CA2302058C - A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one - Google Patents
A process for preparing 5-methoxy-4-methyl-2,4-dihydro-3h-1,2,4-triazol-3-one Download PDFInfo
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
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- 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
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- 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
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- 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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- 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
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- 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
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- 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
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- 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
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Abstract
This invention relates to a process for preparing 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of the formula (II-118) (see formula II-118) which process comprises reacting hydrazino-formic acid phenyl ester with an about equimolar amount of O,N,N-trimethylimino-carbonate.
Description
A Process For Preparing 5-Methoxy-4 Methyl-2,4-DihydrD-3H-1,2,4-Triazol-3-one The present divisional application is divided out of parent application Serial No. 2,189,698 which is a divisional application 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 the present divisional application relates to a process for preparing 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one described in more detail here-inunder. However, the expression "the invention" or the like encompasses the subject matter of both the parent and the divisional.
It is known that certain substituted aminocarbonyl-imadazolinones, such as, for example, 1-isobutylaminocarbonyl-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 general formula (I) O
R3 S02 NH CO- N N R1 (I) ~~ 2 R
in which R1 represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical from 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_Rt W ) in which R1 and R2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the general formula (III) R -S02-N=C=O (III) in which R3 has the abovementioned meanings, if appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) ' CA 02302058 2000-03-29 ~.. ~ , ~, O
Z-CO-N~N-R1 (IY) ~R2 in which R1 and RZ have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphonamides of the general formula (V) R3-502-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) triazolinones of the general formula (II) O
HN~N-R1 (II) ~N---.~ 2 R
in which Rl and RZ have the abovementioned meanings Le A 27 154 _ 3 _ are reacted with-sulphonamide derivatives of the genera 1 formula (VI) R3- 50,7 NH-CO-Z (VI ) ._ in which R3 has the abovvernentioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acc~:=ptor and if appropriate in the presence of a diluent, s.nd, if ap~~ropriate salts are formed by customary methods from the compouz-~cs of the formula (I) prepared by process (a), (b) oa-~ (c) .
The :resent iu~~ention provides a process for prepar-ing 5-methoxy-~4-methyy-.:,-~_-d:~hyc~ro--3H-i,~,4-triazol-3-one of the formula (I_:-118 ) L
~1 (II-118) ~;1~ N-CH3 OCI~.~
which process comprise: reacting hydrazino-fcrmic acid pher~wi 1~- ester with an <about~ eq~::i::~ac>lar amount of O,N,2.T-trimethyliminc-carbonate at elevated t :m~.~r~rature, in t~~: presence of a diluent.
The :zew sulpl~.or.-e ar~5.nocarbonz-1-triazclinones of the general formula (I arc' f..aE:~.r salt:r are dl stirgui.shed by a powerful herbi~zidal act:-iv~.ty . Surprisingly, the new compounds of the formula (I) show a considerably better herbicida 1 action than the known herbicic:ve i-isobutylaminocarbonyl-2-imidazoli-dinone (isoca:rbamide), which has a similar structure.
The new comprunds of the present parent application 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, C1-C4-alkoxy, C1-C4-alk;ylcarbonyl or Cl-C4-alkoxycarbonyl, or repzesents C3-C6-alken~rl or C3-C8-alkinyl, each of which is optionally substituted by fluorine, chlorine and/or bromine, or represents C3-C6-cyc:-loalkyl which is optionally substituted by fluorine, _ q chlorine, bromine and or Cl-C4-alkyl, or represents phenyl-C1-C3-alkyl which ~is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl, C1-C4-alkoxy and/or (:1-C~-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl, Cl-C~-alkoxy, fluorine- and/or chlorine-substituted Cl-C3-alkoxy, C1-C4-alkylthio, f luorine- and/or chlorine-substituted C1-C3-alkylthio, Ca-C4-alkylsul-phinyl, C1-C,-alkylsulphonyl and/or C1-C4-alkoxy-carbonyl, or represents C1-Cg-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, phenyl, C1-C4-alkoxy or Cl-Cy-alkoxy-carbonyl, or represents C3-C,-alkenyloxy, or represents C1-C4-alkylamino which is optionally substituted by fluorine, cyano, C1-C4-alkoxy or C1-C4-alkoxy-car-bonyl, or represents di-(C1-C~-alkyl)-amino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents C1-CB-alkyl which is optionally substitut ed by fluorine, chlorine, bromine, cyano, C3-CB
cycloalkyl, C1-Cy-alkoxy or C1-Cw-alkoxy-carbonyl, or represents C3-CB-cycloal.kyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C,-alkyl, or represents cyclohexenyl, or repre-sents phenyl-C1-C3-alkyl which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, C,-C4-alkoxy and/or C1-C,-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, ,f r Le A 27 154 - 5 -bromine, cyano, vitro, C1-C,-alkyl, trifluoromethyl.
C1-C~-alkoxy, fluorine- and/or chmrm~s-aunstituced C1-C3-alkoxy, C~-C'-alkylthio, fluorine- and/or chlorine-substituted Cl-C3-alkylthio, C,-C,,-alkyl-sulphinyl, Cl-C~-alkylsulphonyl and/or C1-c:,-alkoxy-carbonyl, or represents C1-C6-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, C,-C,-alkoxy or Ci-C,-alkoxy-carbonyl, or represents C1-C~-alkylamino or di-(C1-C~-alkyl)-amino, and R3 represents the group R5 , where R4 and Rs are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, vitro, C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C~-alkoxycarbonyl, Cl-C,-alkyl amino-carbonyl, di-( C1-C4-alkyl ) amino-carbonyl, hydroxyl, C1-C~-alkoxy, formyloxy, C1-C~-alkyl-carbonyloxy, Cl-C,-alkoxy-carbonyloxy, C1-C,-alkyl amino-carbonyloxy, C1-C4_ alkylthio, C~-C4-alkylsulphinyl, C1-C,-alkylsulphonyl, di-(Cl-Cw-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 CZ-Cfi-alkinyl (which is optionally s'ubsti-tuted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent Le A 27 154 _ C1-C~-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C~-alkoxy-carbonyl, C1-C4-alkoxy, C~-C~-alkylthio, C1-C~-alkylsulphinyl or Ci-C~-alkylsulphonyl ) , or represent C1-C~-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-Cy-alkoxy-carbonyl, C1-C,-alkylthio, C1-C~-alkylsulphinyl or C1-C,-alkylsulphonyl ) , or represent C3-C6-alkenyl-oxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C~-alkoxy-carbonyl), ar represent C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C3-alkylthio or C~-C,,-alkoxycarbonyl ) , C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the radical -S ( O ) p-RB 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, C1-C~-alkoxy, C1-C4-alkoxy-Cl-C~-alkyl-amino, Cl-Cy-alkylamino, di- ( C~-C~-alkyl ) -amino or phenyl, or represents the radical -NHOR' where R' represents C,-C,2-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsul phinyl, l C1-C4-alkylsulphonyl, C1-C4-alkyl carbonyl, Cl-C~-alkoxycarbonyl, C1-C,-alkyl amino-carbonyl or di-(Cl-C~-alkyl)-amino carbonyl), or represents C3-C6-alkenyl (which is optionally substituted by fluorine, be A 27 154 - 7 -chlorine or bromine), C3-C6-alkinyl, C3-CB-cycloalkyl, C3-Cs-cycloalkyl-C1-CZ-alkyl, phenyl-C,-C2-alkyl (which is optionally substi-tuted by fluorine, chlorine, vitro, cyano, C1-C~-alkyl, C1-C,-alkoxy or C~-C,-alkoxy-car-bonyl), or represents benzohydryl, or repre-sents phenyl (which is optionally substituted by fluorine, chlorine, vitro, cyano, Cl-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C~-alkylthio, trifluoromethyl-thio or C,-C~-alkoxycarbonyl), R~ and/or Rs furthermore represent phenyl or phenoxy, or represent Ci-C~-alkylcarbonylamino, Cl-Cw-alkoxycarbonylamino, C1-C4-alkylamino-carbonyl-amino, di-(Cl-C~-alkyl)amino-carbonylamino, or represent the radical -CO-Re, where Re represents C1-CB-alkyl, C1-C6-alkoxy, C3-C8-cycloalkoxy, C3-C6-alkenyloxy, Cl-C' alkylthio, C1-C4-alkylamino, C1-C~-alkoxyamino, C1-Cd-alkoxy-C1-Ca-alkyl-amino or di- ( Cl-C~-alkyl ) -amino (each of which is optionally substituted by fluorine and/or chlorine), R4 and/or RS furthermore represent trimethylsilyl, thiazolinyl, Cl-C~-alkylsulphonyloxy, di-(Cl-C~
alkyl)-aminosulphonylamino, or represent the radical -CH=N-Re, where Re represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, ~cyano, carboxyl, C~-C~-alkoxy, C1-C~-alkylthio, C1-C~-alkylsulphinyl or Cl-C~-alkylsulphonyl, or Le A 27 154 - g _ represents benzyl which is optionally substi-tuted by fluorine or chlorine, or represents C3-CB-alkenyl or C3-CB-alkinyl, each of which is optionally substituted by fluorine or chlor-ine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C~-alkyl, C1-C~-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C~-CB-alkoxy, C3-C6-alkenoxy, C3-Cs-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, C1-C~-alkyl-amino, di-(C1-Cy-alkyl)-amino, phenylamino, C1-C,-alkyl-carbonyl-amino, C1-C4-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 -~ , where R10 Ril Rl° represents hydrogen or C,-C,-alkyl, Rll and R'2 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C~-C,-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C,-alkoxy {which is optionally substituted by fluorine and/or chlorine) , carboxyl,~Cl-C,-alkoxy-carbonyl, Le A 27 154 - g -dimethylaminocarbonyl, C1-C~-alkylsulphonyl or di-( C1-C,-alkyl ) -aminosulphonyl;
furthermore R' represents the radical R13 ' ~ ~ R14, where R13 and R14 are identical or different and represent hydrogen, fluorine, chlorine, bromine, vitro, cyano, C1-C,-alkyl (which is optionally substitut ed by fluorine and/or chlorine) or C1-c:~-atxoxy (which is optionally substituted by fluorine and/or chlorine);
furthermore R3 represents the radical where R15 and Rl° are identical or different and represent hydrogen, fluorine, chlorine, bromine, vitro, cyano, Cl-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,-C~-alkylthio, C1-C~-alkylsulphinyl or Cl-C4-alkylsulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represent di-(C,-C~-alkyl)-aminosulphonyl or C1-C~-alkoxy-carbonyl or di-methylaminocarbonyl;
Le A 27 154 - 10 -' furthermore R' represents the radical R1~ ~ ~ ~R18 , where y R1' and R'° are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C,-alkyl (which is optionally substituted by fluorine and/or bromine), Cl-C,-alkoxy (which is optionally substi-tuted by fluorine and/or chlorine), or represent C1-C,-alkylthio, C1-C,-alkylsulphinyl or C,-C,-alkyl-sulphonyl (each of which is optionally substituted by fluorine .and/or chlorine), or represent di-(C1-C,-alkyl)-aminosulphonyl;
furthermore R' represents the radical R19 where A
Rte and RZ° are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, vitro, Cl-C,-alkyl (which is optionally substitut-ed by fluorine ~ and/or chlorine ) , Cl-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C,-alkylthio, C1-C,-alkylsul-phinyl or C1-C,-alkylsulphonyl (which is optional-ly substituted by fluorine. and/or chlorine), di-( C1-C,-alkyl ) -amino-sulphonyl, (:1-C,-alkoxy-car-bonyl or dimethylaminocarbonyl, and A represents oxygen, sulphur or the group N-Zl, Le A 27 154 - 11 -I !
' CA 02302058 2000-03-29 where Z' represents hydrogen, C1-C'-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or vitro), C1-C'-alkylcarbonyl, C1-C~-alkoxy-carbonyl or di-(C,-C,-alkyl)-aminocarbonyl;
furthermore R' represents the radical '~R22 , where Rz' and Rzz are identical or different and represent hydrogen, C1-C'-alkyl, halogen, C1-C'-alkoxy-carbonyl, C1-C'-alkoxy or C1-C'-halogenoalkoxy, Y1 represents sulphur or the group N-Rz', where Rz3 represents hydrogen or C~-C'-alkyl;
furthermore R3 represents the radical ' l where tJ~N~
R
Rz' represents hydrogen, C,-C'-alkyl, benzyl, quinolinyl or phenyl, .
