , where R° and RS are identical or different and represent , hydrogen, fluorine, chlorine, bromine, iodine, vitro, CI-C6-alkyl.(which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C~-C'-alkoxycarbonyl, Cl-C~-alkylamino-carbonyl, .di-(C~-C,,-alkyl)amino-carbonyl, hydroxyl, Ci-C,-alkoxy, formyloxy, C1-C,,-alkyl-carbonyloxy, Cl-C,,-alkoxy-carbonyloxy, C1-C,-alkylamino-carbonyloxy, Cl-C4-alkylthio, C~-C,~-alkylsulphinyl, C~-C~-alkylsulphonyl, di-(C1-C4-alkyl)-aminosulphonyl, C3-C6-cycloalkyl or phenyl ) , or represent Cz-C6-alkenyl ( which is option-ally substituted by fluorine, chlorine, bromine, cyano, C1-C~-alkoxy-carbonyl , carboxyl or phenyl ) , or .
represent C2-C6-alkinyl (which is optionally s'ubsti-.
tuted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent - s --" C1-C4-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-Cy-alkoxy-carbonyl, C1-C4-alkoxy, C1-C~-alkylthio, C1-C~-alkylsulphinyl or C1-C4-alkylsulphonyl ) , or represent C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C,,-alkoxy-carbonyl, C1-C4-alkylthio, Ci-C4-alkyl.sulphinyl or C1-C4-alkylsulphonyl ) , or represent C3-C6-alkenyl-oxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), or represent C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C3-alkylthio or Cl-C4-al.koxycarbonyl ) , C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the radical -S(O)p-R6 where p represents the numbers 1 or 2 and R6 represents C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C4-alkoxy-carbonyl ) , C3-C6-alkenyl ~ C3-C6-alkinyl, Ci-C4-alkoxy, Cl--C~-alkoxy-C1-C4-alkyl-amino, C1-C4-alkylamino, di- ( C,-C4-alkyl ) -amino or phenyl, or represents the radical -NHOR' where R'_ represents C1-C12-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C,-C$-alkoxy, C1-C4-alkylthio, C1-C4-alkylsul phinyl, l C,-C4-alkylsulphonyl, Cl-C4-alkyl carbonyl, C1-Cy-alkoxycarbonyl, C1-C,-alkyl amino-carbonyl or di-(C1-C4-alkyl)-amino carbonyl), or represents C3-G6-alkenyl (which is optionally substituted by fluorine, _ 7 _ _ chlorine or bromine) , C3-C6-alkinyl, C~-C6-cyclaalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substi-tuted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, C1-C4-alkoxy ar C1-C,-alkoxy-car-bonyl), or represents benzohydryl, or repre-sents phenyl (which is optionally substituted by f luorine, chlorine, nitro, cyano, C1-C,,--alkyl-, trifluoromethyl, C~-C,,-alkaxy, C~-C2-fluoroalkoxy, C1-C4-alkyl.thio, trifluoromethyl-thio or C,-C~-alkoxycarbonyl ) , R° and/or Rs furthermore represent phenyl or phenoxy, or represent C1-C~-alkylcarbonylamino, C~-C4-alkoxycarbonylamino, C1-C4~-alkylamino-carbonyl-amino, di-(C1-C4-alkyl)amino-carbonylamino, or represent the radical -CO-R8, where RB represents C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4 alkylthio, C1-C4-alkylamino, C1-Cy-alkoxyamino, C1-C4-alkoxy-C~-C4-alkyl-amino or di- ( C1-C4-alkyl ) -amino ( each of which is optionally substituted by fluorine and/or chlorine), R' and/or Rs furthermore represent tr.i.methylsilyl, thiazolinyl, C1-C,-alkylsulphonylox.y, di-(C1-C~
alkyl)-aminosulphonylamino, or represent the radical -CH=N-R9, where Rs represents Cl-C~-alkyl which is optionally substituted by fluorine, chlorine, .cyano, . carboxyl, Ci-C~-alkoxy, C1-C4-alkylthio, C1-C~
alkylsulpl~inyl or C1-(:4-alkyl sulphonyl, or represents benzyl which is optionally substi-- tuted by fluorine or chlorine, or represents C3-CB-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlor ine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, Cl-C~-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C~-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, Cl-C~-alkyl-amino, di-{Cl-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C,-alkoxy-car-bonylamino or C1-C;-alkyl-sulphonylamino, or represents phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl, furthermore R3 represents the radical -iH , where Rl° represents hydrogen or Ci-C~-alkyl, R'1 and R12 are identical or different and represent hydrogen, fluorine, chlorine, bromine, vitro, cyano, C~-C,-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C~-C~-alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl,'Cl-C,-alkoxy-carbonyl, f - ~ r dimethylaminocarbonyl, C1-C~-alkylsulphonyl or di-(C1-C,-alkyl)-aminosulphonyl;
furthermore R3 represents the radical R13 ~ R , where R'3 and R'~ are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is optionally substitut ed by fluorine and/or chlorine ) or C~-~,,-alxoxy (which is optionally substituted by fluorine and/or chlorine);
furthermore R' represents the radical ~ ~ , where . . ~N
ftib R'S and R'6 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C~-C4-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine , or represent C,-C4-alky l.thio, C1-Cy-alkylsulphinyl or C1-C4-alkylsulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represent di-(Cl-C~-alkyl)-aminosulphonyl or C1-C~-alkoxy-carbonyl or di-methylaminocarbonyl;
- to -furthermore R3 represents the radical R1~ ~ ~ ~ Rla , where ~J
R" and RlB are identical or different and represent hydrogen, fluorine, chlorine, bromine, C~-C,-alkyl (which is optionally substituted by fluorine and/or bromine), Cg-C~-alkoxy (which is optionally substi-tuted by fluorine and/or chlorine), or represent C1-C~-alkylthio, Cl-C4-alkylsulphinyl or C1-C,-alkyl-sulphonyl (each of which is optionally substituted by fluorine and/or chlorine) ~ or represent di-(C1-C4-alkyl)-aminosulphonyl;
furthermore R3 represents the radical , where ~' ~R20 Rte and RZ°.are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine) , C~-C4-alkylthio, C1-C~-ahkylsul-phinyl or Cl-C4-alkylsulphonyl (which is optional-ly substituted by fluorine. and/or chlorine), di-(C1-C4-alkyl)-amino-sulphonyl, C:l-C4-alkoxy-car-bonyl or di.methylaminocarbonyl, and.
A represents oxygen, sulphur or the group N-Z', _ 11 where - Z' represents hydrogen, Cl-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by f luorine, chlorine, bromine or vitro ) , C1-C4-alkylcarbonyl, C1-C,-alkoxy-carbonyl or di-(C,-C~-alkyl)-aminocarbonyl;
furthermore R3 represents the radical .~~R22 r where 1 , R21 and R22 are identical or different and represent hydrogen, C1-Cy-alkyl, halogen, Ci-Ca-alkoxy-carbonyl, Ci-C~-alkoxy or C1-C4-halogenoalkoxy, Y1 represents sulphur or the group N-R23, where Rz3 represents hydrogen or C1-Cu-alkyl g furthermore R3 represents the radical ( , where tJ~N
~24 R
R24 represents hydrogen, C,-C~-alkyl, benzyl, quinolinyl or phenyl, RZS represents hydrogen, halogen, cyano, vitro, C1-C~-alkyl (which is optionally substituted by fluorine and/or chlorine); Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or Cl-C4-alkoxy-carbonyl, and Rz6 represents hydrogen, halogen or C1-C4-alky l furthermore R3 represents one of the groups listed below, \ ~ ~ N'_Ca~9 ' N ~
~S S ~'OCHZCP3 '~ 1 \ o The invention furthermore preferably relates to the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkylammonium, di-(Cl-C~-alkyl)-ammonium, tri-(Cl-C4-alkyl)-ammonium, C5- or C~-cycloalkyl-ammonium and di-(Cl-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which Rl, R2 and R3 have the meanings mentioned above as being preferred.
In particular, the invention of the parent application relates to compounds of the formula (I) in which R1 represents hydrogen, or represents C1-C~-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, methoxy or ethoxy, or represents allyl, or represents C3-C6-cycloalkyl, or repre-sents phenyl, or represents.benzyl, or represents C1-C3-alkoxy, or represents C1-C3-alkylamino, or represents di-(C1-C2-alkyl)-amino, R2 represents hydrogen, or represents Ci-C"-alkyl which is optionally substituted by fluorine and/or chlor ine or by methoxy or ethoxy, or represents C3 cycloalkyl, or represents phenyl, or represents C1-C3-alkoxy, or represents C1-C3-alkylamino, or represents di-(C1-C2-alkyl)-amino, and R3 represents the group , R~ , where R4 represents fluorine, chlorine, bromine,, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, C1-C3-alkylthio, C~-C3-alkylsulphinyl, C1-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylamino-sulphonyl, phenyl, phenoxy or C1-C3-alkoxy-~car-bonyl, and Rs represents hydrogen, fluorine, chlorine or bromine;
furthermore R9 represents the radical _~1~~ , where R'° represents hydrogen, ' , R11 represents fluorine, chlorine, bromine, methyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and R~'2 represents hydrogen, furthermore R~ represents the radical ~J
RO-C S ' IJ
O
where R represents Cl-C4-alkyl, or represents the radical O
I I
RO-C
I ,IN
N
~3 where R represents C1-C4-alkyl.
Examples of the compounds are listed in Table 1 below -- cf. also the Preparation Examples.
R3-S02-N!-~-CO-H~N-~i (I) R
Table 1: Examples of the compounds of the formula (I) R1 R2 ~3 F
H
H
CH2-CH=CHI C2HS
OCH3 C3H7 ~H2_ O-CH2-CH=CH2 S COOCH3 C2H5 C9H9_n - is -Table 1 - cont~.nuation CH3 C3H?
S02N(CH3)2 C3H~
GH3 CzHS C 1_~
~/
Br CHI
~~COOCH3 OC3H~ CH3 'NI~N~
CH3 C3H7 S~COO.CH3 N(CH3)2 CHZ ~H2_ - Table 1 - continuation NH-CH3 ~H
COOCZHS
CH3 C3Hy r/
F~CHO
OCZHS
F
CH~~ CH2~ /
CHZ C3H' ~/
~ .N~
C3H~ ~N
COOCH~
CH~O
CH3 C2H5 ~ SAN-C4H9 Table 1 - continuation ,~ CONtCH312 CH3 CqH9 CON(CHal2 CH3 C3H~ i C3H~ /~
CH3 C3H~-n C3H7-n Tabs _ continuation CF'3 CH3 C4H~ HZ' CH3 ~ v H2_ Cl C2H5 / H2, CFA
CN
CH3 CH(CH3)2 H
~~~COOCZHS
N, ~. ~
Table 1~- continuation ~COOC2H5 N N
OCH3 CaHS ~N
i COOCH(CH3)2 ca CH3 CH3 ..' ! CF3 r ~N--C H 3 C 1.
CON(CH372 CH3 CH3 H3C' N
CH3 CH(CH3)2 H2 Table 1 - continuation R1 R2 ~3 Br OCH2-C~-i=CH2 C2H5 CH3 ~CH3 S02-N., OCH3 C2Hg /
Br CH3 CH(CH3~2 CH3 CHZ-CH=C~2 SO~CH3 SCH(CH3)2 F
F
.~~ CON(CH3)2 CH2-CH=CH2 H
s Table 1 - continuation Ri R2 H3 OCHFZ
CH2-GH=CN2 CH3 r CH2-CH=CHZ G~HS ~N'N
C2Hg S OOCH3 CH3 C3H' ~~__~ H 2 _ Si(CH3)3 i I CON(CH3)~
C2~i5 C~
Table 1 - continuation f~ 1 R2 N3 CON<CH3)2 C2H$ C4H9 S
CH3 C3H? , NHS CH2-CF3 'O
C 2H 5 NwN/'r.
OCH3 CH(CH3)2 / H2~
. i CF'3 CHI H
Table 1 - continuation Ri R2 ~3 CHI, C3H~ f OCH3 C3H? \ 1) O .
O
SOZCH~
Bc OCHF'2 CHZ-CH~GH2 CH2-O-CH3 Table 1 - continuation Rt R2 R3 OCH2CH~-C1 N(CH 3~. N(CH 3~
If, for example, 2-6-difluoraphenyl isocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (a) can be outlined by the following equation:
O
H.N~N~OGH3 _. N=C~O + !
N
P
SOZ NH-CO~ ~ ~OCH3 N N
N
~C 1H
2s If, for example, 2-methylthio-benzenesulphonamide and 2-chlorocarbonyl-4-dimethylamino-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (b) can be outlined by the following equation:
SCH3 ~
r Cl-CO~N~N~N(CH3)2 _ \ , S02-NHZ + N -HCl H
SCHg O
\~/ SOZ-NH-CO~N~N~N(CH3~
N--H
If, for example, N-methoxycarbonyl-2-methoxy-benzenesul-phonamide and 5-diethylamino-4-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are used as starting substances, the course of the reaction in process (c) can be outlined by the following equation:
OCH3 () + H.N~N..CHFa \ ~ SOz~~ ~~~ ~ I
N(C~,Hs~
O
-H c \ / ~°2~~ co,N~..,N'CHF2 N rt(C2H~)a .
'Formula (II) provides a general definition of the triazo-linones to be used as starting substances in processes (a) and (c) for the preparation of compounds of the formula (I).
In formula (II), R1 and R2 preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the - compounds of the formula (I) as being preferred, or f part icularly preferred, far R1 and Rz .
Examples of the starting substances of the formula (II) are listed in Table 2 below.
O
~~~~R1 N (II) Table 2: Examples of the starting substances of the formula (II) H H
C3H~ H
Table 2 - continuation CH(CH3)2 ~
CqH9 ' H
CH2CH(CH~)2 H
C(CH3)3 H C~HS
H CgH~
H cHccNs)2 H C~H9 H CH~CH(CH3)2 H CICH3)3 CHF'2 H
H ' CH20CH3 H CH20CZH~
Table 2 - continuation CHa GZHS
CH3 C~H~
CH3 CHtCH3)2 CH3 C~~9 CH3 CH2C~i t CH3 ) 2 CH3 C(C~~~3 CZHS C~3 , C3H7 CH3.
CH(CH3)2 C~3 CH2CHtCH3)2 CH3 C3H7 C3H~
CFZCHFZ CH
,, v . . ..:,,i i Table 2 , continuation C2H5 C'~Hg C6H5 t:H3 /t:H 2 _C~CH CH3 cH3 ~ ~G~cH
CHI
GH3 NtCH~)~
C2H~ N(CH~) ~, CzHS
C3H~
C~H~
_ 31 -<~ Table 2 - continuation .
~2H5 C3H~
CH3 NHCH~
NHCH~ CH3 NHCH~ C~H' N(CH3)2 CHI
N(CH3)2 C2H5 N(CH3)2 C3H7 a , Table 2 continua~tiox~
.. R~ ~~
OCN3 C~l~
OCH3 C~H~
OCZHS CHI
~C2H5 G2H~
..:.~
CH2'O-C~1-i5 N(CH~>~, O-C3H7 C3H?
O-CH2-CH=CH2 CH~-O-CHZ-CH=CH2 C~HS
O-CH~-CH=CH2 C3H7 O-CHI-~H-CH2-Br C~H7 ;
Hr Table 2 - continuation OC H.3 OCH
OCH3 CHx OCH3 NtCN3)2 O-CH2-COOCH3 C3H~
NtCH3)2 NtCH~)2 NtCH3)2 OC2HS Cgkl7 Table 2 - continuation .. R1 NH-CH3 . C~2-p-CHI
.__L.~ CN2_O_CH3 CH3 Ctl2-p-CH3 - ~5 -', The starting substances of the formula (II) are known w and/or can be prepared by processes known per se (cf.
Chem. Ber. 90 (1957) 909-921 loc.cit. 98 (1965), 3025 3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra hedron 32 (1976), 237-2352; Hely. Chim. Acta 63 (1980), 841-859; J. Chem. Soc. C 196?, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11.1988;
DE-P 3,916,20?/LeA 26,849 dated 18.05.1989;
DE-P 3,916,208/LeA 26,850 dated 18.05.1989;.7. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated 24.05.1989).
For example, the triazoli.nones of the formula (II) are obtained when «) oxadiazolinones of the general formula (V)T) ~N~ t Y I I ) N~R2 in which R2 has the abovementioned meaning are reacted with amino compounds of the general formula (VIII) HZN-Ri (VIII) in which R' has the abovementioned meaning, at temperatures between 20°C and 120°C and, if appropriate, in the presence of a diluent, such as, - for example, water, and the hydrazine derivatives formed by this process, q~ t~~ general formula (IX) H~ ~.CO-N~-R~
H
(IX) .-Nw in which Rl and R2 have the abovementioned meanings, are isolated by customary methods (cf. the Preparation Examples) and - or if appropriate even without intermediate isolation - the compounds of the formula (IX) are condensed at temperatures between 20°C and 120°C and, if appropriate, in the presence of a basic condensation auxiliary, such as, for example, sodium hydroxide, and, if appropriate, in the presence of a diluent, such as, for example, water, to give the compounds of the formula (II) (cf. EP-A 301,946, DE-OS (German Published Specification) 3,743,493/LeA 25,759 and the Preparation Examples ), or when p) amino compounds of the general formula (VIII) H2N'RI (YIII) in which Rl has the abovementioned meaning, are reacted with carbonic acid derivatives, such as, for example, Biphenyl carbonate, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of the general formula (X) ~ Rp~ 30 in which R2 has the abovementioned meaning and R represents lower alkyl, at temperature between 0°C and 150°C and, if appropriate, in the presence of a diluent, such as, for example, ethylene chloride (cf. DE-P
3,920,270/LeA 26,937 dated 21.06.1989, DE-P 3,928,662/LeA
27,137 dated 30.08.1989, and the Preparation Examples).
Some of the compounds of formula II are novel.
According to one aspect of the invention of the divisional application Serial No. 2,189,698, there is provided a triazolinone of the general formula (IIa) HN N~ (IIa) N
A
in which either (1) A1 represents di-(C1-C4-alkyl)-amino and A2 represents hydrogen, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, Cl-C4 alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents C1-C~-alkoxy;
or in which ( 2 ) A1 represents and A2 represents OCIi3 CH3 OCH 3 ~(~ 3)2 OGH2C6Iis CH3 OG2Hs C~.H~
OCH 3 C,~.H9 a OC~H~ C3H~.
OCHZ-CHCH2 ~3 O-CHZ-CHCH2 ~-2H5 O-CH2-CH-CH-Hr C~.H~
Br ~3 ~3 O-CH~_COOCH 3 C3H7 C3H~
CH(CH 3)~
C~~
H
- 39a -NHz OCH3 o CzHs -CHZCH=CHz CH3 CH3 -CHzOCH3 -CHZOC2Hs ~ -N ( CH3 ) z .
According to one aspect of the present divisional invention, there is provided a triazolinone of the formula HN N~ (IIa) I
N Rz wherein R1 is Cl-C6-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, phenyl, Cl-C4-alkoxy or C1-C4-alkoxycarbonyl) or is C3-C4-alkenyloxy and Rz is hydrogen, or represents Cl-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy or Cl-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents phenyl-C1-C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or Cl-C4-alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, methyl, C1-C4-alkoxy, fluorine- and/or chlorine-substituted - 39b -C1-C3-alkoxy, C1-C4-alkylthio, fluorine- and/or chlorine-substituted C1-C3-alkylthio, C1-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl and/or Cl-C4-alkoxy-carbonyl.
According to another aspect of the present divisional invention, there is provided a triazolinone as described herein, wherein R'' is methoxy, ethoxy, propoxy or isopropoxy, and RZ is hydrogen, C2-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl.
According to still another aspect of the present divisional invention, there is provided a triazolinone as described herein, selected from the group consisting of those wherein - 39c -R1 represents and Rz represents OCH3 CzHs OCH3 C3H~
OCZHS
CzHs OCH3 CH ( CH3 ) z OCzHs C3H~
OC3H~ C3H~
O-CHz-CH=CHz CH3 O-CHz-CH=CHz Calls O-CHz-CH=CHz C3H~
0- C H 2 -C H-C H z-B r C3H~
Br H
CHz O-CHz_COOCH3 C3H~
The new triazolinones of the formula (IIa) are obtained either when oxadiazolinones of the general formula (VIIa) - 3 9d -N 0 (VIIa) N-Az in which A2 has the abovementioned meaning, are reacted with amino compounds of the general formula (VIIIa) H2N A1 (VIIIa) in which A1 has the abovementioned meaning, analogously to the process described above under (a), or when amino compounds of the general formula (VIIIa) HzN A1 (VIIIa) are reacted with carbonic acid derivatives, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of - 39e -the general formula (Xa) tR0)3C-A2 (Xa) in which A2 and R have the aboyementio~ed meanings, analogouslx to tile process described above under (,e) (also see the Preparation Examples).
In the general formula (IIa), Al preferably represents C1-C5-alkyl, C3-CS-alkenyl or C3-C6-cycloalkyl, or represents Cl-C6-alkoxy ' which is optionally substituted by fluorine, chlo-rine, bromine, cyano, Cl-C4-alkoxy or Cl-C4-alk-oxy-carbonyl, in particular methyl, ethyl, allyl, .cyclopropyl, methoxy, ethoxy, propoxy or isoprop-oxy;,or represents di-(Cl-C4-alkyl)-amino, in par-ticular dimethylamino or diethylamino, and A2 preferabhy represents hydrogen, or represents C~-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy, C1-C~-alkyl-carbonyl or C~-C~-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or Cl-C~-alkyl, or represents phenyl-C1-C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl, Cl-C4-alkoxy and/or Cl-C~-alkoxycarbonyl, or represents phenyl which is optionallx substituted by fluorine, chlor-ine, bromine, cyano, vitro, C1-C4-alkyl, trifluoro-methyl, Cl-Cw-alkoxy, fluorine- and/or chlorine-substituted C1-C3-alkoxy, C1-C~-alkylthio, fluorine-and/or chlorine-substituted C1-C3-alkylthio, Cl-C4-alkylsulphinyl, C1-C,,-alkylsulphonyl and/or C1-C~-- 40 _ alkoxy-carbonyl, or represents C1-C4-alkoxy, in particular hydrogen, C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl, or represents methoxy or ethoxy, provided that both Al and A2 do not simultaneously represent C1-C6-alkyl.
The compounds of the formulae (VII), (VIIa);
(VTII), (VIIIa) and (X) or (Xa) which are to be used as starting substances for the preparation of the triaxolinones of the formulae (II) or (IIa) are known (cf. Helv. Chim. Acta 55(1972), 1174; EP-A 301,946; DE-OS (German Published Specification) 3,743,493).
Formula (III) provides a general definition of the sulphonyl isocyanates further to be used as starting substances in process (a) for the preparation of compounds of the formula (I).
In formula ( IIT ) , R3 preferably, or in part icular, has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
Examples of the starting substances of the formula (III) which may be mentioned are:
2-fluoro-, 2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, 2-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 2-methylthio-, 2-ethylthio-,. 2-propylthio-, 2-methyl-sulphinyl-, 2-methylsulphonyl-, 2-dimethylaminosulphonyl-.
2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl, 2-propoxycarbonyl- and 2-isopropoxy-carbonyl-phenylsulphonyl isocyanate, 2-fluoro-, 2-chloro-, 2-difluoramethoxy-, 2-trifluorometh-2-methoxycarbonyl- and 2-ethoxycarbonyl-benzylsulphonyl isocyanate, 2-methoxy-carbonyl-3-thienyl-sulphonyl isocyanate, 4-methoxycarbonyl-and 4-ethoxycarbonyl-1-methylpyrazol-5-yl-sulphonyl isocyanate.
The sulphonyl isocyanates of the formula (III) are known and/or can be prepared by processes known per se (cf.
US-P 4,127,405, 4,169,719,'4,371,391;.EF-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (a) for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Suitable diluents in this context are virtually ail inert organic solvents. These preferably include aliphatic and aromatic, optionally haiogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such. as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetra-methylene sulphone and hexamethylphosphoric triamide.
In process (a), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 150°C, preferably at temperatures between 10°C and 80°C.