2g Rzs represents hydrogen, halogen, cyano, vitro, C1-C'-alkyl (which is optionally substituted by Le A 27 154 - 12 -i i, fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or Cl-C4-alkoxy-carbonyl, and R26 represents hydrogen, halogen or Cl-C4-alkyl=
furthermore R3 represents one of the groups listed below, \ ~ ~N-C~9 ' N~
S ~~z~'3 \ O
O
The invention furthermore preferably relates to the sodium, potassium, magnesium, calcium, ammonium, Cl-C4-alkylammonium, di-(Cl-C4-alkyl)-ammonium, tri-(Cl-C4-alkyl)-ammonium, CS- or C6-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 Cl-C4-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 C1-C~-alkyl which is optionally substituted by fluorine and/or chlor ine or by methoxy or ethoxy, or represents C3-C6 cycloalkyl, or represents phenyl, or represents C1-C3-alkoxy, or represents C1-C3-alkylamino, or rEpresents di-(Ci-C2-alkyl)-amino, and R3 represents the group , R5 , where RQ
R" represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, Cl-C3-alkylthio, C1-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 R»
R3 represents the radical _CH~ , where R1° represents hydrogen, r' Le A 27 154 - 14 -i R11 represents fluorine, chlorine, bromine, methyl, methoxy, dif luoromethoxy, t rif luoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and R12 represents hydrogen, furthermore R3 represents the radical IJ
RO-C S ' I
O
where R represents Cl-C4-alkyl, or represents the radical O
I I
RO-C
I ~ IN
N
I
~3 where R represents Cl-C4-alkyl.
Examples of the compounds are listed in Table 1 below - cf. also the Preparation Examples.
O ' R3-S02-NH-CO-N~N-~l (I) R
Table 1: Examples of the compounds of the formula (I) Rl R2 R3 F
H
H
CHZ-CH=CHZ C2H5 ~H2_ OCH3 C3Hy ~H2-O-CH2-CH=CH2 S OOCH3 COOCZHS
C2H5 C4H9 n Le A 27 154 - 16 -~ CA 02302058 2000-03-29 ~ablg 1 - coptinuation CH3 03H' SOZN(CH3)2 C3H~
GH3 C2H5 C 1~
e~r OC3H~ CH3 NON
CH3 C3H~ S OOCH3 1V ( CH3 ) 2 CH2~ ~H2_ Le A 27 154 _ 17 _ i Table 1 - continuation Ri R2 R3 NH-CH3 ~ _ ~H2 CH3 C3H~
F~CHO
OCHFZ
F
C H 2-(. ,) C H 2 ~N-C3H7 ~N
'COOCH3 CH C~HS ~ SAN-C4H9 Le A 27 154 _ 1g _ Table 1 - continuation R1 R2 ~3 CON(CH3)2 CH3 CqH9 CON(CH3)2 CH3 C3H~
- /
C3H~ /~'~
CH3 C3H~-n C3H? n Le A 27 154 - 19 -' CA 02302058 2000-03-29 aT ble 1 - continuation C~3 CH3 C4H~ H2_ v CH3 ( HZ_ ~C Cl C2H5 / H2_ C3H7 C3H7 ~H2_ CN
CH3 CH(CH3)2 ~CH2_ -~ NON I
N~ I
Le A 27 154 - 20 -i , Table 1~- continuation NON
OCH3 C2H5 ' ~N
i COOCH(CH3)2 Cl CH3 CH3 ' I CF'3 r ,N-C H 3 CON(CH3)2 CH3 CH(CH3)2 ~H2-Le A 27 1~4 - 21 -I, Table 1 - continuation R 1 R2 1~3 Br OCHZ-CH=CHZ C2H5 CH3 ~CHS
S02-N~
Br CH3 CH(CH3)2 CH3 CH2-CH=CHZ
SCH(CH3)2 F
F
CH2-CH=CH2 H ~ I CON(CH3)2 Le A 27 154 - 22 -Tab - continuation CH2-CH=CH2 CH3 r CH2-CH=CHZ CZHS ~/~N
Cl 'CHZ -Si(CH3~3 CH3 C3H~
i ~ CON(CH3)2 C2H5 Cl Le A 27 154 - 23 -Table 1 - continuation f~c ~
CON(CH3)2 CH3 C3H~ N~S CHZ-CF3 -O
CH
OCH3 CH(CH3)2 ~ H2-. i ( CF3 I~e A 27 154 - 24 -i i fable 1 - continuation CH3 C3H~
' i 1 OCH3 C3H~ ~ II O
O
Br CH2-CH=CHZ CHZ-O-CH3 Le A 27 154 - 25 -Table 1 - continuation Rt R2 R3 ~2~2'~
N(~3~ N(~3h If, for example, 2-6-difluorophenyl 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:
F O
H.N~N~O(:H3 NaC'O +
N C2Hs F
F
_ O
SO2 NH CO~N~N~OC:H3 I
F N-~-~
~C H
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 0 ~-CO~N~N~N~~3~2 -HCl H
_ O
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:
H.N~N'CH~'2 N N(CZHsh ~3 O
-HOCH3 ~ ~ SOa NH CO~N~N'CHFZ
I
N--~
~N C H .
( 2 s~2 Formula (II) provides a general definition of the triazo-linonea to be used as starting substances in processes (a) and (c) for the preparation of compounds of the formula (I).
In formula (II), Rl and R2 preferably, or in particular, have those meanings which have already been - 27 _ mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R1 and R2.
Examples of the starting substances of the formula (II) are listed in Table 2 below.
O
HN~N_R1 I~ (B) Table 2: Examples of the starting substances of the formula (II) H H
C3H~ H
i Table 2 - continuation ~2 CH(CH3)2 H
CH2CH(CH3)2 H
C(CH3)3 H
H C3H?
H CH(CN3)2 H CH2CH(CH3)2 H C(CH3)3 H ' CH20CH3 Le A 2? 154 _ 29 _ ..
Table 2 - continuation CH3 C3H' CH3 CH(CH3)2 CH3 CHZCH(CH3)Z
CH3 C(CH3)3 CH(CH3)2 CH3 CH2CH(CH3)2 CH3 CHF2 C3H~
C2H5 C3H~
Le A 27 X54 - 30 -Table 2 - continuation f31 R 2 /CHZ
C~CH CH 3 ~H2 CH3 N(CH3)2 C2H5 N(CH3)2 C3H~
Le A 27 154 - 31 -Table 2 - continuation CZH
C3H?
C3H?
3 ?
NLCH3)2 CH
N(CH3)2 C H
N(CH3)2 C H
3 ?
Le A 27 154 - 32 -i , !
Table 2 - continuation OCH3 C~H~
OCZHS GHQ
OCZHS ~~HS
CH2_O-C2H5 NtCHg~2 O_C3H7 C3H7 O-CH2-CH=CHZ CH3 O-CH2-CH=CH2 C2H5 O-CH2-CH=CHZ C3H~
O-CH2-iH-CHZ-Br C3H~
Br Le A 27 154 - 33 -Table 2 - continuation R~ N2 OCH3 N(CH3)2 O-CH2-COOCH3 C3H?
N(CH3)2 N(CH3)2 N(CH3>2 Le A 27 154 - 34 -i t CA 02302058 2000-03-29 fable 2 - continuation C~H
Cli2-O-CH3 Le A 27 154 - 35 -The starting substances of the formula (II) are known and/or can be prepared by processes known per se (cf.
Chem. Her. 90 (1957)i 909-921; loc.cit. 98 (1965), 3025-3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra-hedron 32 (1976), 23#7-2352; Hely. Chim. Acta 63 (1980), 841-859; J. Chem. Soc. C 1967, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301,946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11.1988;
DE-P 3,916,207/LeA 26,849 dated 18.05.1989;
DE-P 3,916,208/LeA 26,850 dated 18.05.1989; J. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated 24.05.1989).
For example, the triazolinones of the formula (II) are obtained when a) oxadiazolinones of the general formula (VII) H~N~ (VII) N~R2 in which R2 has the abovementioned meaning are reacted with amino compounds of the general formula (VIII) HZN'Ri (YIII) in which R1 has the abovementioned meaning, Le A 27 154 - 36 -at temperatures between 20°C and 120°C and, if appropriate, in the presence of a diluent, such as, for example, water, end the hxdrazine derivatives fonued by this proce~a, o~ t#~~ general formula (IX) H~ NCO-NH-Ri H
(IX) ~N~
in which R' and RZ 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) 3,7~3,493/LeA 25,759 and the Preparation Examples), or when p) amino compounds of the general formula (VIII) H2N-R~ (VIII) Le A 27 154 - 37 i i in which R1 has the abovementioned meaning, are reacted with carbonic acid derivatives, such as, for example, diphenyl carbonate, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of the general formula (X) (RO)3C_R2 (X) 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 present divisional application there is provided a triazolinone of the general formula (IIa) O
~~N~A
W ) Az 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, i chlorine, bromine, cyano, Cl-C4-alkoxy, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine andlor C1-C4-alkyl, or represents C1-C4-alkoxy;
or in which ( 2 ) A1 representsand A2 repres~ts ~3 ~3 OCH 3 C2Hs OCH 3 C3H~
OC2Hs C2Hs ~3 ~(~3~2 OCHZC6Hs CH3 ~2Hs C3H~
~3 C4H9 i ' CA 02302058 2000-03-29 ~3 ~2Hs ~3H7 C3H7 ~2'~-~2 ~3 acH2-cH-ci-~2 c2Hs O-CHZ-CH-CH2 C~.H7 O-CH2- ~t,'H-CH-B!C3H7 ~3 ~3 ~3 ~2 O-CH2-COOC'H 3 C3H~
OCZHs C3H~
~~~ 3~1 C4Hg ~3 CZHs C~i~
H
- 39a -i I.
C2Hs -~2~'~2 CHg ~3 -CH20CH 3 '~2~ 3 '~2~2H5 -N~~3h The new triazolinones of the formula (IIa) are obtained either when oxadiazolinones of the general formula (VIIa) O
H~N~O
in which A2 has the abovementioned meaning, are reacted with amino compounds of the general formula (VIIIa) HZN-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) H2N-A1 (VIIIa) - 39b -i are reacted with carbonic acid derivatives, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of - 39c -the general formula (Xa) (RO)3C-AZ (Xa) in which A2 and R have the abovementio~ed meanings, analogously to the process described above under (~) (also see the Preparation Examples).
In the general formula (IIa), A1 preferably represents C1-C6-alkyl, C3-C5-alkenyl or C3-Cb-cycloalkyl, or represents C1-C6-alkoxy Which is optionally substituted by fluorine, chlo-rine, bromine, cyano, C1-C4-alkoxy or C1-C4-alk-oxy-carbonyl, in particular methyl, ethyl, allyl, cyclopropyl, methoxy, ethoxy, propoxy or isoprop-oxy; or represents di-(C1-C4-alkyl)-amino, in par-titular dimethylamino or diethylamino, and A2 preferably represents hydrogen, or represents C~-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C~-alkoxy, C1-C~-alkyl-carbonyl or Cl-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-Cw-alkoxy and/or C1-Cw-alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlor-ine, bromine, cyano, vitro, Cl-C~-alkyl, trifluoro-methyl, C,-C,-alkoxy, fluorine- and/or chlorine-substituted C~-C3-alkoxy, C~-C4-alkylthio, fluorine-and/or chlorine-substituted C1-C3-alkylthio, C1-C~-alkylsulphinyl, C1-C,-alkylsulphonyl and/or C1-C,-Le A 27 154 - 40 -alkoxy-carbonyl, or represents C1-C4-alkoxy, in particular hydrogen, Cl-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 Cl-C6-alkyl.
The compounds of the formulae (VII), (VIIa), (VIII), (VIIIa) and (X) or (Xa) which are to be used as starting substances for the preparation of the triazolinones 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 (III), R3 preferably, or in particular, 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-difluoromethoxy-, 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;.EP-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 all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl 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 t riamide.
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) is 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 sequence. 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 (I) which has been obtained in crystalline form is iso lat ed by f 1 It rat ion with suct ion .
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 (IV), 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 t1) as being preferred, or particularly preferred, for R1 and R2, and Z preferably represents chlorine, C1-C4-alkoxy, benzyloxy 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 Tablp 2 Wand phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or diphenyl 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 triazolit~one derivatives of the formula (IV) are obtained for e~campl~ Whec~ triazolinones of the general formula (II) HN~N~R1 (II) ~R2 in which R1 and R2 have the abovementioned meanings, are reacted with carbonic acid derivatives of the general formula (XI) Z-CO-Z1 (XI) in which Z has the abovementioned meaning and Le A 27 154 _ 44 _ Z1 represents a leaving 4roup, 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 tert-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 (I).