Process (a) 1s generally carried out under atmospheric pressure.
For carrying out process (a), between 1 and 3 moles, preferably between 1 and 2 moles, of sulphonyl isocyanate of the formula (:III) are generally employed per mole of triazolinone of the formula (II).
The reactants can be combined in any desired seguence. The reaction mixture is stirred until the reaction is complete. and concentrated, and the crude product which remains in the residue is crystallized using a suitable solvent, such as, for example, diethyl ether. The product of the formula (T) which has been obtained in crystalline form is isolated by filtration with suction.
Formula (IV) provides a general definition of the triazolinone derivatives to be used as starting substances in process (b) for the preparation of compounds of the formula (I).
In formula (IU), R1 and R2, preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula ( T ) as being preferred, or particularly preferred; for R1 and R2, and Z preferably represents chlorine, Cl-C4-alkoxy, benzylaxy or phenoxy, in particular methoxy or - 43a -- phenoxy.
Examples of the starting substances of the formula (IV) which are possible are the compounds of the formula (IV) to be prepared from the compounds of the formula (II) listed in Table 2 Wand phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or Biphenyl carbonate.
The starting substances of the formula (IV) are known and/or can be prepared by processes known per se (cf. EP-A 283,876; EP-A 294,666; EP-A 298,371.
The triazolinone derivatives of the formula (IV) are obtained for example When ~.riazolinanes of the general formula (II) NN~N~R1 tII>
I RZ
in which R1 and R2 have the abovementioned meanings, are reacted with carbonic said derivatives of the general formula (XIj z-co-z~
in which Z has the abovementioned meaning and _ 44 _ Z1 represents a leaving croup, such as chlorine, methoxy, benzyloxy or phenoxy, at temperatures between -20°C and -+-100°C, if appropriate in the~presence of a diluent, such as, for example, tetrahydrofuran, and, if appropriate, in the presence of an acid acceptor, such as, for example, sodium hydride or potassium tent-butylate (cf. the Preparation Examples).
Formula (V) provides a general definition of the sulphonamides further to be used as starting substances in process (b) for the preparation of compounds of the formula (T). .
In formula ( V ) , R3 preferably, or in part icular, has the meaning which has already been mentioned above in connection with the description of .the compounds of the formula (I) as being preferred, or particularly preferred, for R3.
examples of the starting substances of the formula (V) which may be mentioned are:
2-fluoro-, ~2-chloro-, 2-bromo-, 2-methyl-, 2-methoxy-, ZO 2-t rif luoromethyi- , 2-dif luoro-methoxy- , 2-t rif luoromethoxy- , 2-methylthio-, 2-ethylthio-, 2-propylthio-, 2-methylsulphinyl-, 2-methylsulphonyl-, 2-dimethylamino-sulphonyl-, 2-diethylaminosulphonyl-, 2-(N-methoxy-N-methyl)-aminosulphonyl-, 2-phenyl-, 2-phenoxy-, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-propoxycarbonyl- and 2-isopropoxy-carbonyl-benzenesulphonamide, 2-fluoro-, 2-chloro-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-methoxycarbonyJ.-and 2-ethaxycarbonyl-phenylmethanesulphanamide, 2-methoxy-carbonyl-3-thiaphenesu7_phonamide, 4-methoxycarbonyl- and 4-ethoxycarbonyl-1-methyl-pyrazol-5-sulphonamide.
The sulphonamides of the formula (V) are known and/or can be prepared by processes known per se (cf. US-P
4,127,405, 4,169,719, 4,371,391; EP-A 7,687, 13,480, 21,641, 23,141, 23,422, 30,422, 30,139, 35,893, 44,808, 44,809, 48,143, 51,466, 64,322, 70,041, 173,312).
Process (b) for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Suj.table diluents in this context are virtually all inert organic solvents, for example those which have been indicated above in the case of process (a).
Acid acceptors which can be employed in process (b) are all acid-binding agents which can customarily be used for reactions of this type. The following are preferably suitable: alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate, potassium carbonate, sodium tert-butylate and potassium tert-butylate, furthermore aliphatic, aromatic or heteracyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1-5-diazabicyclo-(4.3.0]-non-5-ene (DBN), 1-8-diazabicyclo-[5.4.U)-undec-7-ene (DHU) and 1,4-diazabicyclo-[2,2,2]-octane (DABCO).
When carrying out process (b), the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C.
In general, process (b) is carried out under atmospheric pressure: However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out process (b), the specifically required starting substances are generally.employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess. In general, the reactions are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in~process (b) is carried out in each case by customary methods.
The triazolinones of the formula (II) which are to be used as starting substances in process (c) for the preparation of compounds of the formula (I) have already been described as starting substances for process (a).
formula (VI) provides a general definition of the sulphonamide derivatives further to be used as starting substances in process (c) for the preparation of compounds of the formula (I).
In formula (VI), R3 and Z preferably, or in particular, have those meanings which have already been ment ioned above in connect ion with 'the descript ion of the _ 47 compounds of the formula (I) or (IV) as being preferred, or particularly preferred, for R3 and Z.
Process (c) is preferably carried out using diluents. Suitable diluents in this context are the same organic solvents as have been mentioned above in connection with the description of process (a).
If appropriate, process (c) is carried out in the presence of an acid acceptor. Suitable acid-binding agents in this context are the same as have been mentioned above in connection with the description of process (b).
When carrying out process (c) the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0°C and 100°C, preferably at temperatures between 10°C
and 60°C.
In general, process (c) is carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.
for carrying out process (c), the specifically required starting substances are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two specifically employed components in a substantial excess.. In general, the reactions' are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the specifically required temperature. Working-up in process (c) is carried out in each case by customary methods.
To convert tlne compounds of the formula ( :I ) into salts, they are stirred with suitable salt formers, such as, for example, sodium hydroxide, sodium methylate, sodium ethylate, potassium hydroxide, potassium methylate or potassium ethylate, ammonia, isopropylamine, dibutylamine or triethylamine, using suitable diluents, such as, for example, water, methanol or ethanol. The salts can be isolated as crystalline products - then if appropriate after concentrating the mixture.
The active compounds can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense; there are to be understood all plants which grow in locations where they are undesired. Whether the substances act as total or selective herbicides depends essentially on the amount used.
The active compounds can be used, for example; in connection. with the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,. Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Tpornoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus; Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, );mex, Datura, Viola, Galeopsis; Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the genera~ Gossypium, Glycine, Heta, Daucus, Phaseolus, Pj.sum, Solanum, Linum, Ipoznaea, Vicia, Nicoti_aIla, Lyropersleon, Arachis, E3rassica, Lar_tuca, Cucumis and Cucurbita.
Monacotyledon weeds of the Genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Branchiaria, Lolium, Bramus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactylactenium, Agrastis, Alopecurus and Apera.
Monocot~edon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However,-the use of-the active compounds is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks,~and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields,. in lawns, turf, meadows and pastures, and for the selective cornbating of weeds in annual cultures.
The compounds of the formula (I) are suitable for combating monocotyledon and dicotyledon weeds both 'in the pre-emergence and the post-emergence method. They are - markedly more effective than, for example, isocarbamide.
To a certain extent, the compounds also Shaw a fungicidal action, far example against powdery mildews and against apple scab, and also against Pyricularia oryzae on rice.
The active campounds ca.n be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-act ive agents, that is emulsifying agents and/or dispersing agents and/or forming agents.
In the case of the use of water. as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions; mineral and vegetable oils, alcohols, such as ~ CA 02420329 2003-03-13 butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dixnethyl sulphoxide, as well as water.
As solid carriers there ~:re suitable: 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 highly disperse silica, alumina and silicates, as solid carriers fox granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as Well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives 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, as well as natural phospholipids, such as cephalir~s and lecithins, and synthetic phospholipids, can be used in the formulations.
Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs, and metal phthalocyanine dyestuffs, and trace nutrients such as salts of ion, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds, the active compounds as such' or in-the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3~(2,2-dimethylpropy'1)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURONj for combating weeds in cereals 4-amino-3-methyl-6-phenyl-1,2,4-t_riazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino=6-(l,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIHUZIN) for combating weeds in soya beans= furthermore also mixtures with 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butric acid (2,4-DH); 2,4-dichlorophenoxypropionic acid (2,4-DP); 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid (ACIFLUORFEN);
2-chloro-2',6'-diethyl-N-methoxy-methyl-- 53a -acetanilide (ALACHLOR); 2-chloro-4-ethylamino-6-iso-propylamino-1,3,5-triazine (ATRAZINE); methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]carbonyl]-amino]-sulphonyl]-methyl]-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitro-benzoate (BTFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)-acetamide (BUTACHLOR); ethyl 2-{[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHT.ORIMURON);2-chloro-N-i[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methyl-phenyl)-urea(CHLORTOLURON); 2-chlaro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine(CYANAZINE);2,6-dichlo-robenzonitrile(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propianic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxazolidin-3-one (DIMET~iAZONE); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(9H)-one (ETHIOZIN); 2-~4-[6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanaic acid, its methyl ester or its ethyl ester (FENOXAPROP);
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); N,N-dimethyl-N'-(3-trifluoromethyl.phenyl)-urea {FLUOMETURON); 1-methyl-3-phenyl-5-(3-triflnoromethylphenyl)-4-pyridone (FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-mett~ylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)~5-oxo-0 1H-imidazol-2-yl]-9(5)-methylbenzoate (IMAZAMETHABENZ);
- 2-(4,5-dihydro-9-methyl-9-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid (IMAZ,APYR); 2-[5-methyl 5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinoli_n carboxylic acid (TMAZAQUIN); 2-[4,5-dihydro-4-methyl-4 isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETIiAPYR); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-iso-propylphenyl)-urea (ISOPROTURON); (2-methyl-4-chloro-phenoxy)-acetic acid {MCPA); (9-chloro-2-methylphenoxy)-propionic acid (MCPP); N-methyl-2-(1,3-benzothiazol-2--yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-di_methyl-phenyl)-N-[(1H)-pyrazol-1-yl-methyl]-acetamide (METAZACHLOR); 2-ethyl-6-methyl-N-(1-methyl- 2-metho-xyethyl)-chloroacetanilide (METOLACHLOR); 2-.{[j((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic aicd or its methyl ester (METSULFURON}; 1-(3-trifluoromethyl-phenyl)-4-methyl-amino-5-chloro-6-pyridazone (NORFLURAZON); N-(1-ethyl-propyl)-3_,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
0-{6-chloro-3-phenyl-pyridazin-9-yl) S-octyl thio-carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETH'YL); 2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); methyl 2-~[(4,6-dimethyl-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl]-benzoate (SULFOMETURON); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate {THIAMETURON); S-(2,3,3-trichloroallyl)-N,N-diisopropylthiocarbamate (TRI-ALLATE), 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN). Surprisingly, some mixtures also show a synergistic effect.
Mixtures with other known active compounds, such as fungicides, 1I18eCtiCideS, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds can he applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 15 kg of active compound per hectare of soil surface, preferably between 0.05 and 10 kg per ha.
The preparation and use of the active compounds can be seen from the following examples.
a Prega~ation~Xamples:
- Examgle 1 (A ,j--S02-NH-CO~N~N
(Process (a)) 3.0 g (17.95 mmol) of 4-cyclopentyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 60 ml of acetonitrile, and 6.9 g (28.6 mmol) of 2-methoxycarbonyl-phenylsulphonyl isocyanate~ dissolved in 20 ml of aceto-nitrile, are added to this solution with stirring. The reaction mixture is stirred for 6 hours at 20°C and then concentrated. The residue which remains is stirred with diethyl ether, and the product Which has been obtained in crystalline form is isolated by filtration with suction.
This gives 6.6 g (90 % of theory) of 4-cyclo pentyl-5-methyl-2-(2-methoxycarbonyl-phenylsulphonyl aminocarbonyl)-2,4-dihydro-3~.-~,2i4-triazol-3-one of melting point 146°C.
- 5? -Example 2 CI
_ O
S02 NH-CO~N"~N~CH3 N---~
'C H
2 l (Process (b)) 1.8 g (11.8 mmol) of 1,8-diazabicyclo-[5,4,0]-under-7-ene (DBU) are added to a stirred mixture of 3.0 g (y2.1 mmol) of 5-ethyl-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 2.5 g (12.2 mmol) of 2-chloro-6-methyl-benzenesulphonamide and 60 ml of acetonitrile. The reaction mixture is stirred for 2 hours at 20°C, then poured into about twice the volume of ice-water, and a pH of about 2 is established by dropwise addition of concentrated hydrochloric acid. The product which has been obtained during this process in crystalline form is isolated by f. l It rat ion with suet ion .
This gives 3.2 g 973.5 $ of theory) of 5-ethyl-4-methyl-2.-(2-chloro-6-methyl-phenylsulphonyl-aminocarbonyl) 2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 176°C.
For example the compounds of the formula (I) listed in Table 3 below can also be prepared analogously to Examples 1 and 2 and following the general instructions of the preparation processes R3-S02-NH-CO~N~N~1 (I) ~R2 Table 3~ Preparation Examples of the compounds of the formula (1y (w. - melting point):
p, Ex . R1 R2 R3 No.
3 CbNS CH3 158 ocHF2 OCNFZ
c~.._r OCHF'2 6 CH3 C3H~ ~ 143 7 C2H5 C2H5 ~ 139 _ 59 _ r Table 3: continuation -EX. R1 R2 R9 m.p. ( "C) No.
CI
8 CH3 C3H~ ~ 141 9 OCH3 CH3 , 121 SOZN(CH3)2 l0 OCH3 CH3 180 11 OCH3 CH3 ~ 149 12 OCH3 C2H5 ~ 144 13 OCH3 C3H~ 128 S02NtCH3)2 14 CH3 C2HS ~ i73 Table 3r - conti~uatiorl EX. R1 R2 R9 m.p. ( °C) No.
SO~NtCH3)2 ~, 16 C2H5 ~ 154 17 OCH3 CH(CH3)2 137 ~i S02N(CH3)2 18 C2H5 ~ 174 19 C3H7 ~ 97 20 CH3 NtCH3)2 168 Cl 22 C2H5 C3H7 ~ 136 C~3 - b1 -Table 3s - continuation Ex. Ri R2 R3 m.p. ( C) No.
23 N(CH3)2 C2H5 ~ a39 24 N(CH3)2 H 197 25 NtCH3)2 CH(CH3)z ~- 148 26 OC2N5 C2H5 ~ 153 T
27 OC2H5 C3H7 ~ 155 28 CH(CH3)2 186 r J~
29 C3H~ ~ 146 30 N ( CHa C3H7 / 1_1 G
) 2 Table 3: - continuation Ex. R1 RZ #i$ m.p. ( °C) No.
COOCt~3 31 N(CH3a2 ~~ 131 32 C2H5 C,~H~ ~ 98 33 CH3 C4H9 ~ 113 34 C3H7 C4H9 ~ 88 35 C4Hg ~ 117 36 OCH3 C4H9 ~ 117 38 C2H5 ~ 130 Table 3s -continuation Ex. R1 RZ ~i$ m.p. ( C~
No.
39 C3H7 ~ -- 139 9 0 lsl 41 ~ CH3 ~ 151 .
92 CH(CH3)2 NHCt-1(CH3)2~ ~ 13s 93 N(CH3)2 N(CH~)2 ~ 171 A4 CH3 C3H~ r 1b8 45 C2H5 N(CH3)2 i34 OC~'3 46 CH3 C2H5 ~ 167 Table 3: - continuation fix. R1 R2 R3 m.p. ( °C) No.
pC~3 47 NH2 C3H~ / 120 4s --~ NH~ 120 coocH~
COOCH3 ' 50 -CH2GH=CH2 G2H5 108 51 -CH2CH=CH2 H ~~ 158 COOC~3 3 CH2--(") H / , 212 - 214 54 C3H7 ~d 168 - 169 Table 3: - continuation - Ex. R1 R2 R3 m.p. ('C) No.
55 C3H7 ~ ~ 103 - 105 OC~'3 57 OCH3 C2H5 ~ ~ 111 - 113 ~
59 -I~HCH3 C3H7-n ~ 196 F -60 CN3 C3H7-n ~ ~ i78 61 ~ H ~ 177 Table 3:
- continuation Ex. R1 R2 R3 mP ~ ~0) No.
COOC#i3 /
62 -CH2CH(CH3)2 C2H5 \ 123 63 -CH2-CH=CH2 C3N7-n (amorphous) 6A CH C ~ 157 / H
~
b5 / CZHS / 117 \ \
__ ~_ bb -C(CH3)3 C2H5 -~ 182 67 ~ C2H5 / \
68 ~ C2H5 69 -CH2-CH=CH2 CH3 120 - 6? -Table 3:
- continuation - EX. R~ R2 No.
70 H C ~- 183 HS
~
73 -OCH3 ~ 138 ~
79 CH(CH3)2 H ~ 191 75 ~ H
76 ~ H ~ 192 77 -C(CH3)3 H ~ ~ 211 6D _ Table 3: - continuation Ex. R' R2 R3 m.p. ( °C) No.
78 -CH2-iH-CH2Br CH3 ~ \ 110 Br 79 CH3 -CH20CH3 / ~ 152 F
80 CH3 C2H5 ~~\ 174 81 CH3 -CH20C2H5 ~ \ 123 CF3:
82 -OCH3 C3H7-n (amorphous) CON(CH3)2 83 C2H5 ' ~ 129 84 -CH20CN3 /'\
85 -CH20CH3 / \ 155 I _ 6g _ Table 3: - continuation - EX. R1 RZ R3 m.p~ ( '~.') No.
COOC~-13 ~
~
OC~'3 87 -CH20C2H5 ~ 99 C~
88 -NiCH3)2 ~ 189 89 -OCH3 C2H5 ~ 155 ~
Ci 91 -OCH3 C3H7-n ~ 125 ~
92 C2H5 ~ 138 ~
S
- 7d -Table 3: - continuation EX. R1 R2 R3 m.p. ( 'C) No.
93 -OC2H5 C2H5 \ 132 ~
94 -OC2H5 C3H~-n \ 107 95 -OCH3 CH(CH3)~ ~ 128 ocF3 ~
96 OCH3 CH3 _\ 119 ~
97 C3H7-n ~ 100 ~
98 ~
\ 140 .
~
99 -N ( CH3 ) -\
~
100 -N(CH3)2 \ 182 Table 3: - continuation Ex. R' RZ R3 m.p. ( 'C) No.
101 CH3 -N(CH3)z ~~ 181 Co0CH3 102 CH3 -OCH3 ~ 150 CI
103 CZHS ~ ~ 147 104 -CH2-CH=CH2 CH3 ~ 132 105 -CH2-CH=CH2 C2H5 ~ ~ 109 106 -CH2-CH=CH2 C3H7-n ~ lpq _ 72 _ Table 3: - continuation EX. R1 RZ R3 m.p. ( ~C) No.
107 -OC2H5 C2N5 , ~ 197 108 -OC2H5 C3H7-n r ' 136 C ~i 3 Cl 109 -OCH3 CH(CH3)2 / ~ 126 110 CH3 CH3 ~ ~ 146 111 CH3 ~ ~ 175 112 CH3 CH(CH3)2 ~ ~ 124 Table 3: - continuation EX. R~ RZ R3 m.p. ( 'C) No.
113 CH3 , ~ 171 C~3 114 CHICH3)2 / \ 132 115 ~ ~ 167 117 CN3 C2H5 ~ ~ 147 118 CH3. C3H7-n ~ 169 - 74 _ Table 3: - continuation ° E x . R1 R2 R3 m . p . ( ' C ) No.
G~ COOCH3 120 -CH2 _C~HS - 132 - ?5 -tartan substances of the formul II s Example (II-11 HN~N-'O C 2 H 5 ~2H5 Step 1:
H-i-CO-NH-OC2H5 (zX-1) A mixture of 68.5 g (0.60 mol) of 5-methyl-1,3,4-oxadiazolin-2-one, 45.8 g (0.75 mol) of 0-ethyl-hydroxyl-amine and 400 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and reconcentrated. The residue which is obtained in this process is stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 77.5 g (74 ~ of theory) of 1-ethoxy-aminocarbonyl-2-propionyl-hydrazine of melting point 122°C.
_ 76 _ Step 2:
O
NN~NipC2H~ (II-11 ~2H5 A mixture of 75.5 g (0.43 mol) of 1-ethoxyamino-carbonyl-2-propionyl-hydrazine, 17.5 g (0.44 mol) of sodium hydroxide and 300 ml of water is refluxed for 12 hours. When the mixture is cold, a ph of between 3 and 4 is established by adding concentrated hydrochloric acid, and the mixture is concentrated. The residue is stirred with ethyl acetate, and the sodium chlaride which has remained undissolved is separated off by filtration with suction. The filtrate is concentrated, the residue is stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtra-tion with suction.
This gives 37 g (55 ~ of theory) of 4-ethoxy-5 ethyl-2,9-dihydro-3II-1,24-triazol-3-one of melting paint 93°C.
Example (II-2~
HN~N~CH3 (II-2) ~C3H7 A mixture of 90 g (0.3i molj of 5-propyl-1,3,4-oxadiazolin-2-one, 109 g of aqueous methylamine solution . (32 $ strength, 1.125 mol of CN3NHz) and 500 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and~reconcentrated. The residua obtained in this process is stirred with diethyl ether, and the product which has been obtained in crys-talline form is isolated by filtration with suction.
Thi$ gives 31.7 g (72 % of theory) of 9-methyl-5-propyl-2,4-dihydro-3H-1,24-triazol-3-one of melting point 86°C.
Example( I I-3 ~, O
HN~N~'N(CH3)2 ~H
856 g ( 4 . 0 mol ) of Biphenyl carbonate are dis-solved in 588 g of ethylene chloride. 295 g (9.0 mol)~of dimethylhydrazine (98 $ pure) are added dropwise with 15, water-cooling, and the mixture is heated slowly and, for 4 hours, stirred at 60°C.
After the mixture has cooled to 20°C, 200 g (4.0 mol) of hydrazine hydrate are added dropwise, and the mixture is then stirred for 12 hours. It is warmed to 70-80°C and, for about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during which process ethylene chloride aid water are removed (final bottom temperature 100°C). The above phenolic ~ dimethyl carbodihydrazide solution is added dropwise in the course of 90 minutes at reflux temperature (about 102°C) to g24 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has farmed is removed by distil-s lation, phenol is distilled off in vacua, after which 282 g of product mixture are obtained at a head temper-ature of 85-105°C. This mixture is boiled with 600 ml of acetone, and filtered at boiling point, and the filtrate is then cooled. The product which has been obtained in this process in crystalline form is isolated by filtra-tion with suction.
This gives 71 g (14 % of theory) of 4-dimethyl-amino-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 127°C.
For example the compounds of the formulae (II) and (IIa) listed in Table 4 below can also be prepared analogously to Examples (II-1) to (II-3).
HN~NiRl (II) Table 4: Preparation examples of ~~e compounds of the formula (TI) -Ex. R' R2 m.p. ( C) No.
II-4 C3H? CN3 . 48 II-S CH(CH3)2 CH3 11B
II-6 C)-I3 CH3 ~ 139 II-8 C3H~ C2HS 42 - 45 II-9 CH(CH3)2 C2H5 102 II-10 C2H$ C3H~ 97 II-il C3H~ C3H~ (amorphous) I1-12 CH(CH3)2 C3H~ 91 II-13 CH3 CH(CH3)2 92 II-14 C2H5 CH(CH3)2 (amorphous) II-1S C3H~ ~ CH(CH3)2 (amorphous) II-16 CH(CH3)2 CH(CH3)2 1b8 I1-21 OCH3 C3H~ 127 Table 4 - continuation I;x. R' R2 m.p. (Cj No.
II-22 OCH3 GH(~H3)2 130 II-23 OCH2CbH~ CHI lOb II-27 C~3tCH3)2 121 II-30 C3H7 C4H9 (amorphous) C4H9 6b II-35 C3H7 ~ 68 - ai -, Table 4 -cQ~~inuation Ex. R1 R2 m.p ('C) No.