In formula (V), R3 preferably, or in particular, 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-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 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-methoxycarbonyl-and 2-ethoxycarbonyl-phenylmethanesulphonamide, 2-methoxy-carbonyl-3-thiophenesulphonamide, 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, 4,371,391f 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. Suitable 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 tent-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1-5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1-8-diazabicyclo-[5.4.0]-undec-7-ene (DHU) and 1,4-diazabicyclo-[2,2,2]-octane (DAHCO).
When carrying out process (b), the reaction I I' 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 (UI), R3 and Z preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the t compounds of toe 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 the compounds of the formula (T) 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, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotvledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, r Ipornoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the ctenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Branchiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon 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 combating of weeds in annual cultures.
The compounds of the formula (I) are suitable for combating monocotyledon and dicotyledon weeds both in the t pre-emergence and the post-emergence method. They are markedly more effective than, far example, isocarbamide.
To a certain extent, the compounds also show a fungicidal action, for example against powdery mildews and against apple scab, and also against Pyricularia oryzae on rice.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or 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 t 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 dimethyl sulphoxide, as well as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural 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 cephalins and lecithins, and Le A 27 154 - 52 -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-5-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURON) for combating weeds in cereals= 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in Soya beanss furthermore also mixtures with 2,4-dichlorophenoxyacetic acid (2,4-D)i 4-(2,4-dichlorophenoxy)-butric acid (2,4-DB)= 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 -f 1 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 (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)-acetamide (HUTACHLOR); ethyl 2-t[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHLORIMURON);2-chloro-N-~[(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-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine(CYANAZINE);2,6-dichlo-robenzonitrile(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxazolidin-3-one (DIMETHAZONE); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(9H)-one (ETHIOZIN); 2-{4-[6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP};
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); N,N-dimethyl-N'-(3-trifluoromethylphenyl)-urea (FLUOMETURON); 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-pyridone (FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-Le A 27 154 - 54 -. , r , 1H-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ);
2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid (IMAZAPYR); 2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolin-carboxylic acid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETHAPYR); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-iso-propylphenyl)-urea (ISOPROTURON); {2-methyl-4-chloro-phenoxy)-acetic acid (MCPA); (4-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-~[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic aicd or its methyl ester (METSUI~FURON); 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-4-yl) S-octyl thio-carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL); 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-Le A 27 154 - 55 -(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, insecticides, 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 be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 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.
. .
Preparation Examples:
Example 1 ~--S O2 - NH - C O~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-3H-1,2,4-triazol-3-one of melting point 146°C.
Le A 27 154 - 57 -f Example 2 CI
O
SO2 NH CO~N~ ~CH3 N
I
N~C H
(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 (~2.1 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 1 It rat ion wit h 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 O
R3-SOZ-NH-CO~N~N~1 II) R
Table 3: Preparation Examples of the compounds of the formula (1j (m.p, - melting point):
EX. R1 RZ R3 m.p. ( 'C) No.
OCHFZ
OCHFZ
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 the present divisional application relates to a process for preparing 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one described in more detail here-inunder. However, the expression "the invention" or the like encompasses the subject matter of both the parent and the divisional.
It is known that certain substituted aminocarbonyl-imadazolinones, such as, for example, 1-isobutylaminocarbonyl-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 general formula (I) O
R3 S02 NH CO- N N R1 (I) ~~ 2 R
in which R1 represents hydrogen, hydroxyl or amino, or represents an optionally substituted radical from 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_Rt W ) in which R1 and R2 have the abovementioned meanings, are reacted with sulphonyl isocyanates of the general formula (III) R -S02-N=C=O (III) in which R3 has the abovementioned meanings, if appropriate in the presence of a diluent, or when b) triazolinone derivatives of the general formula (IV) ' CA 02302058 2000-03-29 ~.. ~ , ~, O
Z-CO-N~N-R1 (IY) ~R2 in which R1 and RZ have the abovementioned meanings and Z represents halogen, alkoxy, aralkoxy or aryloxy, are reacted with sulphonamides of the general formula (V) R3-502-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) triazolinones of the general formula (II) O
HN~N-R1 (II) ~N---.~ 2 R
in which Rl and RZ have the abovementioned meanings Le A 27 154 _ 3 _ are reacted with-sulphonamide derivatives of the genera 1 formula (VI) R3- 50,7 NH-CO-Z (VI ) ._ in which R3 has the abovvernentioned meaning and Z represents halogen, alkoxy, aralkoxy or aryloxy, if appropriate in the presence of an acid acc~:=ptor and if appropriate in the presence of a diluent, s.nd, if ap~~ropriate salts are formed by customary methods from the compouz-~cs of the formula (I) prepared by process (a), (b) oa-~ (c) .
The :resent iu~~ention provides a process for prepar-ing 5-methoxy-~4-methyy-.:,-~_-d:~hyc~ro--3H-i,~,4-triazol-3-one of the formula (I_:-118 ) L
~1 (II-118) ~;1~ N-CH3 OCI~.~
which process comprise: reacting hydrazino-fcrmic acid pher~wi 1~- ester with an <about~ eq~::i::~ac>lar amount of O,N,2.T-trimethyliminc-carbonate at elevated t :m~.~r~rature, in t~~: presence of a diluent.
The :zew sulpl~.or.-e ar~5.nocarbonz-1-triazclinones of the general formula (I arc' f..aE:~.r salt:r are dl stirgui.shed by a powerful herbi~zidal act:-iv~.ty . Surprisingly, the new compounds of the formula (I) show a considerably better herbicida 1 action than the known herbicic:ve i-isobutylaminocarbonyl-2-imidazoli-dinone (isoca:rbamide), which has a similar structure.
The new comprunds of the present parent application 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, C1-C4-alkoxy, C1-C4-alk;ylcarbonyl or Cl-C4-alkoxycarbonyl, or repzesents C3-C6-alken~rl or C3-C8-alkinyl, each of which is optionally substituted by fluorine, chlorine and/or bromine, or represents C3-C6-cyc:-loalkyl which is optionally substituted by fluorine, _ q chlorine, bromine and or Cl-C4-alkyl, or represents phenyl-C1-C3-alkyl which ~is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl, C1-C4-alkoxy and/or (:1-C~-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C~-alkyl, trifluoromethyl, Cl-C~-alkoxy, fluorine- and/or chlorine-substituted Cl-C3-alkoxy, C1-C4-alkylthio, f luorine- and/or chlorine-substituted C1-C3-alkylthio, Ca-C4-alkylsul-phinyl, C1-C,-alkylsulphonyl and/or C1-C4-alkoxy-carbonyl, or represents C1-Cg-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, phenyl, C1-C4-alkoxy or Cl-Cy-alkoxy-carbonyl, or represents C3-C,-alkenyloxy, or represents C1-C4-alkylamino which is optionally substituted by fluorine, cyano, C1-C4-alkoxy or C1-C4-alkoxy-car-bonyl, or represents di-(C1-C~-alkyl)-amino, R2 represents hydrogen, hydroxyl, mercapto or amino, or represents C1-CB-alkyl which is optionally substitut ed by fluorine, chlorine, bromine, cyano, C3-CB
cycloalkyl, C1-Cy-alkoxy or C1-Cw-alkoxy-carbonyl, or represents C3-CB-cycloal.kyl which is optionally substituted by fluorine, chlorine, bromine and/or C1-C,-alkyl, or represents cyclohexenyl, or repre-sents phenyl-C1-C3-alkyl which is optionally substi-tuted by fluorine, chlorine, bromine, cyano, vitro, C1-C4-alkyl, trifluoromethyl, C,-C4-alkoxy and/or C1-C,-alkoxy-carbonyl, or represents phenyl which is optionally substituted by fluorine, chlorine, ,f r Le A 27 154 - 5 -bromine, cyano, vitro, C1-C,-alkyl, trifluoromethyl.
C1-C~-alkoxy, fluorine- and/or chmrm~s-aunstituced C1-C3-alkoxy, C~-C'-alkylthio, fluorine- and/or chlorine-substituted Cl-C3-alkylthio, C,-C,,-alkyl-sulphinyl, Cl-C~-alkylsulphonyl and/or C1-c:,-alkoxy-carbonyl, or represents C1-C6-alkoxy which is option-ally substituted by fluorine, chlorine, cyano, C,-C,-alkoxy or Ci-C,-alkoxy-carbonyl, or represents C1-C~-alkylamino or di-(C1-C~-alkyl)-amino, and R3 represents the group R5 , where R4 and Rs are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, vitro, C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C~-alkoxycarbonyl, Cl-C,-alkyl amino-carbonyl, di-( C1-C4-alkyl ) amino-carbonyl, hydroxyl, C1-C~-alkoxy, formyloxy, C1-C~-alkyl-carbonyloxy, Cl-C,-alkoxy-carbonyloxy, C1-C,-alkyl amino-carbonyloxy, C1-C4_ alkylthio, C~-C4-alkylsulphinyl, C1-C,-alkylsulphonyl, di-(Cl-Cw-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 CZ-Cfi-alkinyl (which is optionally s'ubsti-tuted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), or represent Le A 27 154 _ C1-C~-alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C~-alkoxy-carbonyl, C1-C4-alkoxy, C~-C~-alkylthio, C1-C~-alkylsulphinyl or Ci-C~-alkylsulphonyl ) , or represent C1-C~-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-Cy-alkoxy-carbonyl, C1-C,-alkylthio, C1-C~-alkylsulphinyl or C1-C,-alkylsulphonyl ) , or represent C3-C6-alkenyl-oxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C~-alkoxy-carbonyl), ar represent C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, vitro, C1-C3-alkylthio or C~-C,,-alkoxycarbonyl ) , C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the radical -S ( O ) p-RB 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, C1-C~-alkoxy, C1-C4-alkoxy-Cl-C~-alkyl-amino, Cl-Cy-alkylamino, di- ( C~-C~-alkyl ) -amino or phenyl, or represents the radical -NHOR' where R' represents C,-C,2-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsul phinyl, l C1-C4-alkylsulphonyl, C1-C4-alkyl carbonyl, Cl-C~-alkoxycarbonyl, C1-C,-alkyl amino-carbonyl or di-(Cl-C~-alkyl)-amino carbonyl), or represents C3-C6-alkenyl (which is optionally substituted by fluorine, be A 27 154 - 7 -chlorine or bromine), C3-C6-alkinyl, C3-CB-cycloalkyl, C3-Cs-cycloalkyl-C1-CZ-alkyl, phenyl-C,-C2-alkyl (which is optionally substi-tuted by fluorine, chlorine, vitro, cyano, C1-C~-alkyl, C1-C,-alkoxy or C~-C,-alkoxy-car-bonyl), or represents benzohydryl, or repre-sents phenyl (which is optionally substituted by fluorine, chlorine, vitro, cyano, Cl-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, C1-C2-fluoroalkoxy, C1-C~-alkylthio, trifluoromethyl-thio or C,-C~-alkoxycarbonyl), R~ and/or Rs furthermore represent phenyl or phenoxy, or represent Ci-C~-alkylcarbonylamino, Cl-Cw-alkoxycarbonylamino, C1-C4-alkylamino-carbonyl-amino, di-(Cl-C~-alkyl)amino-carbonylamino, or represent the radical -CO-Re, where Re represents C1-CB-alkyl, C1-C6-alkoxy, C3-C8-cycloalkoxy, C3-C6-alkenyloxy, Cl-C' alkylthio, C1-C4-alkylamino, C1-C~-alkoxyamino, C1-Cd-alkoxy-C1-Ca-alkyl-amino or di- ( Cl-C~-alkyl ) -amino (each of which is optionally substituted by fluorine and/or chlorine), R4 and/or RS furthermore represent trimethylsilyl, thiazolinyl, Cl-C~-alkylsulphonyloxy, di-(Cl-C~
alkyl)-aminosulphonylamino, or represent the radical -CH=N-Re, where Re represents C1-C6-alkyl which is optionally substituted by fluorine, chlorine, ~cyano, carboxyl, C~-C~-alkoxy, C1-C~-alkylthio, C1-C~-alkylsulphinyl or Cl-C~-alkylsulphonyl, or Le A 27 154 - g _ represents benzyl which is optionally substi-tuted by fluorine or chlorine, or represents C3-CB-alkenyl or C3-CB-alkinyl, each of which is optionally substituted by fluorine or chlor-ine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C~-alkyl, C1-C~-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or represents C~-CB-alkoxy, C3-C6-alkenoxy, C3-Cs-alkinoxy or benzyloxy, each of which is optionally substituted by fluorine and/or chlorine, or represents amino, C1-C~-alkyl-amino, di-(C1-Cy-alkyl)-amino, phenylamino, C1-C,-alkyl-carbonyl-amino, C1-C4-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 -~ , where R10 Ril Rl° represents hydrogen or C,-C,-alkyl, Rll and R'2 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C~-C,-alkyl (which is optionally substitut-ed by fluorine and/or chlorine), C1-C,-alkoxy {which is optionally substituted by fluorine and/or chlorine) , carboxyl,~Cl-C,-alkoxy-carbonyl, Le A 27 154 - g -dimethylaminocarbonyl, C1-C~-alkylsulphonyl or di-( C1-C,-alkyl ) -aminosulphonyl;
furthermore R' represents the radical R13 ' ~ ~ R14, where R13 and R14 are identical or different and represent hydrogen, fluorine, chlorine, bromine, vitro, cyano, C1-C,-alkyl (which is optionally substitut ed by fluorine and/or chlorine) or C1-c:~-atxoxy (which is optionally substituted by fluorine and/or chlorine);
furthermore R3 represents the radical where R15 and Rl° are identical or different and represent hydrogen, fluorine, chlorine, bromine, vitro, cyano, Cl-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,-C~-alkylthio, C1-C~-alkylsulphinyl or Cl-C4-alkylsulphonyl (each of which is optionally substituted by fluorine and/or chlorine), or represent di-(C,-C~-alkyl)-aminosulphonyl or C1-C~-alkoxy-carbonyl or di-methylaminocarbonyl;
Le A 27 154 - 10 -' furthermore R' represents the radical R1~ ~ ~ ~R18 , where y R1' and R'° are identical or different and represent hydrogen, fluorine, chlorine, bromine, C1-C,-alkyl (which is optionally substituted by fluorine and/or bromine), Cl-C,-alkoxy (which is optionally substi-tuted by fluorine and/or chlorine), or represent C1-C,-alkylthio, C1-C,-alkylsulphinyl or C,-C,-alkyl-sulphonyl (each of which is optionally substituted by fluorine .and/or chlorine), or represent di-(C1-C,-alkyl)-aminosulphonyl;
furthermore R' represents the radical R19 where A
Rte and RZ° are identical or different and represent hydrogen, fluorine, chlorine, bromine, cyano, vitro, Cl-C,-alkyl (which is optionally substitut-ed by fluorine ~ and/or chlorine ) , Cl-C,-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C,-alkylthio, C1-C,-alkylsul-phinyl or C1-C,-alkylsulphonyl (which is optional-ly substituted by fluorine. and/or chlorine), di-( C1-C,-alkyl ) -amino-sulphonyl, (:1-C,-alkoxy-car-bonyl or dimethylaminocarbonyl, and A represents oxygen, sulphur or the group N-Zl, Le A 27 154 - 11 -I !