II-37 NtCH3)2 CH3 153 II-38 N(CH3)2 C2H~ 114 II-39 N(CH3)2 C3H7 108 II-40 N(CH3)2 CH(CH3)2 100 II-41 CH3 N(CH3)2 80 II-42 N(CH3)2 134 II-43 CHtCH3)2 NHCH(Ctl3)2 205 II-44 N(CN3)2 N(CH3)2 93 II-45 CZHS NtCH3~2 50 II-47 ~ CH3 163 II-53 ' CF'3 163 t ~ Table 4 - continuation Ex. Ri R~ m.p. ( C) No.
II-54 NHCH3 CHiCH3)2 105 II-55 NHCH3 ~ 95 iI-58 NHCH3 NHCH3 137 II.-61 NHCH3 N(Ct~3)2 129 II-63 NH2 ~ I 248 II-64 NH2 -~HC2H5 176 II-68 NH2 N(C2H5)2 196 - g3 _ Table 4 - continuation Ex. R1 R2 mP ( oC) No.
II-69 NH2 ~N- 233 II-70 NH2 CH(CN3D2 172 II-71 NH2 C(CH3)3 261 II-73 NH2 C(CH3)2C~H5 213 II-74 NH2 ~lHC2H5 220 II-75 . NH2 OCH3 (amorphous) II-76 HH~ ~ CH20GH3 134 II-78 N(CH3)2 GH3 153 II-80 -CH2CH(CH3)2 C2H5 105 II-82 N(CH3)2 CH(CH3)2 (amorphous) II-84 NH2 CH2CbH5 168 II-85 NH2 N(CH3)2 207 II-86 NH2 CbHS 230 CA
Table 4 - continuation Ex. R1 Rz m.p. ( C}
No.
II-.87 NH2 223 II-88 NH2 NHCH(CH3)2 152 II-89 NHCH3 NHCH(CH3)2 120 II-90 ~ NH~ 254 ---II-91 N(C~3)2 II-92 GH2C6H5 H ill II-93 C3H7 y~ 48 II-94 C6H5 C2H5 , 124 II-95 C(CH3)3 C2~j5 158 II-96 CH3 ~ 157 H
II-98 ~ C H
iI-99 -CH2CH=CH2 CH3 108 II-101 ~ CH3 116 II-102 ~ C2H5 146 II-104 CH(CH3)2 H 105 Table 9 - continuation - Ex. R' RZ m.p. ( C) No.
II-105 ~ H 79 II-106 ~ H 162 II-107 C(CH3)3 H 194 II-108 -CN2-iH-CH2Br CH3 111 W
II-1.10 _ CH3 -CH20C2H5 102 II-112 ~ -CH20C2H5 119 II-113 -~ -N(CH3)2 130 iCH3 \C2H5 ~.CN3 ~C3H7-n ~2H5 II-l1b NH2 -N 186 .
,.C3H7_n II-117 NH2 -N O 2b7 U
_ 86 _ k The compound of Example (II-118) disclosed in Table 4 (above) can be prepared as follows;
O
HN~N~CH3 tII-118) ~CH3 50.2 g (0.33 mol) of hydrazino-formic acid phenyl ester (= 1-phenoxycarbonyl-hydrazine) and 36.6 g (0.33 mol;
90 ~ purity) of O,O,N-trimethyl-iminocarbonate are mixed at 40 °C With 100 ml of 1,2-dichlorobenzene, and this mixture is then stirred for two hours at 60 °C. There-after the mixture is heated further up to 120 °C, while methanol (formed during the reaction) is being distilled off. Then the reaction mixture is cooled and heated again in vacuo (0.01 mbar) to Ia temperature of 120 °C in order to remove any remaining volatile com-pounds (methanol, phenol and 1,2-dichlorobenzene) from .
the reaction mixture. At a temperature above 120 °C the reaction product is distilled roughly and then crystal-lized from toluene.
This gives 7.5 g (18 ~ of theory) of 5-methoxy-4-methyl-2,4-dihydro-3l~-1,2,4-triazol-one as colorless crystals of melting point 144°C.
~- S 3 Examples of hydrazine derivatives of the formula (IX) which can be obtained analogously to Ex-ample {II-1), step listed in Table 5 below, 1, are H-N-CO-NH-Ri tIX) Table 5: Examples o~ the hxdr~~ine derivatives of the formula (IX) Ex. R1 RZ m.p. ( C) No.
IX-4 OCH3 CHtCH3)2 127 IX-6 C2H~ 17Q
IX-7 C~H7 180 IX-8 OOHS C3H~ 119 IX-9 CH t t:j~3 ) 150 IX-10 OCH3 CgH9 134 Table 5 - continuation EX. R1 ~t2 m~p~ ( '~') No.
IX-I2 ~ 188 IX-19 CH2-CH=CH2 C3H7 134 _~
IX-15 ~ -CH20C2H5 97 Startin substances of the formula IV
- Example (IV-1~
O
- C O'~N~N~C H 3 °' '''2H5 6.4 g (0.05 mol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in BO m1 of tetra-s hydrofuran, and 1.8 g (0.06 mol) of sodium hydride (80 $
of substance) are added under nitrogen. After the mixture has been stirred for one hour at 20°C, 7.9 g (0.05 mol) of phenyl chloroformate are added dropwise, and the reaction mixture is stirred at 20°C for a further 20 hours. After the mixture has been concentrated, the residue is taken up in methylene chloride, and the mixture is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated, the residue is triturated with diethyl ethers and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 4.5 g (36 $ of theory) of 5-ethyl-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 141°C.
For example the compounds of the formula (IV) listed in Table 6 below can also be prepared analogously to Example (IV-1).
Z - C O~N~N~Fi 1 ( I V ) R
Table 6: Examples of the compounds of the formula {IV) Ex. R1 RZ Z m.p. ('C) No.
I V-2 C3?~~ C3H~ . C6H5 88 IV-3 OCH3 C3H~ CbHS 82 IV-4 CH3 C3N~ C6H5 84 IV-5 NH2 C3Hy GbHS 133 IV-6 NH2 CH3 C6?~5 82 iV-8 OC2H5 C2H5 CbHS
IV-9 OCH2CH=CH2 CH3 C6H5 CA 02420329 2003-03-13 _ a _ Table 6 - continuation EX. R~ R2 Z m.p. ('C) No.
IV-13 CH3 CH2CbH5 C6H5 IY-14 CH3 NHCH(CH3)2 C6H5 IV-15 N(CHa)2 N(CN3)~ C6H5 IV-19 C2H5 CqH9 C6H5 IV-2Q CHfCH3)2 CH(CH3)2 CbE~5 iv-21 OcH3 C2H5 C6H5 89 IV-22 C3H7-r~ C6H5 109 Use Examples:
In the following us-e examples, the known herbicide isocarbamide, of formula (A) below, is used as comparison substance:
HN~~ N-CO-NH--CI~zCH(CIi3~ ( A ) O
The formulae of the compounds used in the Use Examples are listed individually below in conjunction with the number of the Preparation Examples:
OC~H~2 C
SOZ-NH-CU~N~N~CH3 ( 4 I
N---~
'C H
2. 5 OCHFZ
O
~~/ -S02-NH-CO~N~~~CxHs ( 5 ) I
N ~C2H5 SOz NH-CO~N~ ~CH3 ( 6 N
I
N C
O
SO2 Nii CO~N~ ~CH3 ( 2 ) N
I
CH3 N----~
~C ~I
2 s Cl O
~ S02-1JH-CO~N~PJ~'C2H5 ( 7 ) CH 3 TT"-"1C 2H 5 Cl O
~ SOZ-NH-CO~N~N-'CH3 ( g ) CHI 1~3H~
("J-S02-NH-CO~N~N~OCH3 (12) ~C2H5 COOCtf3 O
502-NH-CO~N~N~'OCI~i3 ( 1 3 ) -"3H7 S02N(CH3)2 O
~SOZ-NH-CO~N~N~CH3 (1A) ~.~%
. ~2H5 S02N(CH3)2 O
~ SO~-NH-CO'~N~1J~CH3 ( 15 ~c 3 ti ~
~S02-NH-CO~N~ , (16D
~2ti5 S02-NH-CO''~N~N~OCH3 t 1 7 ) ~H(CH~)2 r' so2N ( cl-i3 ) 2 0 ~S0 -NH-CO'~
~
-~
2 N ( 1 ~ D
-Nl~-CO~N~
~ t 1 2 N--~c 9 y ) i ~
50 ( 20 -NH-CO~N~N~'CH ) I-~_~~~~
I~NtCH
) COOCHS O
50 (26) -NH-CO'~N~N~OC
H
S
-"2H5 ~S0 -1JH-CO~N~
~
2 OC2tl5 t 27 N ) ~I~ ~
~
COOCH~ O
-Nti-CO~1J~~
~
2 N ( 28 ~H ) tCH3)2 C1 p -NH-CO~N~
2 1 t29) CH
COOCJi3 O
-NH-CO~N~
' ~ N- t aO
2 N ( CH ) ) ~
~N~
w COOCH~ 0 - ~'SOZ'NH-CO~N~N~'G2H5 ( 32 ~4H9 S02-NH-CO~N~N~'CH3 ( 33 502-NH-CO~N~N~C3H~ (3q l N'~4H9 S02-NH-CO~N~ (3S
S02-NH-CO~N~N~'CH3 ( 3y to ,l--S02-NH-CO'~N~N~'C3H~ ( 39 -I
S02-NH-CO~N~ (40) 502-NH-CO'N~N~'OC1-~~ ( 9 ) ~CH3 S02-NH-CO'i I~N(CH3)2 (31) S02-NH-CO'IJ~N~OC~-I3 ( 36 t Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier; 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the~preparation of active compound, It is expedient here to keep constant the amount of water per unit area. The concentration of active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage of the plants is rated in % damage in comparison with the development of the untreated control. The figures denotes 0 % = no action (like untreated control) 100 % = total destruction In. this test a clearly superior activity com pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 6, 8, 12, 13, 16, 17, 1B, 19, 20, 26, 2?, 28, 29, 34, 3?, 39 and 40.
i ~' Example H
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Test plants having a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way that the specifically desired amounts of active compound per unit area are applied. The concentration of the spray liquor is chosen in such a way that the speci fically desired amounts of active substance are applied in 1000 1 of water/ha. After three weeks, the.degree of damage of the plants is rated in % damage in comparison with the development of the untreated control. The figures denote:
0 % = no action (like untreated control) 100 % = total destruction In this test a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 4, 5, 6, 7, 8, 12, 13, 14, 15, 16, 17, 1B, 19, 20, 26, 27, 28, 29, 30, 32, 33, 34, 35, 37, 39 and 4p.
Example G
Pyricularia test (rice) / protective Solvent: 12,5 parts by weight of acetone ET:rulsifier: 0,3 parts by weight of alkylaxylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and~the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.
To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated with an aqueous spore suspension of Pyricularia orycae. The plants arc then placed in a greenhouse at 100 ~ relative atmospheric humidity and 25°C.
Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, a very good activity is shown, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 3Q, 31, 32, 33, 34, 35, 36 ,37.
- i00 -Example D
Pyricularia Test (rice) / systemic Solvent . 12,5 parts by weight of acetone Emulsifier: 0,3 parts by weight of alkylaryl-poly-glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.
To test for systemic properties, standard soil in which young plants have been grown is watered with 90 ml of the preparation of active compoun d. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.
Thereafter, the plants remain in a greenhouse at a temperature of . 25° and a relative atmospheric humidity of 100 until they are evaluatedo Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, an excellent activity is shown, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 3b, 37.
- l
SO~NtCH3)2 ~, 16 C2H5 ~ 154 17 OCH3 CH(CH3)2 137 ~i S02N(CH3)2 18 C2H5 ~ 174 19 C3H7 ~ 97 20 CH3 NtCH3)2 168 Cl 22 C2H5 C3H7 ~ 136 C~3 - b1 -Table 3s - continuation Ex. Ri R2 R3 m.p. ( C) No.
23 N(CH3)2 C2H5 ~ a39 24 N(CH3)2 H 197 25 NtCH3)2 CH(CH3)z ~- 148 26 OC2N5 C2H5 ~ 153 T
27 OC2H5 C3H7 ~ 155 28 CH(CH3)2 186 r J~
29 C3H~ ~ 146 30 N ( CHa C3H7 / 1_1 G
) 2 Table 3: - continuation Ex. R1 RZ #i$ m.p. ( °C) No.
COOCt~3 31 N(CH3a2 ~~ 131 32 C2H5 C,~H~ ~ 98 33 CH3 C4H9 ~ 113 34 C3H7 C4H9 ~ 88 35 C4Hg ~ 117 36 OCH3 C4H9 ~ 117 38 C2H5 ~ 130 Table 3s -continuation Ex. R1 RZ ~i$ m.p. ( C~
No.
39 C3H7 ~ -- 139 9 0 lsl 41 ~ CH3 ~ 151 .
92 CH(CH3)2 NHCt-1(CH3)2~ ~ 13s 93 N(CH3)2 N(CH~)2 ~ 171 A4 CH3 C3H~ r 1b8 45 C2H5 N(CH3)2 i34 OC~'3 46 CH3 C2H5 ~ 167 Table 3: - continuation fix. R1 R2 R3 m.p. ( °C) No.
pC~3 47 NH2 C3H~ / 120 4s --~ NH~ 120 coocH~
COOCH3 ' 50 -CH2GH=CH2 G2H5 108 51 -CH2CH=CH2 H ~~ 158 COOC~3 3 CH2--(") H / , 212 - 214 54 C3H7 ~d 168 - 169 Table 3: - continuation - Ex. R1 R2 R3 m.p. ('C) No.
55 C3H7 ~ ~ 103 - 105 OC~'3 57 OCH3 C2H5 ~ ~ 111 - 113 ~
59 -I~HCH3 C3H7-n ~ 196 F -60 CN3 C3H7-n ~ ~ i78 61 ~ H ~ 177 Table 3:
- continuation Ex. R1 R2 R3 mP ~ ~0) No.
COOC#i3 /
62 -CH2CH(CH3)2 C2H5 \ 123 63 -CH2-CH=CH2 C3N7-n (amorphous) 6A CH C ~ 157 / H
~
b5 / CZHS / 117 \ \
__ ~_ bb -C(CH3)3 C2H5 -~ 182 67 ~ C2H5 / \
68 ~ C2H5 69 -CH2-CH=CH2 CH3 120 - 6? -Table 3:
- continuation - EX. R~ R2 No.
70 H C ~- 183 HS
~
73 -OCH3 ~ 138 ~
79 CH(CH3)2 H ~ 191 75 ~ H
76 ~ H ~ 192 77 -C(CH3)3 H ~ ~ 211 6D _ Table 3: - continuation Ex. R' R2 R3 m.p. ( °C) No.
78 -CH2-iH-CH2Br CH3 ~ \ 110 Br 79 CH3 -CH20CH3 / ~ 152 F
80 CH3 C2H5 ~~\ 174 81 CH3 -CH20C2H5 ~ \ 123 CF3:
82 -OCH3 C3H7-n (amorphous) CON(CH3)2 83 C2H5 ' ~ 129 84 -CH20CN3 /'\
85 -CH20CH3 / \ 155 I _ 6g _ Table 3: - continuation - EX. R1 RZ R3 m.p~ ( '~.') No.
COOC~-13 ~
~
OC~'3 87 -CH20C2H5 ~ 99 C~
88 -NiCH3)2 ~ 189 89 -OCH3 C2H5 ~ 155 ~
Ci 91 -OCH3 C3H7-n ~ 125 ~
92 C2H5 ~ 138 ~
S
- 7d -Table 3: - continuation EX. R1 R2 R3 m.p. ( 'C) No.
93 -OC2H5 C2H5 \ 132 ~
94 -OC2H5 C3H~-n \ 107 95 -OCH3 CH(CH3)~ ~ 128 ocF3 ~
96 OCH3 CH3 _\ 119 ~
97 C3H7-n ~ 100 ~
98 ~
\ 140 .
~
99 -N ( CH3 ) -\
~
100 -N(CH3)2 \ 182 Table 3: - continuation Ex. R' RZ R3 m.p. ( 'C) No.
101 CH3 -N(CH3)z ~~ 181 Co0CH3 102 CH3 -OCH3 ~ 150 CI
103 CZHS ~ ~ 147 104 -CH2-CH=CH2 CH3 ~ 132 105 -CH2-CH=CH2 C2H5 ~ ~ 109 106 -CH2-CH=CH2 C3H7-n ~ lpq _ 72 _ Table 3: - continuation EX. R1 RZ R3 m.p. ( ~C) No.
107 -OC2H5 C2N5 , ~ 197 108 -OC2H5 C3H7-n r ' 136 C ~i 3 Cl 109 -OCH3 CH(CH3)2 / ~ 126 110 CH3 CH3 ~ ~ 146 111 CH3 ~ ~ 175 112 CH3 CH(CH3)2 ~ ~ 124 Table 3: - continuation EX. R~ RZ R3 m.p. ( 'C) No.
113 CH3 , ~ 171 C~3 114 CHICH3)2 / \ 132 115 ~ ~ 167 117 CN3 C2H5 ~ ~ 147 118 CH3. C3H7-n ~ 169 - 74 _ Table 3: - continuation ° E x . R1 R2 R3 m . p . ( ' C ) No.
G~ COOCH3 120 -CH2 _C~HS - 132 - ?5 -tartan substances of the formul II s Example (II-11 HN~N-'O C 2 H 5 ~2H5 Step 1:
H-i-CO-NH-OC2H5 (zX-1) A mixture of 68.5 g (0.60 mol) of 5-methyl-1,3,4-oxadiazolin-2-one, 45.8 g (0.75 mol) of 0-ethyl-hydroxyl-amine and 400 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and reconcentrated. The residue which is obtained in this process is stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 77.5 g (74 ~ of theory) of 1-ethoxy-aminocarbonyl-2-propionyl-hydrazine of melting point 122°C.
_ 76 _ Step 2:
O
NN~NipC2H~ (II-11 ~2H5 A mixture of 75.5 g (0.43 mol) of 1-ethoxyamino-carbonyl-2-propionyl-hydrazine, 17.5 g (0.44 mol) of sodium hydroxide and 300 ml of water is refluxed for 12 hours. When the mixture is cold, a ph of between 3 and 4 is established by adding concentrated hydrochloric acid, and the mixture is concentrated. The residue is stirred with ethyl acetate, and the sodium chlaride which has remained undissolved is separated off by filtration with suction. The filtrate is concentrated, the residue is stirred with diethyl ether, and the product which has been obtained in crystalline form is isolated by filtra-tion with suction.
This gives 37 g (55 ~ of theory) of 4-ethoxy-5 ethyl-2,9-dihydro-3II-1,24-triazol-3-one of melting paint 93°C.
Example (II-2~
HN~N~CH3 (II-2) ~C3H7 A mixture of 90 g (0.3i molj of 5-propyl-1,3,4-oxadiazolin-2-one, 109 g of aqueous methylamine solution . (32 $ strength, 1.125 mol of CN3NHz) and 500 ml of water is refluxed for 12 hours and then concentrated. The residue is taken up in ethanol and~reconcentrated. The residua obtained in this process is stirred with diethyl ether, and the product which has been obtained in crys-talline form is isolated by filtration with suction.
Thi$ gives 31.7 g (72 % of theory) of 9-methyl-5-propyl-2,4-dihydro-3H-1,24-triazol-3-one of melting point 86°C.
Example( I I-3 ~, O
HN~N~'N(CH3)2 ~H
856 g ( 4 . 0 mol ) of Biphenyl carbonate are dis-solved in 588 g of ethylene chloride. 295 g (9.0 mol)~of dimethylhydrazine (98 $ pure) are added dropwise with 15, water-cooling, and the mixture is heated slowly and, for 4 hours, stirred at 60°C.
After the mixture has cooled to 20°C, 200 g (4.0 mol) of hydrazine hydrate are added dropwise, and the mixture is then stirred for 12 hours. It is warmed to 70-80°C and, for about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during which process ethylene chloride aid water are removed (final bottom temperature 100°C). The above phenolic ~ dimethyl carbodihydrazide solution is added dropwise in the course of 90 minutes at reflux temperature (about 102°C) to g24 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has farmed is removed by distil-s lation, phenol is distilled off in vacua, after which 282 g of product mixture are obtained at a head temper-ature of 85-105°C. This mixture is boiled with 600 ml of acetone, and filtered at boiling point, and the filtrate is then cooled. The product which has been obtained in this process in crystalline form is isolated by filtra-tion with suction.
This gives 71 g (14 % of theory) of 4-dimethyl-amino-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 127°C.
For example the compounds of the formulae (II) and (IIa) listed in Table 4 below can also be prepared analogously to Examples (II-1) to (II-3).
HN~NiRl (II) Table 4: Preparation examples of ~~e compounds of the formula (TI) -Ex. R' R2 m.p. ( C) No.
II-4 C3H? CN3 . 48 II-S CH(CH3)2 CH3 11B
II-6 C)-I3 CH3 ~ 139 II-8 C3H~ C2HS 42 - 45 II-9 CH(CH3)2 C2H5 102 II-10 C2H$ C3H~ 97 II-il C3H~ C3H~ (amorphous) I1-12 CH(CH3)2 C3H~ 91 II-13 CH3 CH(CH3)2 92 II-14 C2H5 CH(CH3)2 (amorphous) II-1S C3H~ ~ CH(CH3)2 (amorphous) II-16 CH(CH3)2 CH(CH3)2 1b8 I1-21 OCH3 C3H~ 127 Table 4 - continuation I;x. R' R2 m.p. (Cj No.
II-22 OCH3 GH(~H3)2 130 II-23 OCH2CbH~ CHI lOb II-27 C~3tCH3)2 121 II-30 C3H7 C4H9 (amorphous) C4H9 6b II-35 C3H7 ~ 68 - ai -, Table 4 -cQ~~inuation Ex. R1 R2 m.p ('C) No.
II-37 NtCH3)2 CH3 153 II-38 N(CH3)2 C2H~ 114 II-39 N(CH3)2 C3H7 108 II-40 N(CH3)2 CH(CH3)2 100 II-41 CH3 N(CH3)2 80 II-42 N(CH3)2 134 II-43 CHtCH3)2 NHCH(Ctl3)2 205 II-44 N(CN3)2 N(CH3)2 93 II-45 CZHS NtCH3~2 50 II-47 ~ CH3 163 II-53 ' CF'3 163 t ~ Table 4 - continuation Ex. Ri R~ m.p. ( C) No.
II-54 NHCH3 CHiCH3)2 105 II-55 NHCH3 ~ 95 iI-58 NHCH3 NHCH3 137 II.-61 NHCH3 N(Ct~3)2 129 II-63 NH2 ~ I 248 II-64 NH2 -~HC2H5 176 II-68 NH2 N(C2H5)2 196 - g3 _ Table 4 - continuation Ex. R1 R2 mP ( oC) No.
II-69 NH2 ~N- 233 II-70 NH2 CH(CN3D2 172 II-71 NH2 C(CH3)3 261 II-73 NH2 C(CH3)2C~H5 213 II-74 NH2 ~lHC2H5 220 II-75 . NH2 OCH3 (amorphous) II-76 HH~ ~ CH20GH3 134 II-78 N(CH3)2 GH3 153 II-80 -CH2CH(CH3)2 C2H5 105 II-82 N(CH3)2 CH(CH3)2 (amorphous) II-84 NH2 CH2CbH5 168 II-85 NH2 N(CH3)2 207 II-86 NH2 CbHS 230 CA
Table 4 - continuation Ex. R1 Rz m.p. ( C}
No.
II-.87 NH2 223 II-88 NH2 NHCH(CH3)2 152 II-89 NHCH3 NHCH(CH3)2 120 II-90 ~ NH~ 254 ---II-91 N(C~3)2 II-92 GH2C6H5 H ill II-93 C3H7 y~ 48 II-94 C6H5 C2H5 , 124 II-95 C(CH3)3 C2~j5 158 II-96 CH3 ~ 157 H
II-98 ~ C H
iI-99 -CH2CH=CH2 CH3 108 II-101 ~ CH3 116 II-102 ~ C2H5 146 II-104 CH(CH3)2 H 105 Table 9 - continuation - Ex. R' RZ m.p. ( C) No.