' CA 02302058 2000-03-29 where Z' represents hydrogen, C1-C'-alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or vitro), C1-C'-alkylcarbonyl, C1-C~-alkoxy-carbonyl or di-(C,-C,-alkyl)-aminocarbonyl;
furthermore R' represents the radical '~R22 , where Rz' and Rzz are identical or different and represent hydrogen, C1-C'-alkyl, halogen, C1-C'-alkoxy-carbonyl, C1-C'-alkoxy or C1-C'-halogenoalkoxy, Y1 represents sulphur or the group N-Rz', where Rz3 represents hydrogen or C~-C'-alkyl;
furthermore R3 represents the radical ' l where tJ~N~
R
Rz' represents hydrogen, C,-C'-alkyl, benzyl, quinolinyl or phenyl, .
2g Rzs represents hydrogen, halogen, cyano, vitro, C1-C'-alkyl (which is optionally substituted by Le A 27 154 - 12 -i i, fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), dioxolanyl or Cl-C4-alkoxy-carbonyl, and R26 represents hydrogen, halogen or Cl-C4-alkyl=
furthermore R3 represents one of the groups listed below, \ ~ ~N-C~9 ' N~
S ~~z~'3 \ O
O
The invention furthermore preferably relates to the sodium, potassium, magnesium, calcium, ammonium, Cl-C4-alkylammonium, di-(Cl-C4-alkyl)-ammonium, tri-(Cl-C4-alkyl)-ammonium, CS- or C6-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 Cl-C4-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 C1-C~-alkyl which is optionally substituted by fluorine and/or chlor ine or by methoxy or ethoxy, or represents C3-C6 cycloalkyl, or represents phenyl, or represents C1-C3-alkoxy, or represents C1-C3-alkylamino, or rEpresents di-(Ci-C2-alkyl)-amino, and R3 represents the group , R5 , where RQ
R" represents fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, 2-chloro-ethoxy, 2-methoxy-ethoxy, Cl-C3-alkylthio, C1-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 R»
R3 represents the radical _CH~ , where R1° represents hydrogen, r' Le A 27 154 - 14 -i R11 represents fluorine, chlorine, bromine, methyl, methoxy, dif luoromethoxy, t rif luoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl, and R12 represents hydrogen, furthermore R3 represents the radical IJ
RO-C S ' I
O
where R represents Cl-C4-alkyl, or represents the radical O
I I
RO-C
I ~ IN
N
I
~3 where R represents Cl-C4-alkyl.
Examples of the compounds are listed in Table 1 below - cf. also the Preparation Examples.
O ' R3-S02-NH-CO-N~N-~l (I) R
Table 1: Examples of the compounds of the formula (I) Rl R2 R3 F
H
H
CHZ-CH=CHZ C2H5 ~H2_ OCH3 C3Hy ~H2-O-CH2-CH=CH2 S OOCH3 COOCZHS
C2H5 C4H9 n Le A 27 154 - 16 -~ CA 02302058 2000-03-29 ~ablg 1 - coptinuation CH3 03H' SOZN(CH3)2 C3H~
GH3 C2H5 C 1~
e~r OC3H~ CH3 NON
CH3 C3H~ S OOCH3 1V ( CH3 ) 2 CH2~ ~H2_ Le A 27 154 _ 17 _ i Table 1 - continuation Ri R2 R3 NH-CH3 ~ _ ~H2 CH3 C3H~
F~CHO
OCHFZ
F
C H 2-(. ,) C H 2 ~N-C3H7 ~N
'COOCH3 CH C~HS ~ SAN-C4H9 Le A 27 154 _ 1g _ Table 1 - continuation R1 R2 ~3 CON(CH3)2 CH3 CqH9 CON(CH3)2 CH3 C3H~
- /
C3H~ /~'~
CH3 C3H~-n C3H? n Le A 27 154 - 19 -' CA 02302058 2000-03-29 aT ble 1 - continuation C~3 CH3 C4H~ H2_ v CH3 ( HZ_ ~C Cl C2H5 / H2_ C3H7 C3H7 ~H2_ CN
CH3 CH(CH3)2 ~CH2_ -~ NON I
N~ I
Le A 27 154 - 20 -i , Table 1~- continuation NON
OCH3 C2H5 ' ~N
i COOCH(CH3)2 Cl CH3 CH3 ' I CF'3 r ,N-C H 3 CON(CH3)2 CH3 CH(CH3)2 ~H2-Le A 27 1~4 - 21 -I, Table 1 - continuation R 1 R2 1~3 Br OCHZ-CH=CHZ C2H5 CH3 ~CHS
S02-N~
Br CH3 CH(CH3)2 CH3 CH2-CH=CHZ
SCH(CH3)2 F
F
CH2-CH=CH2 H ~ I CON(CH3)2 Le A 27 154 - 22 -Tab - continuation CH2-CH=CH2 CH3 r CH2-CH=CHZ CZHS ~/~N
Cl 'CHZ -Si(CH3~3 CH3 C3H~
i ~ CON(CH3)2 C2H5 Cl Le A 27 154 - 23 -Table 1 - continuation f~c ~
CON(CH3)2 CH3 C3H~ N~S CHZ-CF3 -O
CH
OCH3 CH(CH3)2 ~ H2-. i ( CF3 I~e A 27 154 - 24 -i i fable 1 - continuation CH3 C3H~
' i 1 OCH3 C3H~ ~ II O
O
Br CH2-CH=CHZ CHZ-O-CH3 Le A 27 154 - 25 -Table 1 - continuation Rt R2 R3 ~2~2'~
N(~3~ N(~3h If, for example, 2-6-difluorophenyl 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:
F O
H.N~N~O(:H3 NaC'O +
N C2Hs F
F
_ O
SO2 NH CO~N~N~OC:H3 I
F N-~-~
~C H
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 0 ~-CO~N~N~N~~3~2 -HCl H
_ O
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:
H.N~N'CH~'2 N N(CZHsh ~3 O
-HOCH3 ~ ~ SOa NH CO~N~N'CHFZ
I
N--~
~N C H .
( 2 s~2 Formula (II) provides a general definition of the triazo-linonea to be used as starting substances in processes (a) and (c) for the preparation of compounds of the formula (I).
In formula (II), Rl and R2 preferably, or in particular, have those meanings which have already been - 27 _ mentioned above in connection with the description of the compounds of the formula (I) as being preferred, or particularly preferred, for R1 and R2.
Examples of the starting substances of the formula (II) are listed in Table 2 below.
O
HN~N_R1 I~ (B) Table 2: Examples of the starting substances of the formula (II) H H
C3H~ H
i Table 2 - continuation ~2 CH(CH3)2 H
CH2CH(CH3)2 H
C(CH3)3 H
H C3H?
H CH(CN3)2 H CH2CH(CH3)2 H C(CH3)3 H ' CH20CH3 Le A 2? 154 _ 29 _ ..
Table 2 - continuation CH3 C3H' CH3 CH(CH3)2 CH3 CHZCH(CH3)Z
CH3 C(CH3)3 CH(CH3)2 CH3 CH2CH(CH3)2 CH3 CHF2 C3H~
C2H5 C3H~
Le A 27 X54 - 30 -Table 2 - continuation f31 R 2 /CHZ
C~CH CH 3 ~H2 CH3 N(CH3)2 C2H5 N(CH3)2 C3H~
Le A 27 154 - 31 -Table 2 - continuation CZH
C3H?
C3H?
3 ?
NLCH3)2 CH
N(CH3)2 C H
N(CH3)2 C H
3 ?
Le A 27 154 - 32 -i , !
Table 2 - continuation OCH3 C~H~
OCZHS GHQ
OCZHS ~~HS
CH2_O-C2H5 NtCHg~2 O_C3H7 C3H7 O-CH2-CH=CHZ CH3 O-CH2-CH=CH2 C2H5 O-CH2-CH=CHZ C3H~
O-CH2-iH-CHZ-Br C3H~
Br Le A 27 154 - 33 -Table 2 - continuation R~ N2 OCH3 N(CH3)2 O-CH2-COOCH3 C3H?
N(CH3)2 N(CH3)2 N(CH3>2 Le A 27 154 - 34 -i t CA 02302058 2000-03-29 fable 2 - continuation C~H
Cli2-O-CH3 Le A 27 154 - 35 -The starting substances of the formula (II) are known and/or can be prepared by processes known per se (cf.
Chem. Her. 90 (1957)i 909-921; loc.cit. 98 (1965), 3025-3099; J. Heterocycl. Chem. 15 (1978), 237-240; Tetra-hedron 32 (1976), 23#7-2352; Hely. Chim. Acta 63 (1980), 841-859; J. Chem. Soc. C 1967, 746-751; EP-A 283,876;
EP-A 294,666; EP-A 301,946; EP-A 298,371;
DE-P 3,839,206/LeA 26,538 dated 19.11.1988;
DE-P 3,916,207/LeA 26,849 dated 18.05.1989;
DE-P 3,916,208/LeA 26,850 dated 18.05.1989; J. Chem. Soc.
C 1970, 26-34; DE-P 3,916,930/LeA 26,886 dated 24.05.1989).
For example, the triazolinones of the formula (II) are obtained when a) oxadiazolinones of the general formula (VII) H~N~ (VII) N~R2 in which R2 has the abovementioned meaning are reacted with amino compounds of the general formula (VIII) HZN'Ri (YIII) in which R1 has the abovementioned meaning, Le A 27 154 - 36 -at temperatures between 20°C and 120°C and, if appropriate, in the presence of a diluent, such as, for example, water, end the hxdrazine derivatives fonued by this proce~a, o~ t#~~ general formula (IX) H~ NCO-NH-Ri H
(IX) ~N~
in which R' and RZ 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) 3,7~3,493/LeA 25,759 and the Preparation Examples), or when p) amino compounds of the general formula (VIII) H2N-R~ (VIII) Le A 27 154 - 37 i i in which R1 has the abovementioned meaning, are reacted with carbonic acid derivatives, such as, for example, diphenyl carbonate, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of the general formula (X) (RO)3C_R2 (X) 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 present divisional application there is provided a triazolinone of the general formula (IIa) O
~~N~A
W ) Az 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, i chlorine, bromine, cyano, Cl-C4-alkoxy, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl, or represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine andlor C1-C4-alkyl, or represents C1-C4-alkoxy;
or in which ( 2 ) A1 representsand A2 repres~ts ~3 ~3 OCH 3 C2Hs OCH 3 C3H~
OC2Hs C2Hs ~3 ~(~3~2 OCHZC6Hs CH3 ~2Hs C3H~
~3 C4H9 i ' CA 02302058 2000-03-29 ~3 ~2Hs ~3H7 C3H7 ~2'~-~2 ~3 acH2-cH-ci-~2 c2Hs O-CHZ-CH-CH2 C~.H7 O-CH2- ~t,'H-CH-B!C3H7 ~3 ~3 ~3 ~2 O-CH2-COOC'H 3 C3H~
OCZHs C3H~
~~~ 3~1 C4Hg ~3 CZHs C~i~
H
- 39a -i I.
C2Hs -~2~'~2 CHg ~3 -CH20CH 3 '~2~ 3 '~2~2H5 -N~~3h The new triazolinones of the formula (IIa) are obtained either when oxadiazolinones of the general formula (VIIa) O
H~N~O
in which A2 has the abovementioned meaning, are reacted with amino compounds of the general formula (VIIIa) HZN-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) H2N-A1 (VIIIa) - 39b -i are reacted with carbonic acid derivatives, then with hydrazine or hydrazine hydrate and eventually with a carboxylic acid derivative or carbonic acid derivative of - 39c -the general formula (Xa) (RO)3C-AZ (Xa) in which A2 and R have the abovementio~ed meanings, analogously to the process described above under (~) (also see the Preparation Examples).
In the general formula (IIa), A1 preferably represents C1-C6-alkyl, C3-C5-alkenyl or C3-Cb-cycloalkyl, or represents C1-C6-alkoxy Which is optionally substituted by fluorine, chlo-rine, bromine, cyano, C1-C4-alkoxy or C1-C4-alk-oxy-carbonyl, in particular methyl, ethyl, allyl, cyclopropyl, methoxy, ethoxy, propoxy or isoprop-oxy; or represents di-(C1-C4-alkyl)-amino, in par-titular dimethylamino or diethylamino, and A2 preferably represents hydrogen, or represents C~-C6-alkyl which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C~-alkoxy, C1-C~-alkyl-carbonyl or Cl-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-Cw-alkoxy and/or C1-Cw-alkoxycarbonyl, or represents phenyl which is optionally substituted by fluorine, chlor-ine, bromine, cyano, vitro, Cl-C~-alkyl, trifluoro-methyl, C,-C,-alkoxy, fluorine- and/or chlorine-substituted C~-C3-alkoxy, C~-C4-alkylthio, fluorine-and/or chlorine-substituted C1-C3-alkylthio, C1-C~-alkylsulphinyl, C1-C,-alkylsulphonyl and/or C1-C,-Le A 27 154 - 40 -alkoxy-carbonyl, or represents C1-C4-alkoxy, in particular hydrogen, Cl-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 Cl-C6-alkyl.
The compounds of the formulae (VII), (VIIa), (VIII), (VIIIa) and (X) or (Xa) which are to be used as starting substances for the preparation of the triazolinones 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 (III), R3 preferably, or in particular, 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-difluoromethoxy-, 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;.EP-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 all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl 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 t riamide.
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) is 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 sequence. 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 (I) which has been obtained in crystalline form is iso lat ed by f 1 It rat ion with suct ion .
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 (IV), 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 t1) as being preferred, or particularly preferred, for R1 and R2, and Z preferably represents chlorine, C1-C4-alkoxy, benzyloxy 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 Tablp 2 Wand phosgene, methyl chloroformate, benzyl chloroformate, phenyl chloroformate or diphenyl 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 triazolit~one derivatives of the formula (IV) are obtained for e~campl~ Whec~ triazolinones of the general formula (II) HN~N~R1 (II) ~R2 in which R1 and R2 have the abovementioned meanings, are reacted with carbonic acid derivatives of the general formula (XI) Z-CO-Z1 (XI) in which Z has the abovementioned meaning and Le A 27 154 _ 44 _ Z1 represents a leaving 4roup, 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 tert-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 (I).
In formula (V), R3 preferably, or in particular, 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-trifluoromethyl-, 2-difluoro-methoxy-, 2-trifluoromethoxy-, 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-methoxycarbonyl-and 2-ethoxycarbonyl-phenylmethanesulphonamide, 2-methoxy-carbonyl-3-thiophenesulphonamide, 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, 4,371,391f 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. Suitable 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 tent-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1-5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1-8-diazabicyclo-[5.4.0]-undec-7-ene (DHU) and 1,4-diazabicyclo-[2,2,2]-octane (DAHCO).
When carrying out process (b), the reaction I I' 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 (UI), R3 and Z preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the t compounds of toe 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 the compounds of the formula (T) 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, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotvledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, r Ipornoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the ctenera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Branchiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon 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 combating of weeds in annual cultures.
The compounds of the formula (I) are suitable for combating monocotyledon and dicotyledon weeds both in the t pre-emergence and the post-emergence method. They are markedly more effective than, far example, isocarbamide.
To a certain extent, the compounds also show a fungicidal action, for example against powdery mildews and against apple scab, and also against Pyricularia oryzae on rice.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or 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 t 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 dimethyl sulphoxide, as well as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural 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 cephalins and lecithins, and Le A 27 154 - 52 -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-5-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMETHYDIONE) or N-(2-benzothiazolyl)-N, N'-dimethylurea (METABENZTHIAZURON) for combating weeds in cereals= 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in Soya beanss furthermore also mixtures with 2,4-dichlorophenoxyacetic acid (2,4-D)i 4-(2,4-dichlorophenoxy)-butric acid (2,4-DB)= 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 -f 1 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 (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitrile;
(BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethyl-phenyl)-acetamide (HUTACHLOR); ethyl 2-t[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHLORIMURON);2-chloro-N-~[(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-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazine(CYANAZINE);2,6-dichlo-robenzonitrile(DICHLOBENIL);2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxazolidin-3-one (DIMETHAZONE); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(9H)-one (ETHIOZIN); 2-{4-[6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP};
2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (FLUAZIFOP); N,N-dimethyl-N'-(3-trifluoromethylphenyl)-urea (FLUOMETURON); 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-pyridone (FLURIDONE); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); N-phos-phonomethyl-glycine (GLYPHOSATE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-Le A 27 154 - 54 -. , r , 1H-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ);
2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid (IMAZAPYR); 2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolin-carboxylic acid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethylpyridin-3-carboxylic acid (IMAZETHAPYR); 3,5-diiodo-4-hydroxy-benzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-iso-propylphenyl)-urea (ISOPROTURON); {2-methyl-4-chloro-phenoxy)-acetic acid (MCPA); (4-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-~[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic aicd or its methyl ester (METSUI~FURON); 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-4-yl) S-octyl thio-carbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL); 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-Le A 27 154 - 55 -(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, insecticides, 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 be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 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.
. .
Preparation Examples:
Example 1 ~--S O2 - NH - C O~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-3H-1,2,4-triazol-3-one of melting point 146°C.
Le A 27 154 - 57 -f Example 2 CI
O
SO2 NH CO~N~ ~CH3 N
I
N~C H
(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 (~2.1 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 1 It rat ion wit h 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 O
R3-SOZ-NH-CO~N~N~1 II) R
Table 3: Preparation Examples of the compounds of the formula (1j (m.p, - melting point):
EX. R1 RZ R3 m.p. ( 'C) No.
OCHFZ
OCHFZ
6 CH3 C3H~ 143 Cl 7 C2H5 C2H5 ~ 139 Le A 27 154 _ 5g _ i ~
Table 3s - continuation EX. R1 R2 A9 m.p. ( °C) No.
c1 8 CH3- C3H~ ~ 141 Sb2N(CH3)2 11 OCH3 CH3 ~ 149 12 OCH3 C2H5 ~ 144 13 OCH3 C3H7 ~ 128 SOZN(CH3)2 14 CH3 C2H5 ~ 173 Le A 27 154 - 60 -z Table 3: - continuatiop EX. R1 Ra ~t9 m.p. ( °C) No.
SO~N(CH3)2 15 CH3 C3H7 ~ 133 CooCH~
16 C2H5 ~" 154 17 OCH3 CH(CH3)2 ~ 137 S02N<CH3)2 18 C2H5 ~/ '- 174 20 CH3 N(CH3)2 168 22 C2H5 C3H7 ~ . 136 Le A 27 154 - 61 -fable 3~ - continuation Ex. R1 R2 R9 m.p. ( ~C) No.
23 N(CH3)2 C2H5 139 24 N(CH3)2 H 197 25 N(CH3)2 CH(CH3)2 ~ 148 27 OC2H5 C3H7 ~ 155 28 CHICH3)2 186 29 C3H7 ~ 146 30 N ( CH3 ) C3H7 ~ 1-10 Le A 27 154 - 62 -r Table 3: - continuation Ex. R1 R2 ~i3 m~P~
No.
31 N(CH3)2 32 C2H5 C4ti~ ~~ 98 33 CH3 C4H9 ~ 113 34 C3H7 C4H9 ~/ 88 36 OCH3 C4H9 ~ 117 Le A 27 154 - 63 -' CA 02302058 2000-03-29 Table 3: - continuation Ex. R1 R2 g' m.p. ( ~C) No.
41 ~ CH3 42 CH(CH3)Z NHCI~(CH3)2 ~ 135 43 N(CH3)2 N(CH3)2 ~ 171 44 CH3 C3H? ~ 168 CZHS N(CH3)2 ~ 134 46 CH3 CZHS ~ 167 ~e A 27 154 - 64 -Table 3: - continuation Ex. R1 Rz R3 m.p. ( °C) No.
ocF3 47 NH2 C3H' 120 4e -O NH~ 120 50 -CH2CH=CH2 C2H5 108 51 -CH2CH=CH2 H 158 52 OCH3 C3H7 ~ 110 - 111 53 CH2~ H 212 - 214 Le A 27 154 - 65 -Table 3: - continuation EX. R1 R2 R3 m~P~ ('C) No.
55 C3H7 ~ 103 - 105 57 OCH3 C2H5 ~ 111 - 113 59 -~~HCH3 C3H7-n ~ 196 F
6D CH3 C3H7-n ~ 178 61 ~ H ~ 177 Le A 27 154 - 66 -Table 3: - continuation Ex. R' R2 R3 m.p. ( C) No.
62 -CH2CH(CN3) 2 C2H5 ~ 123 63 -CH2-CH=CH2 C3H7-n ~ (amorphous) -t ) 2 ~
65 ~ C2H8 ~ 117 ~
__ 66 -C(CH3)3 C2H5 ~ 182 67 ~ C2H5 , ~ ~ 133 c_ ~ ~
69 -CH2-CH=CH2 CH3 ~ 120 Le A 27 154 - 6? -r' Table 3: - continuation Ex. R1 R2 R3 m.p. ( 'C) No.
COOC1~3 ~ ~
~
73 -OCH3 ~ 138 79 CH(CH3)2 H ~ 191 75 ~ H ~ 191 76 ~ H ~ 192 77 -C(CH3)3 H ~ 211 Le A 27 154 _ 6g -a, Table 3: - continuation EX. R1 R2 R~ m.p. ('C) No.
,, 78 -CH2-iH-CH2Br CH3 ' 110 Br 79 CH3 -CH20CH3 ~ 152 F
80 CH3 C2H5 ~ 174 81 CH3 -CH20C2H5 ~ 123 ~
82 -OCH3 C3H7-n (amorphous) CON(CH3)2 83 C2H5 ' ~ 124 ~ ~
84 -CH20CH3 -~ 102 ~
85 -CH20CH3 ~ 155 Le A 27 154 - 69 -r Table 3: - cor~tinuatfon Ex. R1 R2 R3 m.p. ('C) No.
COOC~3 ~
OC~'3 8? -CH20C2H5 ' 99 88 -N(CH3)2 ~ 189 89 -OCH3 C2H5 ~ 155 9D C2H5 ~ 133 91 -OCH3 C3H7-n ~ 125 ~
92 C2H5 ~ 138 ~
~~
OOCH
S
Le A 27 154 - ?p _ r Table 3: - continuation Ex. R' R2 R3 m.p. ('C) No.
93 -OC2H5 C2H5 \ 132 94 -OC2H5 C3H7-n \ 107 95 -OCN3 CHtCH3)2 ~ 128 97 C3H7-n ~ 100 ~
98 \ 140 ~
99 -N(CH3)2 ~ 163 100 -N(CH3)2 ~ 182 Le A 27 154 _ 71 _ Table 3: - continuation EX. R1 R2 R~ m.p. ( C) No.
101 CH3 -N(CH3)2 1 181 102 CH3 -OCH3 ~ 150 103 C2H5 ~ 197 109 -CH2-CH=CH2 CH3 ~ 132 105 -CH2-CH=CH2 C2H5 ~ 109 106 -CH2-CH=CH2 C3H7-n ~ 104 Le A 27 154 - 72 -Table 3: - continuation EX. R1 RZ R3 m.p. ( C) No.
107 -OC2H5 C2H5 \ 147 108 -OC2H5 C3H~-n \ 136 109 -OCH3 CH(CH3)2 ~ \ 126 Cl 110 CH3 CH3 \ 146 112 CH3 CH(CH3)2 \ 124 Le A 27 159 _ 73 _ Table 3: - continuation EX. R1 RZ Rg m.p. ( °C) No.
113 CH3 ~ 171 114 CN~CN3)2 ~ 132 115 CH3 CH3 ~ ~ 155 117 CH3 C2H5 ~ ~ 197 118 CH3 C3H7-n ~ 169 Le A 27 154 - 74 _ Table 3: - continuation Ex. R1 RZ R3 m.p. ('C) No.
119 OCH3 C2H5 ~
BROOCH
C~ COOCH3 r 1.e A 2? 154 - ?5 -r' ~tartinq substances of the formula (I, example (II-1) O
HN~N~OC2H5 ~2H5 to H-i-CO-NH-OC2H~
(IX-1) A mixture of 6B . 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 theor~,r) of 1-ethoxy-aminocarbonyl-2-propionyl-hydrazine of melting point 122°C.
I,e A 27 154 - 76 -m step 2s O
riN~N~OC2H5 ( I I -1 >
n ''r2H5 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 chloride 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-2,4-dihydro-3H-1,24-triazol-3-one of melting point 93°C.
Example (II-21 HN~N~CH3 (II-2) -"3H7 A mixture of 40 g (0.31 mol) of 5-propyl-1,3,4-Le A 27 154 - 77 -oxadiazolin-2-one, 109 g of aqueous methylamine solution (32 % strength, 1.125 mol of CH3NH2) and 500 ml of water is refluxed for 12 hours and then concentrated. The res idue is taken up in ethanol and ~ reconcentrated . The residue 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.
This gives 31.7 g (72 % of theory) of 4-methyl 5-propyl-2,4-dihydro-3H-1,24-tri~zol-3-one of melting point 86°C.
example (II-31_ O
HN~N~NtCH3)2 ~H
856 g ( 4 . 0 mol ) of Biphenyl carbonate are dis-solved in 588 g of ethylene chloride. 245 g (4.0 mol) of dimethylhydrazine (98 % pure) are added dropwise with 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, far about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during which process ethylene chloride and water are removed (final bottom temperature 100'C). The above phenolic Le A 27 154 - 78 _ r dimethyl carbodihydrazide solution is added dropwise in the course of 90 minutes at reflux temperature (about 102°C) to 424 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has formed is removed by distil-s lation, phenol is distilled off in vacuo, 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 9 below can also be prepared analogously to Examples (II-1) to (II-3).
O
HN~N~R1 (II) N~R 2 Le A 27 154 - 79 -. r Table 4: Preparation example$ of the compounds of the formula (II) Ex. A' R2 m.p. ( C) No.
II-4 C3H7 CH3 _ 48 II-5 CH(CH3)2 CH3 118 II-6 C~13 CH3 139 II-8 ~ C3H7 C2H5 42 - 45 II-9 CHtCH3)2 C~HS 102 II-11 C3H7 C3H7 (amorphous) I1-12 CHtCH3)2 C3H7 91 II-13 CH3 CH(CH3)2 92 II-14 C2H5 CH(CH3)2 (amorphous) II-15 C3H7 ~ CH(CH3)2 (amorphous) II-16 CH(CH3)2 CH(CH3)2 168 Le A 27 154 - 80 -t fable 4 - continuation hx. R' RZ m.p. ( C) No.
II-22 OCH3 GHtCi'13I2 130 II-23 OCl~2C6HS CHI 106 II-27 CN(CH3)2 121 II-29 C2H5 C4Hy 76 II-30 C3H7 C4H9 (amorphous) II-32 CqH9 66 Le A 27 154 _ g1 _ ~~ble 4 - continuation Ex. R1 RZ m.p. ( C) No.
II-37 N(CH3)2 CH3 153 II-38 N(CH3)2 C2H$ 114 II-39 N(CH3)2 C3H7 108 II-40 N(CH3)2 CH(CN3)2 100 II-41 CH3 N(CH3)2 80 II-42 N(CH3)2 134 II-43 CH(CH3)2 NHCH(CH3)2 205 II-44 N(CH3)2 N(CH3)2 93 II-45 C2H5 N(CH3)2 50 II-47 ~ CH3 163 II-53 ' CF3 163 Le A 27 154 - 82 -t, fable 4 - continuation Ex. R' Rz m.p. ('C) Ho.
II-54 NHCH3 CHICH3)2 105 II-55 NHCH3 ~ 95 CZHS i70 II-59 CH2CbH5 C2H5 125 II-61 NHCH3 N(CH3)2 129 ~ 48 II-64 NH2 -iHC2H5 176 II-65 NH2 ~ 183 CF'3 II-68 NH2 N(C2H5)2 196 Le A 27 154 - 83 -,.
Table 4 - continuation EX. R1 #ta m.p. ( C) No.
II-69 NH2 ' .N- 233 II-70 NH2 CN(CH3)2 172 II-?1 NN2 C(CH3)~ 261 I I -72 NH2 CH2CH20C~i3 98 II-73 NH2 C(CH3)2C~H5 213 ~ 2 3 (amorphous) II-76 TiH2 ~ CH~OCH3 134 II-78 N(CH3)2 CH3 153 II-79 -CH2 Cl C2H5 103 Cl I I -80 -CH2Cti ( CH3 ) C2H5 105 II-82 N(CH3)2 CH(CH3)2 (amorphous) II-85 NH2 N(CH3)2 207 Le A 27 154 - 84 -i T b1 - cpntinuation Ex. R' Rz m.p. ( C) No.
II-88 NH2 NHCH(CH3)2 152 II-89 NHCH3 NHCH(CH3)2 120 II-90 ~ NH~ 254 II-91 N(CH3)2 II-94 C6H5 C2H5 , 124 II-95 C(CH3)3 C2H5 158 II-96 CH3 #~ 157 H
C
II-98 ~ C H
II-99 -CH2CH=CH2 CH3 108 II-101 ~ CH3 116 II-102 ~ C2H5 196 II-104 CH(CH3)2 H 105 Le A 27 154 - g5 ' r' Table 4 - continuation Ex. Al Ri m.p. ('C) No.
II-105 ~ H 7g II-106 ~ H 162 II-107 C(CH3)3 H 194 II-108 -CH2-iH-CH28r CH3 111 6 c-I I -1 ---a -CH20C2H5 1 19 II-113 --~ -N(CH3)2 130 ~CH3 'C2H5 ~H3 ~C3H7-n I I -116NH2 -N~ 186 C3H7_n Le A 27 154 _ g6 _ The compound of Example (II-118) disclosed in Table 4 (above) can be prepared as follows;
O
HN~N~CH3 (II-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 .a 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 x of theory) of 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-one as colorless crystals of melting point 144°C.
Le A 27 154 - 8? -i a Examples of hydrazine derivatives of the formula (IX) which can be obtained analogously to Ex-ample (II-1), isted in Table 5 below, step 1, are l ( IX) fable 5: Examples #hydrazinederivatives of the of the fonaula ( IX) EX. R1 Ra m.p. ( C) No.
IX-3 OCH3 C3H? 125 IX-4 OCH3 CH(CH3)2 127 IX-7 C~H~ 180 IX-8 OCZHS C3H~ 119 IX-9 CH(CH3)2 150 Le A 27 154 - 8B -r.
Table - continuation ' Ex. Rl RZ m.p. ('C) No.
IX-12 ' 188 IX-14 CH2-CH=CH2 C3H7 134 Le A 27 154 _ 89 ' . r, ~ta__rti~~ substances of the formula ~IV~s Example ( IV-11 O
-CO~N~N~CHg ~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 80 ml of tetra-s hydrofuran, and 1.B 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 etherr 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).
Le A 27 154 _ g0 -CA 02302058 2000-03-29 '.
.. , s O
Z-CO~N~iRl (IV) R
Table 6: Examples of the compounds of the formula (IV) EX. R1 R2 Z m.p. ('C) No.
IV-2 C3H~ C3H? . C6H5 88 IV-3 OCH3 C3H~ C6H5 82 IV-4 CH3 C3H~ C6H5 84 IV-5 NH2 C3H~ C6H5 133 IV-7 , C2H5 C6H5 152 IV-9 OCH2CH=CH2 CH3 C6H5 IV-li CH3 C6H5 IV-12 NHCH3 C2H5 CbHs Le A 27 154 _ g1 _ c Table - continuation Ex. RI R2 2 m.p. (~C~
No.
IY-13 CH3 CH2C6H5 CbHs I V-14 CH3 NHCH ( Cl~l3 C6H5 ) 2 IY-15 N(CH~)2 N(CH3)~ C6H5 IV-16 C6H~
IV-17 OC2H~ C6H5 IV-18 OC3H7 C2H5 CbHS
IV-20 CH(CH3)2 CHtCH3)2 C6H5 IV-22 C3H7-n C6H8 104 Le A 27 154 _ 92 _ Use Examples:
In the following use examples, the known herbicide isocarbamide, of formula (A) below, is used as comparison substance:
HN~~N-CO-NH-CHZCH(CH3~ ( 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=
~~~ 2 _ O
/ SOZ NH-CO~N~N~CH3 ( 4 ) N--~
'C Hs _ O
SOZ NH-CO~N~N~C2H3 ( 3 ) N--~
~C H
2 s O
SOZ NH CO~N~N'CH3 ( 6 ) I
N--~
~C i 3F ~
SO2 NH CO~N~N~CH3 ( z ) I
CH 3 N--~
~C H
2 s Cl O
~
N~C2H5 (7) 502-NH-CO'N
~C
H
CH3 i Cl O
' t8) ~
~
N
N
~
H
~
N~OCH3 t12) ~S02-NH-CO'N
-'C
H
N
~
NiOCH3 t13) S02-NH-CO'N
H
~3 S02N(CH3)2 O
~
N~CH3 t14) S02-NH-CO'N
~
H
S02N(CH3)2 O
~
N~'CH3 t 15 S02-NH-CO'N ) ~C
H
~
S0 t16) -NH-CO'N~
, H
~
S02-NH-CO'N N~OCH3 (17) ~
HtCH3)2 ..-Le A 27 154 - 94 -S02N(CH3)2 O
(s ,t-S02-NH-CO~N~N~ (18) -"2H5 S02-NH-CO~N~ (19) N'~C 3 H 7 ("j-S02-NH-CO~N~N~CH3 (20) ~N(CH3)2 (A ,j--S02-NH-CO~N~N~OC2H5 ( 26 " -"2H5 ~S02-NH-CO~N~N~OC2H5 (27) -"3H7 ("J--S02-NH-CO~N~N~ ( 28 ~H(CH3)2 S02-NH-CO~N~ (29) CH3 ~3H7 ("j-S02-NH-CO~N~N~'N I CH3 ) 2 ( 30 ) ~3H7 r Le A 7 154 - 95 -,)-S0 -NH-CO~N~N~C
H
(32) ~
S0 CO~N~N~CH
-NH- (33) H
502-NH- CO~N~N~C
H
(34) ' ~
~S0 CO~
-NH- ~
~
N
(35) ~
H
S02-NH- CO~N~N~CH
(37) 502-NH-CO~N~N~C3H7 (39) N
("r-S02-NH-CO~N~ (40) Le A 27 154 - 96 -~SOZ-NH-CO~N~N~OCH~ (9) ~CH 3 .
4 ,?-S02-NH-CO~N N~N(CH3)2 (31) ~J
502-NH-CO~N~N~OCH3 (36) ~4N9 Le A 27 154 - 9~ -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 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, 6, 8, 12, 13, 16, 17, 18, 19, 20, 26, 27, 28, 29, 34, 37, 39 and 40.
Le A 27 154 - 9g -, . ~
~Xample B
Post-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.
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, 18, 19, 20, 26, 27, 28, 29, 30, 32, 33, 34, 35, 37, 39 and 4p.
Le A 27 154 - 99 -,.
Example Pyricularia test (rice) / protective Solvent: 12,5 parts by weight of acetone Emulsifier: 0, 3 parts by weight of alkylarylpolyglycol 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 are 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, 30, 31, 32, 33, 34, 35, 36, 37.
~e A 27 154 - 100 -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 compound. 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 evaluated.
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, 36, 37.
Le A 27 154 - 101 -
Table 3s - continuation EX. R1 R2 A9 m.p. ( °C) No.
c1 8 CH3- C3H~ ~ 141 Sb2N(CH3)2 11 OCH3 CH3 ~ 149 12 OCH3 C2H5 ~ 144 13 OCH3 C3H7 ~ 128 SOZN(CH3)2 14 CH3 C2H5 ~ 173 Le A 27 154 - 60 -z Table 3: - continuatiop EX. R1 Ra ~t9 m.p. ( °C) No.
SO~N(CH3)2 15 CH3 C3H7 ~ 133 CooCH~
16 C2H5 ~" 154 17 OCH3 CH(CH3)2 ~ 137 S02N<CH3)2 18 C2H5 ~/ '- 174 20 CH3 N(CH3)2 168 22 C2H5 C3H7 ~ . 136 Le A 27 154 - 61 -fable 3~ - continuation Ex. R1 R2 R9 m.p. ( ~C) No.
23 N(CH3)2 C2H5 139 24 N(CH3)2 H 197 25 N(CH3)2 CH(CH3)2 ~ 148 27 OC2H5 C3H7 ~ 155 28 CHICH3)2 186 29 C3H7 ~ 146 30 N ( CH3 ) C3H7 ~ 1-10 Le A 27 154 - 62 -r Table 3: - continuation Ex. R1 R2 ~i3 m~P~
No.
31 N(CH3)2 32 C2H5 C4ti~ ~~ 98 33 CH3 C4H9 ~ 113 34 C3H7 C4H9 ~/ 88 36 OCH3 C4H9 ~ 117 Le A 27 154 - 63 -' CA 02302058 2000-03-29 Table 3: - continuation Ex. R1 R2 g' m.p. ( ~C) No.
41 ~ CH3 42 CH(CH3)Z NHCI~(CH3)2 ~ 135 43 N(CH3)2 N(CH3)2 ~ 171 44 CH3 C3H? ~ 168 CZHS N(CH3)2 ~ 134 46 CH3 CZHS ~ 167 ~e A 27 154 - 64 -Table 3: - continuation Ex. R1 Rz R3 m.p. ( °C) No.
ocF3 47 NH2 C3H' 120 4e -O NH~ 120 50 -CH2CH=CH2 C2H5 108 51 -CH2CH=CH2 H 158 52 OCH3 C3H7 ~ 110 - 111 53 CH2~ H 212 - 214 Le A 27 154 - 65 -Table 3: - continuation EX. R1 R2 R3 m~P~ ('C) No.
55 C3H7 ~ 103 - 105 57 OCH3 C2H5 ~ 111 - 113 59 -~~HCH3 C3H7-n ~ 196 F
6D CH3 C3H7-n ~ 178 61 ~ H ~ 177 Le A 27 154 - 66 -Table 3: - continuation Ex. R' R2 R3 m.p. ( C) No.
62 -CH2CH(CN3) 2 C2H5 ~ 123 63 -CH2-CH=CH2 C3H7-n ~ (amorphous) -t ) 2 ~
65 ~ C2H8 ~ 117 ~
__ 66 -C(CH3)3 C2H5 ~ 182 67 ~ C2H5 , ~ ~ 133 c_ ~ ~
69 -CH2-CH=CH2 CH3 ~ 120 Le A 27 154 - 6? -r' Table 3: - continuation Ex. R1 R2 R3 m.p. ( 'C) No.
COOC1~3 ~ ~
~
73 -OCH3 ~ 138 79 CH(CH3)2 H ~ 191 75 ~ H ~ 191 76 ~ H ~ 192 77 -C(CH3)3 H ~ 211 Le A 27 154 _ 6g -a, Table 3: - continuation EX. R1 R2 R~ m.p. ('C) No.
,, 78 -CH2-iH-CH2Br CH3 ' 110 Br 79 CH3 -CH20CH3 ~ 152 F
80 CH3 C2H5 ~ 174 81 CH3 -CH20C2H5 ~ 123 ~
82 -OCH3 C3H7-n (amorphous) CON(CH3)2 83 C2H5 ' ~ 124 ~ ~
84 -CH20CH3 -~ 102 ~
85 -CH20CH3 ~ 155 Le A 27 154 - 69 -r Table 3: - cor~tinuatfon Ex. R1 R2 R3 m.p. ('C) No.
COOC~3 ~
OC~'3 8? -CH20C2H5 ' 99 88 -N(CH3)2 ~ 189 89 -OCH3 C2H5 ~ 155 9D C2H5 ~ 133 91 -OCH3 C3H7-n ~ 125 ~
92 C2H5 ~ 138 ~
~~
OOCH
S
Le A 27 154 - ?p _ r Table 3: - continuation Ex. R' R2 R3 m.p. ('C) No.
93 -OC2H5 C2H5 \ 132 94 -OC2H5 C3H7-n \ 107 95 -OCN3 CHtCH3)2 ~ 128 97 C3H7-n ~ 100 ~
98 \ 140 ~
99 -N(CH3)2 ~ 163 100 -N(CH3)2 ~ 182 Le A 27 154 _ 71 _ Table 3: - continuation EX. R1 R2 R~ m.p. ( C) No.
101 CH3 -N(CH3)2 1 181 102 CH3 -OCH3 ~ 150 103 C2H5 ~ 197 109 -CH2-CH=CH2 CH3 ~ 132 105 -CH2-CH=CH2 C2H5 ~ 109 106 -CH2-CH=CH2 C3H7-n ~ 104 Le A 27 154 - 72 -Table 3: - continuation EX. R1 RZ R3 m.p. ( C) No.
107 -OC2H5 C2H5 \ 147 108 -OC2H5 C3H~-n \ 136 109 -OCH3 CH(CH3)2 ~ \ 126 Cl 110 CH3 CH3 \ 146 112 CH3 CH(CH3)2 \ 124 Le A 27 159 _ 73 _ Table 3: - continuation EX. R1 RZ Rg m.p. ( °C) No.
113 CH3 ~ 171 114 CN~CN3)2 ~ 132 115 CH3 CH3 ~ ~ 155 117 CH3 C2H5 ~ ~ 197 118 CH3 C3H7-n ~ 169 Le A 27 154 - 74 _ Table 3: - continuation Ex. R1 RZ R3 m.p. ('C) No.
119 OCH3 C2H5 ~
BROOCH
C~ COOCH3 r 1.e A 2? 154 - ?5 -r' ~tartinq substances of the formula (I, example (II-1) O
HN~N~OC2H5 ~2H5 to H-i-CO-NH-OC2H~
(IX-1) A mixture of 6B . 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 theor~,r) of 1-ethoxy-aminocarbonyl-2-propionyl-hydrazine of melting point 122°C.
I,e A 27 154 - 76 -m step 2s O
riN~N~OC2H5 ( I I -1 >
n ''r2H5 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 chloride 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-2,4-dihydro-3H-1,24-triazol-3-one of melting point 93°C.
Example (II-21 HN~N~CH3 (II-2) -"3H7 A mixture of 40 g (0.31 mol) of 5-propyl-1,3,4-Le A 27 154 - 77 -oxadiazolin-2-one, 109 g of aqueous methylamine solution (32 % strength, 1.125 mol of CH3NH2) and 500 ml of water is refluxed for 12 hours and then concentrated. The res idue is taken up in ethanol and ~ reconcentrated . The residue 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.
This gives 31.7 g (72 % of theory) of 4-methyl 5-propyl-2,4-dihydro-3H-1,24-tri~zol-3-one of melting point 86°C.
example (II-31_ O
HN~N~NtCH3)2 ~H
856 g ( 4 . 0 mol ) of Biphenyl carbonate are dis-solved in 588 g of ethylene chloride. 245 g (4.0 mol) of dimethylhydrazine (98 % pure) are added dropwise with 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, far about 1 hour, stirring is continued.
When cold, the solution is distilled in vacuo, during which process ethylene chloride and water are removed (final bottom temperature 100'C). The above phenolic Le A 27 154 - 78 _ r dimethyl carbodihydrazide solution is added dropwise in the course of 90 minutes at reflux temperature (about 102°C) to 424 g (4.0 mol) of trimethyl orthoformate.
After the methanol which has formed is removed by distil-s lation, phenol is distilled off in vacuo, 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 9 below can also be prepared analogously to Examples (II-1) to (II-3).
O
HN~N~R1 (II) N~R 2 Le A 27 154 - 79 -. r Table 4: Preparation example$ of the compounds of the formula (II) Ex. A' R2 m.p. ( C) No.
II-4 C3H7 CH3 _ 48 II-5 CH(CH3)2 CH3 118 II-6 C~13 CH3 139 II-8 ~ C3H7 C2H5 42 - 45 II-9 CHtCH3)2 C~HS 102 II-11 C3H7 C3H7 (amorphous) I1-12 CHtCH3)2 C3H7 91 II-13 CH3 CH(CH3)2 92 II-14 C2H5 CH(CH3)2 (amorphous) II-15 C3H7 ~ CH(CH3)2 (amorphous) II-16 CH(CH3)2 CH(CH3)2 168 Le A 27 154 - 80 -t fable 4 - continuation hx. R' RZ m.p. ( C) No.
II-22 OCH3 GHtCi'13I2 130 II-23 OCl~2C6HS CHI 106 II-27 CN(CH3)2 121 II-29 C2H5 C4Hy 76 II-30 C3H7 C4H9 (amorphous) II-32 CqH9 66 Le A 27 154 _ g1 _ ~~ble 4 - continuation Ex. R1 RZ m.p. ( C) No.
II-37 N(CH3)2 CH3 153 II-38 N(CH3)2 C2H$ 114 II-39 N(CH3)2 C3H7 108 II-40 N(CH3)2 CH(CN3)2 100 II-41 CH3 N(CH3)2 80 II-42 N(CH3)2 134 II-43 CH(CH3)2 NHCH(CH3)2 205 II-44 N(CH3)2 N(CH3)2 93 II-45 C2H5 N(CH3)2 50 II-47 ~ CH3 163 II-53 ' CF3 163 Le A 27 154 - 82 -t, fable 4 - continuation Ex. R' Rz m.p. ('C) Ho.
II-54 NHCH3 CHICH3)2 105 II-55 NHCH3 ~ 95 CZHS i70 II-59 CH2CbH5 C2H5 125 II-61 NHCH3 N(CH3)2 129 ~ 48 II-64 NH2 -iHC2H5 176 II-65 NH2 ~ 183 CF'3 II-68 NH2 N(C2H5)2 196 Le A 27 154 - 83 -,.
Table 4 - continuation EX. R1 #ta m.p. ( C) No.
II-69 NH2 ' .N- 233 II-70 NH2 CN(CH3)2 172 II-?1 NN2 C(CH3)~ 261 I I -72 NH2 CH2CH20C~i3 98 II-73 NH2 C(CH3)2C~H5 213 ~ 2 3 (amorphous) II-76 TiH2 ~ CH~OCH3 134 II-78 N(CH3)2 CH3 153 II-79 -CH2 Cl C2H5 103 Cl I I -80 -CH2Cti ( CH3 ) C2H5 105 II-82 N(CH3)2 CH(CH3)2 (amorphous) II-85 NH2 N(CH3)2 207 Le A 27 154 - 84 -i T b1 - cpntinuation Ex. R' Rz m.p. ( C) No.
II-88 NH2 NHCH(CH3)2 152 II-89 NHCH3 NHCH(CH3)2 120 II-90 ~ NH~ 254 II-91 N(CH3)2 II-94 C6H5 C2H5 , 124 II-95 C(CH3)3 C2H5 158 II-96 CH3 #~ 157 H
C
II-98 ~ C H
II-99 -CH2CH=CH2 CH3 108 II-101 ~ CH3 116 II-102 ~ C2H5 196 II-104 CH(CH3)2 H 105 Le A 27 154 - g5 ' r' Table 4 - continuation Ex. Al Ri m.p. ('C) No.
II-105 ~ H 7g II-106 ~ H 162 II-107 C(CH3)3 H 194 II-108 -CH2-iH-CH28r CH3 111 6 c-I I -1 ---a -CH20C2H5 1 19 II-113 --~ -N(CH3)2 130 ~CH3 'C2H5 ~H3 ~C3H7-n I I -116NH2 -N~ 186 C3H7_n Le A 27 154 _ g6 _ The compound of Example (II-118) disclosed in Table 4 (above) can be prepared as follows;
O
HN~N~CH3 (II-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 .a 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 x of theory) of 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-one as colorless crystals of melting point 144°C.
Le A 27 154 - 8? -i a Examples of hydrazine derivatives of the formula (IX) which can be obtained analogously to Ex-ample (II-1), isted in Table 5 below, step 1, are l ( IX) fable 5: Examples #hydrazinederivatives of the of the fonaula ( IX) EX. R1 Ra m.p. ( C) No.
IX-3 OCH3 C3H? 125 IX-4 OCH3 CH(CH3)2 127 IX-7 C~H~ 180 IX-8 OCZHS C3H~ 119 IX-9 CH(CH3)2 150 Le A 27 154 - 8B -r.
Table - continuation ' Ex. Rl RZ m.p. ('C) No.
IX-12 ' 188 IX-14 CH2-CH=CH2 C3H7 134 Le A 27 154 _ 89 ' . r, ~ta__rti~~ substances of the formula ~IV~s Example ( IV-11 O
-CO~N~N~CHg ~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 80 ml of tetra-s hydrofuran, and 1.B 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 etherr 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).
Le A 27 154 _ g0 -CA 02302058 2000-03-29 '.
.. , s O
Z-CO~N~iRl (IV) R
Table 6: Examples of the compounds of the formula (IV) EX. R1 R2 Z m.p. ('C) No.
IV-2 C3H~ C3H? . C6H5 88 IV-3 OCH3 C3H~ C6H5 82 IV-4 CH3 C3H~ C6H5 84 IV-5 NH2 C3H~ C6H5 133 IV-7 , C2H5 C6H5 152 IV-9 OCH2CH=CH2 CH3 C6H5 IV-li CH3 C6H5 IV-12 NHCH3 C2H5 CbHs Le A 27 154 _ g1 _ c Table - continuation Ex. RI R2 2 m.p. (~C~
No.
IY-13 CH3 CH2C6H5 CbHs I V-14 CH3 NHCH ( Cl~l3 C6H5 ) 2 IY-15 N(CH~)2 N(CH3)~ C6H5 IV-16 C6H~
IV-17 OC2H~ C6H5 IV-18 OC3H7 C2H5 CbHS
IV-20 CH(CH3)2 CHtCH3)2 C6H5 IV-22 C3H7-n C6H8 104 Le A 27 154 _ 92 _ Use Examples:
In the following use examples, the known herbicide isocarbamide, of formula (A) below, is used as comparison substance:
HN~~N-CO-NH-CHZCH(CH3~ ( 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=
~~~ 2 _ O
/ SOZ NH-CO~N~N~CH3 ( 4 ) N--~
'C Hs _ O
SOZ NH-CO~N~N~C2H3 ( 3 ) N--~
~C H
2 s O
SOZ NH CO~N~N'CH3 ( 6 ) I
N--~
~C i 3F ~
SO2 NH CO~N~N~CH3 ( z ) I
CH 3 N--~
~C H
2 s Cl O
~
N~C2H5 (7) 502-NH-CO'N
~C
H
CH3 i Cl O
' t8) ~
~
N
N
~
H
~
N~OCH3 t12) ~S02-NH-CO'N
-'C
H
N
~
NiOCH3 t13) S02-NH-CO'N
H
~3 S02N(CH3)2 O
~
N~CH3 t14) S02-NH-CO'N
~
H
S02N(CH3)2 O
~
N~'CH3 t 15 S02-NH-CO'N ) ~C
H
~
S0 t16) -NH-CO'N~
, H
~
S02-NH-CO'N N~OCH3 (17) ~
HtCH3)2 ..-Le A 27 154 - 94 -S02N(CH3)2 O
(s ,t-S02-NH-CO~N~N~ (18) -"2H5 S02-NH-CO~N~ (19) N'~C 3 H 7 ("j-S02-NH-CO~N~N~CH3 (20) ~N(CH3)2 (A ,j--S02-NH-CO~N~N~OC2H5 ( 26 " -"2H5 ~S02-NH-CO~N~N~OC2H5 (27) -"3H7 ("J--S02-NH-CO~N~N~ ( 28 ~H(CH3)2 S02-NH-CO~N~ (29) CH3 ~3H7 ("j-S02-NH-CO~N~N~'N I CH3 ) 2 ( 30 ) ~3H7 r Le A 7 154 - 95 -,)-S0 -NH-CO~N~N~C
H
(32) ~
S0 CO~N~N~CH
-NH- (33) H
502-NH- CO~N~N~C
H
(34) ' ~
~S0 CO~
-NH- ~
~
N
(35) ~
H
S02-NH- CO~N~N~CH
(37) 502-NH-CO~N~N~C3H7 (39) N
("r-S02-NH-CO~N~ (40) Le A 27 154 - 96 -~SOZ-NH-CO~N~N~OCH~ (9) ~CH 3 .
4 ,?-S02-NH-CO~N N~N(CH3)2 (31) ~J
502-NH-CO~N~N~OCH3 (36) ~4N9 Le A 27 154 - 9~ -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 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, 6, 8, 12, 13, 16, 17, 18, 19, 20, 26, 27, 28, 29, 34, 37, 39 and 40.
Le A 27 154 - 9g -, . ~
~Xample B
Post-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.
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, 18, 19, 20, 26, 27, 28, 29, 30, 32, 33, 34, 35, 37, 39 and 4p.
Le A 27 154 - 99 -,.
Example Pyricularia test (rice) / protective Solvent: 12,5 parts by weight of acetone Emulsifier: 0, 3 parts by weight of alkylarylpolyglycol 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 are 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, 30, 31, 32, 33, 34, 35, 36, 37.
~e A 27 154 - 100 -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 compound. 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 evaluated.
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, 36, 37.
Le A 27 154 - 101 -
Claims
1. A process ion preparing 5-methoxy-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of the formula (II-118) which process comprises reacting hydrazino-formic acid phenyl ester with an about equimolar amount of O,N,N-trimethylimino-carbonate at elevated temperature in the presence of a diluent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002420329A CA2420329C (en) | 1989-10-12 | 1990-10-10 | Sulphonylaminocarbonyltriazolinones |
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 | ||
| CA002189698A CA2189698C (en) | 1989-10-12 | 1990-10-10 | Substituted 1,2,3-triazol-3-ones |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002189698A Division CA2189698C (en) | 1989-10-12 | 1990-10-10 | Substituted 1,2,3-triazol-3-ones |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002420329A Division CA2420329C (en) | 1989-10-12 | 1990-10-10 | Sulphonylaminocarbonyltriazolinones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2302058A1 CA2302058A1 (en) | 1991-04-13 |
| CA2302058C true CA2302058C (en) | 2004-05-25 |
Family
ID=6391328
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
| 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 |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002027206A Expired - Lifetime CA2027206C (en) | 1989-10-12 | 1990-10-10 | Sulphonylaminocarbonyltriazolinones |
Country Status (13)
| Country | Link |
|---|---|
| EP (2) | EP0422469B1 (en) |
| JP (1) | JPH03133966A (en) |
| KR (1) | KR0171400B1 (en) |
| AU (1) | AU627080B2 (en) |
| BR (1) | BR9005095A (en) |
| CA (4) | CA2189698C (en) |
| CZ (1) | CZ281525B6 (en) |
| DE (3) | DE3934081A1 (en) |
| DK (2) | DK0422469T3 (en) |
| ES (2) | ES2087107T3 (en) |
| HU (1) | HU218976B (en) |
| PL (1) | PL165494B1 (en) |
| SK (1) | SK280209B6 (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 |
| 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 |
| DE4131842A1 (en) * | 1991-09-25 | 1993-04-01 | Bayer Ag | SULFONYLAMINOCARBONYLTRIAZOLINONE WITH TWO OXYGEN SUBSTITUTES |
| 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 |
| 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 |
| DE19845408A1 (en) * | 1998-10-02 | 2000-04-27 | Bayer Ag | 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 |
| EP2822931B1 (en) | 2012-03-09 | 2017-05-03 | Inception 2, Inc. | Triazolone compounds and uses thereof |
| US9676754B2 (en) | 2012-12-20 | 2017-06-13 | Inception 2, Inc. | Triazolone compounds and uses thereof |
| BR112015031291A2 (en) | 2013-06-20 | 2017-07-25 | Bayer Cropscience Ag | aryl sulfide derivatives and arylalkyl sulfoxide derivatives as acaricides and insecticides |
| CA2921420A1 (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 |
| 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 |
| DE3709574A1 (en) * | 1987-03-24 | 1988-10-06 | Bayer Ag | SUBSTITUTED TRIAZOLINONES |
| EP0332133B1 (en) * | 1988-03-07 | 1994-08-24 | Chugai Seiyaku Kabushiki Kaisha | Novel triazole compounds, process for producing the same, and herbicidal compositions containing the same |
-
1989
- 1989-10-12 DE DE3934081A patent/DE3934081A1/en not_active Withdrawn
-
1990
- 1990-09-29 EP EP90118750A patent/EP0422469B1/en not_active Expired - Lifetime
- 1990-09-29 DK DK90118750.0T patent/DK0422469T3/en active
- 1990-09-29 DE DE59010314T patent/DE59010314D1/en not_active Expired - Lifetime
- 1990-09-29 DE DE59010938T patent/DE59010938D1/en not_active Expired - Lifetime
- 1990-09-29 ES ES90118750T patent/ES2087107T3/en not_active Expired - Lifetime
- 1990-09-29 DK DK95111736T patent/DK0683157T3/en active
- 1990-09-29 ES ES95111736T patent/ES2222457T3/en not_active Expired - Lifetime
- 1990-09-29 EP EP95111736A patent/EP0683157B1/en not_active Expired - Lifetime
- 1990-10-09 JP JP2269742A patent/JPH03133966A/en active Pending
- 1990-10-10 PL PL90287259A patent/PL165494B1/en unknown
- 1990-10-10 CA CA002189698A patent/CA2189698C/en not_active Expired - Lifetime
- 1990-10-10 CA CA002420329A patent/CA2420329C/en not_active Expired - Lifetime
- 1990-10-10 CA CA002302058A patent/CA2302058C/en not_active Expired - Lifetime
- 1990-10-10 CA CA002027206A patent/CA2027206C/en not_active Expired - Lifetime
- 1990-10-11 KR KR1019900016081A patent/KR0171400B1/en not_active IP Right Cessation
- 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/SK280209B6/en not_active IP Right Cessation
- 1990-10-11 HU HU419/90A patent/HU218976B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2189698C (en) | 2003-05-06 |
| CA2420329A1 (en) | 1991-04-13 |
| CA2027206A1 (en) | 1991-04-13 |
| SK495090A3 (en) | 1999-09-10 |
| PL165494B1 (en) | 1994-12-30 |
| DE3934081A1 (en) | 1991-04-18 |
| EP0683157B1 (en) | 2004-05-26 |
| AU627080B2 (en) | 1992-08-13 |
| SK280209B6 (en) | 1999-09-10 |
| CA2027206C (en) | 1997-12-23 |
| CZ281525B6 (en) | 1996-10-16 |
| AU6459190A (en) | 1991-04-18 |
| KR0171400B1 (en) | 1999-02-01 |
| ES2087107T3 (en) | 1996-07-16 |
| HU218976B (en) | 2001-01-29 |
| HU906419D0 (en) | 1991-04-29 |
| JPH03133966A (en) | 1991-06-07 |
| DE59010314D1 (en) | 1996-06-13 |
| PL287259A1 (en) | 1992-01-27 |
| CA2302058A1 (en) | 1991-04-13 |
| DE59010938D1 (en) | 2004-07-01 |
| CA2189698A1 (en) | 1991-04-13 |
| EP0683157A1 (en) | 1995-11-22 |
| CZ495090A3 (en) | 1996-07-17 |
| HUT55369A (en) | 1991-05-28 |
| ES2222457T3 (en) | 2005-02-01 |
| KR910007893A (en) | 1991-05-30 |
| CA2420329C (en) | 2005-11-29 |
| DK0683157T3 (en) | 2004-09-27 |
| EP0422469A2 (en) | 1991-04-17 |
| EP0422469B1 (en) | 1996-05-08 |
| BR9005095A (en) | 1991-09-17 |
| EP0422469A3 (en) | 1992-01-08 |
| DK0422469T3 (en) | 1996-08-26 |
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