II-105 ~ H 79 II-106 ~ H 162 II-107 C(CH3)3 H 194 II-108 -CN2-iH-CH2Br CH3 111 W
II-1.10 _ CH3 -CH20C2H5 102 II-112 ~ -CH20C2H5 119 II-113 -~ -N(CH3)2 130 iCH3 \C2H5 ~.CN3 ~C3H7-n ~2H5 II-l1b NH2 -N 186 .
,.C3H7_n II-117 NH2 -N O 2b7 U
_ 86 _ k The compound of Example (II-118) disclosed in Table 4 (above) can be prepared as follows;
O
HN~N~CH3 tII-118) ~CH3 50.2 g (0.33 mol) of hydrazino-formic acid phenyl ester (= 1-phenoxycarbonyl-hydrazine) and 36.6 g (0.33 mol;
90 ~ purity) of O,O,N-trimethyl-iminocarbonate are mixed at 40 °C With 100 ml of 1,2-dichlorobenzene, and this mixture is then stirred for two hours at 60 °C. There-after the mixture is heated further up to 120 °C, while methanol (formed during the reaction) is being distilled off. Then the reaction mixture is cooled and heated again in vacuo (0.01 mbar) to Ia temperature of 120 °C in order to remove any remaining volatile com-pounds (methanol, phenol and 1,2-dichlorobenzene) from .
the reaction mixture. At a temperature above 120 °C the reaction product is distilled roughly and then crystal-lized from toluene.
This gives 7.5 g (18 ~ of theory) of 5-methoxy-4-methyl-2,4-dihydro-3l~-1,2,4-triazol-one as colorless crystals of melting point 144°C.
~- S 3 Examples of hydrazine derivatives of the formula (IX) which can be obtained analogously to Ex-ample {II-1), step listed in Table 5 below, 1, are H-N-CO-NH-Ri tIX) Table 5: Examples o~ the hxdr~~ine derivatives of the formula (IX) Ex. R1 RZ m.p. ( C) No.
IX-4 OCH3 CHtCH3)2 127 IX-6 C2H~ 17Q
IX-7 C~H7 180 IX-8 OOHS C3H~ 119 IX-9 CH t t:j~3 ) 150 IX-10 OCH3 CgH9 134 Table 5 - continuation EX. R1 ~t2 m~p~ ( '~') No.
IX-I2 ~ 188 IX-19 CH2-CH=CH2 C3H7 134 _~
IX-15 ~ -CH20C2H5 97 Startin substances of the formula IV
- Example (IV-1~
O
- C O'~N~N~C H 3 °' '''2H5 6.4 g (0.05 mol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in BO m1 of tetra-s hydrofuran, and 1.8 g (0.06 mol) of sodium hydride (80 $
of substance) are added under nitrogen. After the mixture has been stirred for one hour at 20°C, 7.9 g (0.05 mol) of phenyl chloroformate are added dropwise, and the reaction mixture is stirred at 20°C for a further 20 hours. After the mixture has been concentrated, the residue is taken up in methylene chloride, and the mixture is washed with water, dried with sodium sulphate and filtered. The filtrate is concentrated, the residue is triturated with diethyl ethers and the product which has been obtained in crystalline form is isolated by filtration with suction.
This gives 4.5 g (36 $ of theory) of 5-ethyl-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 141°C.
For example the compounds of the formula (IV) listed in Table 6 below can also be prepared analogously to Example (IV-1).
Z - C O~N~N~Fi 1 ( I V ) R
Table 6: Examples of the compounds of the formula {IV) Ex. R1 RZ Z m.p. ('C) No.
I V-2 C3?~~ C3H~ . C6H5 88 IV-3 OCH3 C3H~ CbHS 82 IV-4 CH3 C3N~ C6H5 84 IV-5 NH2 C3Hy GbHS 133 IV-6 NH2 CH3 C6?~5 82 iV-8 OC2H5 C2H5 CbHS
IV-9 OCH2CH=CH2 CH3 C6H5 CA 02420329 2003-03-13 _ a _ Table 6 - continuation EX. R~ R2 Z m.p. ('C) No.
IV-13 CH3 CH2CbH5 C6H5 IY-14 CH3 NHCH(CH3)2 C6H5 IV-15 N(CHa)2 N(CN3)~ C6H5 IV-19 C2H5 CqH9 C6H5 IV-2Q CHfCH3)2 CH(CH3)2 CbE~5 iv-21 OcH3 C2H5 C6H5 89 IV-22 C3H7-r~ C6H5 109 Use Examples:
In the following us-e examples, the known herbicide isocarbamide, of formula (A) below, is used as comparison substance:
HN~~ N-CO-NH--CI~zCH(CIi3~ ( A ) O
The formulae of the compounds used in the Use Examples are listed individually below in conjunction with the number of the Preparation Examples:
OC~H~2 C
SOZ-NH-CU~N~N~CH3 ( 4 I
N---~
'C H
2. 5 OCHFZ
O
~~/ -S02-NH-CO~N~~~CxHs ( 5 ) I
N ~C2H5 SOz NH-CO~N~ ~CH3 ( 6 N
I
N C
O
SO2 Nii CO~N~ ~CH3 ( 2 ) N
I
CH3 N----~
~C ~I
2 s Cl O
~ S02-1JH-CO~N~PJ~'C2H5 ( 7 ) CH 3 TT"-"1C 2H 5 Cl O
~ SOZ-NH-CO~N~N-'CH3 ( g ) CHI 1~3H~
("J-S02-NH-CO~N~N~OCH3 (12) ~C2H5 COOCtf3 O
502-NH-CO~N~N~'OCI~i3 ( 1 3 ) -"3H7 S02N(CH3)2 O
~SOZ-NH-CO~N~N~CH3 (1A) ~.~%
. ~2H5 S02N(CH3)2 O
~ SO~-NH-CO'~N~1J~CH3 ( 15 ~c 3 ti ~
~S02-NH-CO~N~ , (16D
~2ti5 S02-NH-CO''~N~N~OCH3 t 1 7 ) ~H(CH~)2 r' so2N ( cl-i3 ) 2 0 ~S0 -NH-CO'~
~
-~
2 N ( 1 ~ D
-Nl~-CO~N~
~ t 1 2 N--~c 9 y ) i ~
50 ( 20 -NH-CO~N~N~'CH ) I-~_~~~~
I~NtCH
) COOCHS O
50 (26) -NH-CO'~N~N~OC
H
S
-"2H5 ~S0 -1JH-CO~N~
~
2 OC2tl5 t 27 N ) ~I~ ~
~
COOCH~ O
-Nti-CO~1J~~
~
2 N ( 28 ~H ) tCH3)2 C1 p -NH-CO~N~
2 1 t29) CH
COOCJi3 O
-NH-CO~N~
' ~ N- t aO
2 N ( CH ) ) ~
~N~
w COOCH~ 0 - ~'SOZ'NH-CO~N~N~'G2H5 ( 32 ~4H9 S02-NH-CO~N~N~'CH3 ( 33 502-NH-CO~N~N~C3H~ (3q l N'~4H9 S02-NH-CO~N~ (3S
S02-NH-CO~N~N~'CH3 ( 3y to ,l--S02-NH-CO'~N~N~'C3H~ ( 39 -I
S02-NH-CO~N~ (40) 502-NH-CO'N~N~'OC1-~~ ( 9 ) ~CH3 S02-NH-CO'i I~N(CH3)2 (31) S02-NH-CO'IJ~N~OC~-I3 ( 36 t Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier; 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the~preparation of active compound, It is expedient here to keep constant the amount of water per unit area. The concentration of active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage of the plants is rated in % damage in comparison with the development of the untreated control. The figures denotes 0 % = no action (like untreated control) 100 % = total destruction In. this test a clearly superior activity com pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 6, 8, 12, 13, 16, 17, 1B, 19, 20, 26, 2?, 28, 29, 34, 3?, 39 and 40.
i ~' Example H
Post-emergence test Solvent: 5 parts by weight of acetone Emulsifiers 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.
Test plants having a height of 5 - 15 cm are sprayed with the preparation of active compound in such a way that the specifically desired amounts of active compound per unit area are applied. The concentration of the spray liquor is chosen in such a way that the speci fically desired amounts of active substance are applied in 1000 1 of water/ha. After three weeks, the.degree of damage of the plants is rated in % damage in comparison with the development of the untreated control. The figures denote:
0 % = no action (like untreated control) 100 % = total destruction In this test a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of Preparation Examples 2, 4, 5, 6, 7, 8, 12, 13, 14, 15, 16, 17, 1B, 19, 20, 26, 27, 28, 29, 30, 32, 33, 34, 35, 37, 39 and 4p.
Example G
Pyricularia test (rice) / protective Solvent: 12,5 parts by weight of acetone ET:rulsifier: 0,3 parts by weight of alkylaxylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and~the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.
To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated with an aqueous spore suspension of Pyricularia orycae. The plants arc then placed in a greenhouse at 100 ~ relative atmospheric humidity and 25°C.
Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, a very good activity is shown, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 3Q, 31, 32, 33, 34, 35, 36 ,37.
- i00 -Example D
Pyricularia Test (rice) / systemic Solvent . 12,5 parts by weight of acetone Emulsifier: 0,3 parts by weight of alkylaryl-poly-glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, to the desired concentration.
To test for systemic properties, standard soil in which young plants have been grown is watered with 90 ml of the preparation of active compoun d. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.
Thereafter, the plants remain in a greenhouse at a temperature of . 25° and a relative atmospheric humidity of 100 until they are evaluatedo Evaluation of the disease infestation is carried out 4 days after the inoculation.
In this test, an excellent activity is shown, for example, by the compounds according to the following preparation examples:
9, 12, 13, 20, 30, 31, 32, 33, 34, 35, 3b, 37.
- l
Claims (12)
1. A triazolinone of the formula wherein R1 is C1-C6-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, phenyl, C1-C4-alkoxy or C1-C4-alkoxycarbonyl) or is C3-C4-alkenyloxy and R2 is hydrogen, or represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy or C1-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C4-alkyl, or represents phenyl-C1-C3-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy and/or C1-C4-alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, trifluoromethyl, methyl, C1-C4-alkoxy, fluorine- and/or chlorine-substituted C1-C3-alkoxy, C1-C4-alkylthio, fluorine- and/or chlorine-substituted C1-C3-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl and/or C1-C4-alkoxy-carbonyl.
2. A triazolinone according to claim 1, wherein R1 is methoxy, ethoxy, propoxy or isopropoxy, and R2 is hydrogen, C1-C4-alkyl which is optionally substituted by fluorine and/or chlorine, methoxy or ethoxy, or represents C3-C6-cycloalkyl.
3. A triazolinone according to claim 1, selected from the group consisting of those wherein R1 represents ~and R2 represents OCH3 CH(CH3)2 OCH3 O-CH2-CH=CH2 ~CH3 O-CH2-CH=CH2~C2H5 O-CH2-CH=CH2 ~C3H7 ~~C3H7 OCH3 OCH3 OCH3 OCH3 O-CH2-COOCH3~C3H7 OC2H5
4. A triazolinone according to claim 3, wherein R1 is OCH3 and R2 is CH3.
5. A triazolinone according to claim 3, wherein R1 is OCH3 and R2 is C2H5.
6. A triazolinone according to claim 3, wherein R1 is OCH3 and R2 i s C3H7.
7. A triazolinone according to claim 3, wherein R1 is OC2H5 and R2 is C2H5.
8. A triazolinone according to claim 3, wherein R1 is OCH3 and R2 is CH(CH3)2.
9. A triazolinone according to claim 3, wherein R1 is OCH2C6H5 and R2 is CH3.
10. A triazolinone according to claim 3, wherein R1 is OC2H5 and R2 is C3H7.
11. A triazolinone according to claim 3, wherein R1 is OCH3 and R2 i s C4H9.
12. A triazolinone according to claim 3, wherein R1 is OCH3 and R2 is
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3934081A DE3934081A1 (en) | 1989-10-12 | 1989-10-12 | SULFONYLAMINOCARBONYLTRIAZOLINONE |
| DEP3934081.3 | 1989-10-12 | ||
| CA002302058A CA2302058C (en) | 1989-10-12 | 1990-10-10 | A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002302058A Division CA2302058C (en) | 1989-10-12 | 1990-10-10 | A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2420329A1 CA2420329A1 (en) | 1991-04-13 |
| CA2420329C true CA2420329C (en) | 2005-11-29 |
Family
ID=6391328
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002302058A Expired - Lifetime CA2302058C (en) | 1989-10-12 | 1990-10-10 | A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one |
| CA002027206A Expired - Lifetime CA2027206C (en) | 1989-10-12 | 1990-10-10 | Sulphonylaminocarbonyltriazolinones |
| CA002189698A Expired - Lifetime CA2189698C (en) | 1989-10-12 | 1990-10-10 | Substituted 1,2,3-triazol-3-ones |
| CA002420329A Expired - Lifetime CA2420329C (en) | 1989-10-12 | 1990-10-10 | Sulphonylaminocarbonyltriazolinones |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002302058A Expired - Lifetime CA2302058C (en) | 1989-10-12 | 1990-10-10 | A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one |
| CA002027206A Expired - Lifetime CA2027206C (en) | 1989-10-12 | 1990-10-10 | Sulphonylaminocarbonyltriazolinones |
| CA002189698A Expired - Lifetime CA2189698C (en) | 1989-10-12 | 1990-10-10 | Substituted 1,2,3-triazol-3-ones |
Country Status (13)
| Country | Link |
|---|---|
| EP (2) | EP0683157B1 (en) |
| JP (1) | JPH03133966A (en) |
| KR (1) | KR0171400B1 (en) |
| AU (1) | AU627080B2 (en) |
| BR (1) | BR9005095A (en) |
| CA (4) | CA2302058C (en) |
| CZ (1) | CZ281525B6 (en) |
| DE (3) | DE3934081A1 (en) |
| DK (2) | DK0422469T3 (en) |
| ES (2) | ES2222457T3 (en) |
| HU (1) | HU218976B (en) |
| PL (1) | PL165494B1 (en) |
| SK (1) | SK495090A3 (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE4030063A1 (en) * | 1990-09-22 | 1992-03-26 | Bayer Ag | SUBSTITUTED 5-ALKOXY-1,2,4, -TRIAZOL-3- (THI) ONE |
| DE4238125A1 (en) * | 1992-11-12 | 1994-05-19 | Bayer Ag | Substituted triazolinones |
| US6906006B1 (en) | 1988-11-23 | 2005-06-14 | Bayer Aktiengesellschaft | N-arly-substituted nitrogen-containing heterocycles, processes and novel intermediates for their preparation, and their use as herbicides and plant growth regulators |
| DE3928662A1 (en) * | 1989-08-30 | 1991-03-07 | Bayer Ag | SUBSTITUTED 4,5-DIAMINO-1,2,4-TRIAZOL-3- (THI) ONE |
| US5534486A (en) * | 1991-04-04 | 1996-07-09 | Bayer Aktiengesellschaft | Herbicidal sulphonylaminocarbonyl triazolinones having substituents bonded via oxygen |
| DE4316430A1 (en) * | 1993-05-17 | 1994-11-24 | Bayer Ag | Substituted triazolinones |
| DE4343595A1 (en) * | 1993-12-21 | 1995-06-22 | Bayer Ag | Process for the preparation of sulfonylaminocarbonyltriazolinones |
| DE4411913A1 (en) * | 1994-04-07 | 1995-10-12 | Bayer Ag | Substituted sulfonylaminocarbonyltriazolinones |
| DE4435547A1 (en) * | 1994-10-05 | 1996-04-11 | Bayer Ag | Sulfonylaminocarbonyltriazolinone with substituents bonded via oxygen and sulfur |
| DE19502579A1 (en) * | 1995-01-27 | 1996-08-01 | Bayer Ag | Sulfonylamino (thio) carbonyl-triazolin (thi) one |
| DE19525974A1 (en) * | 1995-07-17 | 1997-01-23 | Bayer Ag | Substituted arylsulfonylamino (thio) carbonyltriazolin (thi) one |
| DE19530450A1 (en) * | 1995-08-18 | 1997-02-20 | Bayer Ag | Process for the preparation of substituted aminotriazolinones |
| ZA974703B (en) * | 1996-05-30 | 1997-12-30 | Bayer Ag | Substituted sulfonylamino(thio)carbonyl compounds. |
| DE19632945A1 (en) * | 1996-08-16 | 1998-02-19 | Bayer Ag | Substituted sulfonylamino (thio) carbonyl compounds |
| DE19802697A1 (en) | 1998-01-24 | 1999-07-29 | Bayer Ag | Selective, synergistic herbicidal composition, especially for weed control in wheat |
| DE19823131A1 (en) * | 1998-05-23 | 1999-11-25 | Bayer Ag | New sulfonylaminocarbonyl-triazolinone derivatives, used as herbicides or as fungicides or bactericides for plant protection |
| DE19843766A1 (en) | 1998-09-24 | 2000-03-30 | Bayer Ag | Substituted thiazole (in) ylidene aminosulfonylamino (thio) carbonyl triazolinones |
| DE19845408A1 (en) | 1998-10-02 | 2000-04-27 | Bayer Ag | Selective herbicides based on a substituted phenylsulfonylaminocarbonyl-triazolinone |
| DE19845407B4 (en) | 1998-10-02 | 2012-06-28 | Arysta LifeScience North America Corp.(n.d.Ges.d.Staates Californien) | Selective herbicides based on a substituted phenylsulfonylaminocarbonyl-triazolinone |
| US5912354A (en) * | 1998-12-11 | 1999-06-15 | Bayer Corporation | Process for preparing 4-amino-1,2,4-triazolin-5-ones |
| KR100704718B1 (en) * | 1999-12-27 | 2007-04-09 | 바이엘 코포레이션 | A process for the manufacture of the salts of sulfonylaminocarbonyl triazolinones |
| KR100431154B1 (en) * | 2002-04-12 | 2004-05-12 | (주)하나실업 | Patterning method for denim |
| EP1717228A1 (en) | 2005-04-28 | 2006-11-02 | Bayer CropScience GmbH | Sulfonylamino(thio)carbonylderivatives as herbicides or plant growth regulators |
| DE102008060967A1 (en) | 2008-12-06 | 2010-06-10 | Bayer Schering Pharma Aktiengesellschaft | Substituted phenylsulfonyltriazolones and their use |
| US9505728B2 (en) | 2012-03-09 | 2016-11-29 | Inception 2, Inc. | Triazolone compounds and uses thereof |
| MX2015007433A (en) | 2012-12-20 | 2015-12-07 | Inception 2 Inc | Triazolone compounds and uses thereof. |
| WO2014202510A1 (en) | 2013-06-20 | 2014-12-24 | Bayer Cropscience Ag | Aryl sulfide derivatives and aryl sulfoxide derivatives as acaricides and insecticides |
| WO2015035059A1 (en) | 2013-09-06 | 2015-03-12 | Inception 2, Inc. | Triazolone compounds and uses thereof |
| JOP20190094A1 (en) | 2016-10-27 | 2019-04-25 | Broad Inst Inc | 2,4,5-trisubstituted 1,2,4-triazolones useful as inhibitors of dhodh |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1126882B (en) * | 1960-05-03 | 1962-04-05 | Boehringer Sohn Ingelheim | Process for the preparation of 1,2,4-triazolonen- (5) |
| US4487773A (en) * | 1981-03-16 | 1984-12-11 | Mead Johnson & Company | 1,2,4-Triazol-3-one antidepressants |
| BE894856A (en) * | 1982-10-28 | 1983-02-14 | Fahlberg List Veb | 1,2,4-Triazoline-5-one herbicides for galium species - give good control of resistant weeds in cereal and sugar beet e.g. the 3-benzyl-4-para methoxyphenyl cpd. |
| US4575555A (en) * | 1983-06-29 | 1986-03-11 | Mead Johnson & Company | 4-(3-Chlorophenyl)-1,2,3,6-tetrahydropyridine derivative |
| DE3709574A1 (en) * | 1987-03-24 | 1988-10-06 | Bayer Ag | SUBSTITUTED TRIAZOLINONES |
| 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 |
| ES2063065T3 (en) * | 1988-03-07 | 1995-01-01 | Chugai Pharmaceutical Co Ltd | DERIVATIVES OF TRIAZOL, PROCEDURE FOR ITS PREPARATION AND HERBICIDE COMPOSITIONS THAT CONTAIN THEM. |
-
1989
- 1989-10-12 DE DE3934081A patent/DE3934081A1/en not_active Withdrawn
-
1990
- 1990-09-29 DK DK90118750.0T patent/DK0422469T3/en active
- 1990-09-29 DK DK95111736T patent/DK0683157T3/en active
- 1990-09-29 EP EP95111736A patent/EP0683157B1/en not_active Expired - Lifetime
- 1990-09-29 DE DE59010938T patent/DE59010938D1/en not_active Expired - Lifetime
- 1990-09-29 ES ES95111736T patent/ES2222457T3/en not_active Expired - Lifetime
- 1990-09-29 DE DE59010314T patent/DE59010314D1/en not_active Expired - Lifetime
- 1990-09-29 EP EP90118750A patent/EP0422469B1/en not_active Expired - Lifetime
- 1990-09-29 ES ES90118750T patent/ES2087107T3/en not_active Expired - Lifetime
- 1990-10-09 JP JP2269742A patent/JPH03133966A/en active Pending
- 1990-10-10 CA CA002302058A patent/CA2302058C/en not_active Expired - Lifetime
- 1990-10-10 CA CA002027206A patent/CA2027206C/en not_active Expired - Lifetime
- 1990-10-10 CA CA002189698A patent/CA2189698C/en not_active Expired - Lifetime
- 1990-10-10 PL PL90287259A patent/PL165494B1/en unknown
- 1990-10-10 CA CA002420329A patent/CA2420329C/en not_active Expired - Lifetime
- 1990-10-11 KR KR1019900016081A patent/KR0171400B1/en not_active IP Right Cessation
- 1990-10-11 HU HU419/90A patent/HU218976B/en unknown
- 1990-10-11 CZ CS904950A patent/CZ281525B6/en not_active IP Right Cessation
- 1990-10-11 AU AU64591/90A patent/AU627080B2/en not_active Expired
- 1990-10-11 BR BR909005095A patent/BR9005095A/en not_active IP Right Cessation
- 1990-10-11 SK SK4950-90A patent/SK495090A3/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CZ495090A3 (en) | 1996-07-17 |
| CA2027206A1 (en) | 1991-04-13 |
| DE3934081A1 (en) | 1991-04-18 |
| EP0683157B1 (en) | 2004-05-26 |
| CA2027206C (en) | 1997-12-23 |
| CA2302058A1 (en) | 1991-04-13 |
| AU6459190A (en) | 1991-04-18 |
| HU906419D0 (en) | 1991-04-29 |
| DE59010938D1 (en) | 2004-07-01 |
| EP0422469A2 (en) | 1991-04-17 |
| CZ281525B6 (en) | 1996-10-16 |
| PL287259A1 (en) | 1992-01-27 |
| CA2189698A1 (en) | 1991-04-13 |
| DK0422469T3 (en) | 1996-08-26 |
| BR9005095A (en) | 1991-09-17 |
| DK0683157T3 (en) | 2004-09-27 |
| AU627080B2 (en) | 1992-08-13 |
| JPH03133966A (en) | 1991-06-07 |
| KR0171400B1 (en) | 1999-02-01 |
| KR910007893A (en) | 1991-05-30 |
| CA2420329A1 (en) | 1991-04-13 |
| ES2222457T3 (en) | 2005-02-01 |
| EP0422469A3 (en) | 1992-01-08 |
| CA2302058C (en) | 2004-05-25 |
| HUT55369A (en) | 1991-05-28 |
| SK280209B6 (en) | 1999-09-10 |
| EP0683157A1 (en) | 1995-11-22 |
| PL165494B1 (en) | 1994-12-30 |
| EP0422469B1 (en) | 1996-05-08 |
| DE59010314D1 (en) | 1996-06-13 |
| ES2087107T3 (en) | 1996-07-16 |
| HU218976B (en) | 2001-01-29 |
| SK495090A3 (en) | 1999-09-10 |
| CA2189698C (en) | 2003-05-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |