CA2032398A1 - Process for preparing sulphonylurea salts, new sulphonylurea salts, and their use as herbicides - Google Patents
Process for preparing sulphonylurea salts, new sulphonylurea salts, and their use as herbicidesInfo
- Publication number
- CA2032398A1 CA2032398A1 CA002032398A CA2032398A CA2032398A1 CA 2032398 A1 CA2032398 A1 CA 2032398A1 CA 002032398 A CA002032398 A CA 002032398A CA 2032398 A CA2032398 A CA 2032398A CA 2032398 A1 CA2032398 A1 CA 2032398A1
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- CA
- Canada
- Prior art keywords
- alkyl
- methyl
- ethyl
- methoxy
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
-
- 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<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Abstract
Abstract A process for preparing a sulphonylurea salt of the formula (I) in which M? represents an alkali metal ion or the counterion, formed by protonation, of a basic organic nitrogen compound, R represents halogenoalkyl, R1 represents optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl ox aral-kyl, R2 represents hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkyl-thio, amino, alkylamino or dialkylamino, X represents nitrogen or a -CH group, Y represents nitrogen or a -CR3 group where R3 represents hydrogen, halogen, cyano, alkyl, formyl, alkyl-carbonyl or alkoxy-carbonyl, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, which comprises reacting a sulphonylurea of the formula (II) Le A 27 329 Abstract (continued) with an alkali metal hydroxide or with a basic organic nitrogen compound in the presence of a hydrocarbon as diluent at a temperature from about 0 to 100°C.
Compounds wherein Y is nitrogen are new herbicides.
Le A 27 329
Compounds wherein Y is nitrogen are new herbicides.
Le A 27 329
Description
2 ~
The invention relates 1o a new process for preparing sulphonylurea salts, to new sulphonylurea salts and to their use as herbicides.
It is known that sulphonylurea salts are obtained when solutions of sulphonylureas in halogenohydrocarbon solvents are reacted with alkali metal hydroxides or alkaline earth metal hydroxides and the solvent is dis-tilled off, if appropriate, after filtration (cf. EP-A
304,382).
Since in this procedure the product generally does not crystallize from the solution, it is necPssary for the solvent to be distilled, which requires large amounts of energy, and the chances of obtaining a purifi-cation effect are low.
The invention relates 1o a new process for preparing sulphonylurea salts, to new sulphonylurea salts and to their use as herbicides.
It is known that sulphonylurea salts are obtained when solutions of sulphonylureas in halogenohydrocarbon solvents are reacted with alkali metal hydroxides or alkaline earth metal hydroxides and the solvent is dis-tilled off, if appropriate, after filtration (cf. EP-A
304,382).
Since in this procedure the product generally does not crystallize from the solution, it is necPssary for the solvent to be distilled, which requires large amounts of energy, and the chances of obtaining a purifi-cation effect are low.
3-Substituted-1-(2-halogenoalkoxy-benzene-sulphonyl)-3-heteroaryl-(thio)ureas are known as herbi-cides (cf. EP-A 251,079). However, in aqueous medium, these compounds are suhject to relatively rapid hydroly-tic degradation. It has not yet been possible to prepare salts of these compounds, which should be more stable, of sufficient quality.
A process has now been found for preparing sulphonylurea salts of the general formula (I) N--Z~
~S02-N-CO-N~ `Y ( I ) Le A 27 329 - 1 -2 ~ ~, 2 ~ 3 in which M~ represents an ~lkali metal ion or the counterion, formed by protonation, of a basic organic nitrogen compound, R represents halogenoalkyl, R1 represents optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl or aral-kyl, RZ represents hydrogen, halogen, alkyl, halogenoalkyl, 10alkoxy, halogenoalkoxy, alkylthio, halogenoalkyl-thio, amino, alkylamino or dialkylamino, X represents nitrogen or a -CH group, Y represents nitrogen or a -CR3 group where R3 represents hydrogen, halogen, cyano, alkyl, 15formyl, alkyl-carbonyl or alkoxy carbonyl, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, which is characterized in that sulphonylureas of the general formula (II) ~ SO2-NH-CO-N ~ ~ (II) in which R, R1, R2, X, Y and Z have the abovementioned meanings Le A 27 329 - 2 -are reacted with alkali metal hy~droxides or wl~t~ bas organic nitrogen compounds in the presence of hydro-carbons as diluents at temperatures between 0C and 100C, and the products which are obtained in crystalline form in this procefis are isolatedl by customary methods.
Furthermore, it has been found that the sul-phonylurea salts of the formula (:[) to be prepared by the process according to the invention are distinguished by a powerful herbicidal activity.
The sulphonylurea salts of the formula (I) in which Y represents nitrogen, to be prepared by the process according to the invention, are new and, as new substances, likewise a subject of the present invention.
It is to be regarded as surprising that the sulphonylurea salts of the formula (I) are obtained by the process according to the invention in a very simple manner in very good yields and in high purity, since a smooth reaction of the polar reaction components in hydrocarbons as non-polar solvents was not to be expected.
As comparison experiments have shown addition-ally, an analogous reaction in polar solvents results in the formation of a more or less large proportion of degradation products which virtually do not occur in the reaction of the process according to the invention.
Compared with the corresponding ~free~ sulphonyl-ureas, the new sulphonylurea salts show, in particular, the advantageous property of considerably more stable storage and use forms (formulations and spray liquors).
The process according to the invention preferably Le A 27_329 - 3 -rel~tes to preparing sulphonylurea salts and - if Y
represents nitrogen ~ new sulphonylurea salts of the formula (I) in which M~ represents a lithium, sodium or potassium ion, a tri-(Cl-C4-alkyl)-ammonium ion, a N-(C3-C6-cyclo-alkyl)-NlN-di-(Cl-C4-alkyl)-ammonium ion or in each case the counterion, formed by protonation, of N-(Cl-C4-alkyl)-pyrrolidine, N-(Cl-C4-alXyl)-piperidine, N-(Cl-C4-alkyl)-morpholine, N,N'-di-(Cl-C4-alkyl)-piperazine, N,N-di-(C1-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBM), 1,8-diazabi-cyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-[2.2.2]-octane [DABCO], R represents halogeno-Cl-C4-alkyl, R1 represents Cl-C6-alkyl (which is optionally substi-tuted by fluorine, cyano, C1-C4-alkoxy or C1-C4-alkylthio), or represents C3-C6-alkenyl and C3-C6-alkinyl twhich are optionally substituted by fluor-ine or chlorine), or represents phenyl-C1-C2-alkyl (which is optionally substituted in the phenyl moiety by fluorine, chlorine, nitro, cyano, methyl, methoxy or C1-C2-alkoxycarbonyl), R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethyl-amino, represents nitrogen or a -CH group, ~ represents nitrogen or a -CR3 group where 3C R3 represents hydrogen, fluorine, chlorine, Le A 27 329 - 4 -f~ 3 ~ 3 ~
bromine, methyl, formyl, acetyl, methoxy-carbonyl or ethoxycarbonyl, and Z represen~s nitrogen or a -C~4 group where R4 xepresents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino, dime~hylamino or diethylamino.
In particular, the process according to the invention relates to preparin~ sulphonylurea salts and -if Y represents nitrog~n - new sulphonylurea salts of the formula (I) in which N~ represents a sodium ion or a potassium ion, or represents a trimethyl-, triethyl-, tripropyl- or tributylammonium ion, or a N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclopentyl = onium ion, a N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclo-hexylammonium ion, or in each case the counterion, formed by protonation, of N-methyl-, N-ethyl- or N-propyl-pyrrolidine, N-methyl-, N-ethyl- or N-propyl-piperidine, N-methyl-, N-ethyl- or N-propyl-morpholine, N,N'-dimethyl-, N,N'-diethyl- or N,N'-dipropyl-piperazine, N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-~2.2.2]-octane (DABC0), 30 R represents difluoromethyl or trifluoromethyl, Le A 27 329 _ 5 _ ~t~32~ ~
Rl represents methyl, R2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen, Y represents nitrogen or a CH group ~very particularly preferably nitrogen), and Z represents a C-R4 group where R4 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl,methoxy, etho~y, difluorometh-oxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
If, for example, 3-(4,6-dimethoxy-pyrimidin-2-yl)-3-methyl-1-(2-difluoromethoxy-phenylsulphonyl)-urea and trimethylamine are used as starting substances, the course of the reaction in the process according to the invention can be outlined by the following equation:
SO2-NH-CO-N ~ ~ I N(CH3)3 (for example OCHF2 fH3 OCH3 - ~ 02-N-CO-N--~
toluene) N
HN( CH3)3 OCH3 Le A 27 329- 6 -2~32~8 Formula (II) provides a general definition of the sulphonylureas to be used as starting substances in the process according to the invent:ion for preparing com-pounds of the formula (I)~
In formula (II), R, R1, R2, X, Y and Z preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) accord.ing to the invention as being preferred, or particularly preferred, for R, R1, R2, X, Y and Z.
Examples of the starting substances of the formula (II) are listed in Table 1 below.
~ SO2-NH-CO-N ~ ~ (II) Table 1: Examples of the starting substances of the formula (II) R Rl R2 X Y Z
. .
CF3 . CH3 OCH3 N CH C-OCH3 CF3 CH~ CH3 N N C-OCH3 CF3 CH3 C2H5 N CH C-OCH~
CHF2 CH3 OCH3 N CH C-Cl Le A 27 329 _ 7 _ ~JI~L~L~.J~
Table 1 - continuation CF3 ~H3 CH3 N N 5-CH3 ~e A 27 329 - 8 2~
The starting substances of ~he formula (II) are known and/or can be prepared by processes knvwn per se (cf. EP-A 251,079).
The process according to the invention is carried out using alkali metal hydroxides or basic organic nitrogen compounds. Preferred substances are lithium hydroxide, sodium hydroxide and potassium hydroxide, tri-(C~-C4-alkyl)-amine, N-(C3-C6-cycloalkyl)-N,N-di-(Cl-C4-alkyl)-amine, N-(Cl-C4-alkyl)-pyrrolidine, N-(Cl-C4-alkyl)-piperidine, N-(Cl-C4-alkyl)-morpholine, N,N'-di-(Cl-C4-alkyl)-piperazine, N,N-di-(C1-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabi-cyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).
Particularly preferred substances are sodium hydroxide and potassium hydroxide, trimethyl-, triethyl-, txipropyl- and tributylamine, N,N-dimethyl-,N,N-diethyl-and N,N-dipropyl-cyclopentylamine, N,N-dimethyl-, N,N-diethyl- and N,N-dipropyl-cyclohexylamine, N-methyl-l N-ethyl- and N-propyl-pyrrolidine, N-methyl-, N-ethyl- and N-propyl-piperidine, N-methyl-, N-ethyl- and N-propyl-morpholine, N,N'-dimethyl-, N,N'-diethyl- and N,N'~
dipropyl-piperazine, N,N-dimethyl-, N,N-diethyl- and N,N-dipropyl-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).
The process accordiny to the invention is carried out in the presence of hydrocarbons as diluents. Diluents which are preferred in the process according to the invention are aromatic, in particular benzoidal Le A 27 329 - 9 -3 2 ~
hydrocarbons, which contain, if appropriate, 1 to 3 alkyl substituents, each of which has 1 to 3 carbon atoms.
Examples of these which may be mentioned are: benzene, toluene, o-, m- and p-xylene, ethylbenzene, propyl-benzene, cumene, 1,2,3-trLmethylbenzene, 1,2,4-trLmethyl-ben~ene and I,3,5-trimethylbenzlene. Toluene is very particularly preferred as a diluent in the process according to the invention.
In the process according to the invention, the reaction temperatures can be varied within a substantial range7 In general, the process is carried out at tempera-~ures between 0C and 100C, preferably at temperatures between 10C and 50C.
In general, the process according to the inven-tion is carried out under atmospheric pre sure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out the process according to the invention, between 0.9 and 1.5 moles, preferably between 1.0 and 1.3 moles, of an alkali metal hydroxide or a basic organic nitrogen compound are generally employed per mole of sulphonylurea of the formula (I).
The reactants can be combined in any desired sequence. In a preferred embodiment of the process according to the invention, the sulphonylurea of the formula (I) is first stirred with the hydrocarbon diluent, and an alkali metal hydroxide or a basic organic nitrogen compound is then added. The reaction mixture is stirred until crystallization of the product is virtually complete; the product is subsequently isolated by Le A 27 329 - 10 -~,~332~
filtration with suction.
The active compounds of the formula (I) 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 ~he substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the follow-ing plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, ~rtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsiu~, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the aenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, FLmbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Le A 27 329 - 11 -J ~ 9~
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 accord-ing to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the 10 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, 15 decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee planta-tions, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop-fields, on lawn, turf and pasture-land, and for the 20 selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the invention are particularly suitable for selectively combating dicotyledon weeds in monocotyledon cultures as a pre-emergence or post-emergence method.
~he 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 Lmpregnated 30 with active compound, and very fine capsules in polymeric Le A 27 329 - 12 -2 ~
substances.
These formulations are produced in a known manner, for example by mixing th~e 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 foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suit-able in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol-vents, 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, montmo-rillonite or diatomaceous earth, and ground syntheticminerals, 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 Le A 27 329 - 13 -~ g~
organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxy-ethy ene 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 latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phos-pholipids, such as cephalins and lecithins, and syntheticphospholipids, 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 phthalocyanir.e dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds, the active compounds accord-ing to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being Le A 2? 329 - 14 -possible. ~y~
Suitable herbicides for the mixtures are known herbicides, such as, for example, l-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMæTHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethyl-urea (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combatin~ weeds in sugar beet, and 4-amino-6-(l,l~dimethylethyl)-3~methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soya beans;
furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D);
A process has now been found for preparing sulphonylurea salts of the general formula (I) N--Z~
~S02-N-CO-N~ `Y ( I ) Le A 27 329 - 1 -2 ~ ~, 2 ~ 3 in which M~ represents an ~lkali metal ion or the counterion, formed by protonation, of a basic organic nitrogen compound, R represents halogenoalkyl, R1 represents optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl or aral-kyl, RZ represents hydrogen, halogen, alkyl, halogenoalkyl, 10alkoxy, halogenoalkoxy, alkylthio, halogenoalkyl-thio, amino, alkylamino or dialkylamino, X represents nitrogen or a -CH group, Y represents nitrogen or a -CR3 group where R3 represents hydrogen, halogen, cyano, alkyl, 15formyl, alkyl-carbonyl or alkoxy carbonyl, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, which is characterized in that sulphonylureas of the general formula (II) ~ SO2-NH-CO-N ~ ~ (II) in which R, R1, R2, X, Y and Z have the abovementioned meanings Le A 27 329 - 2 -are reacted with alkali metal hy~droxides or wl~t~ bas organic nitrogen compounds in the presence of hydro-carbons as diluents at temperatures between 0C and 100C, and the products which are obtained in crystalline form in this procefis are isolatedl by customary methods.
Furthermore, it has been found that the sul-phonylurea salts of the formula (:[) to be prepared by the process according to the invention are distinguished by a powerful herbicidal activity.
The sulphonylurea salts of the formula (I) in which Y represents nitrogen, to be prepared by the process according to the invention, are new and, as new substances, likewise a subject of the present invention.
It is to be regarded as surprising that the sulphonylurea salts of the formula (I) are obtained by the process according to the invention in a very simple manner in very good yields and in high purity, since a smooth reaction of the polar reaction components in hydrocarbons as non-polar solvents was not to be expected.
As comparison experiments have shown addition-ally, an analogous reaction in polar solvents results in the formation of a more or less large proportion of degradation products which virtually do not occur in the reaction of the process according to the invention.
Compared with the corresponding ~free~ sulphonyl-ureas, the new sulphonylurea salts show, in particular, the advantageous property of considerably more stable storage and use forms (formulations and spray liquors).
The process according to the invention preferably Le A 27_329 - 3 -rel~tes to preparing sulphonylurea salts and - if Y
represents nitrogen ~ new sulphonylurea salts of the formula (I) in which M~ represents a lithium, sodium or potassium ion, a tri-(Cl-C4-alkyl)-ammonium ion, a N-(C3-C6-cyclo-alkyl)-NlN-di-(Cl-C4-alkyl)-ammonium ion or in each case the counterion, formed by protonation, of N-(Cl-C4-alkyl)-pyrrolidine, N-(Cl-C4-alXyl)-piperidine, N-(Cl-C4-alkyl)-morpholine, N,N'-di-(Cl-C4-alkyl)-piperazine, N,N-di-(C1-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBM), 1,8-diazabi-cyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-[2.2.2]-octane [DABCO], R represents halogeno-Cl-C4-alkyl, R1 represents Cl-C6-alkyl (which is optionally substi-tuted by fluorine, cyano, C1-C4-alkoxy or C1-C4-alkylthio), or represents C3-C6-alkenyl and C3-C6-alkinyl twhich are optionally substituted by fluor-ine or chlorine), or represents phenyl-C1-C2-alkyl (which is optionally substituted in the phenyl moiety by fluorine, chlorine, nitro, cyano, methyl, methoxy or C1-C2-alkoxycarbonyl), R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethyl-amino, represents nitrogen or a -CH group, ~ represents nitrogen or a -CR3 group where 3C R3 represents hydrogen, fluorine, chlorine, Le A 27 329 - 4 -f~ 3 ~ 3 ~
bromine, methyl, formyl, acetyl, methoxy-carbonyl or ethoxycarbonyl, and Z represen~s nitrogen or a -C~4 group where R4 xepresents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino, dime~hylamino or diethylamino.
In particular, the process according to the invention relates to preparin~ sulphonylurea salts and -if Y represents nitrog~n - new sulphonylurea salts of the formula (I) in which N~ represents a sodium ion or a potassium ion, or represents a trimethyl-, triethyl-, tripropyl- or tributylammonium ion, or a N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclopentyl = onium ion, a N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclo-hexylammonium ion, or in each case the counterion, formed by protonation, of N-methyl-, N-ethyl- or N-propyl-pyrrolidine, N-methyl-, N-ethyl- or N-propyl-piperidine, N-methyl-, N-ethyl- or N-propyl-morpholine, N,N'-dimethyl-, N,N'-diethyl- or N,N'-dipropyl-piperazine, N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-~2.2.2]-octane (DABC0), 30 R represents difluoromethyl or trifluoromethyl, Le A 27 329 _ 5 _ ~t~32~ ~
Rl represents methyl, R2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen, Y represents nitrogen or a CH group ~very particularly preferably nitrogen), and Z represents a C-R4 group where R4 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl,methoxy, etho~y, difluorometh-oxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
If, for example, 3-(4,6-dimethoxy-pyrimidin-2-yl)-3-methyl-1-(2-difluoromethoxy-phenylsulphonyl)-urea and trimethylamine are used as starting substances, the course of the reaction in the process according to the invention can be outlined by the following equation:
SO2-NH-CO-N ~ ~ I N(CH3)3 (for example OCHF2 fH3 OCH3 - ~ 02-N-CO-N--~
toluene) N
HN( CH3)3 OCH3 Le A 27 329- 6 -2~32~8 Formula (II) provides a general definition of the sulphonylureas to be used as starting substances in the process according to the invent:ion for preparing com-pounds of the formula (I)~
In formula (II), R, R1, R2, X, Y and Z preferably, or in particular, have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) accord.ing to the invention as being preferred, or particularly preferred, for R, R1, R2, X, Y and Z.
Examples of the starting substances of the formula (II) are listed in Table 1 below.
~ SO2-NH-CO-N ~ ~ (II) Table 1: Examples of the starting substances of the formula (II) R Rl R2 X Y Z
. .
CF3 . CH3 OCH3 N CH C-OCH3 CF3 CH~ CH3 N N C-OCH3 CF3 CH3 C2H5 N CH C-OCH~
CHF2 CH3 OCH3 N CH C-Cl Le A 27 329 _ 7 _ ~JI~L~L~.J~
Table 1 - continuation CF3 ~H3 CH3 N N 5-CH3 ~e A 27 329 - 8 2~
The starting substances of ~he formula (II) are known and/or can be prepared by processes knvwn per se (cf. EP-A 251,079).
The process according to the invention is carried out using alkali metal hydroxides or basic organic nitrogen compounds. Preferred substances are lithium hydroxide, sodium hydroxide and potassium hydroxide, tri-(C~-C4-alkyl)-amine, N-(C3-C6-cycloalkyl)-N,N-di-(Cl-C4-alkyl)-amine, N-(Cl-C4-alkyl)-pyrrolidine, N-(Cl-C4-alkyl)-piperidine, N-(Cl-C4-alkyl)-morpholine, N,N'-di-(Cl-C4-alkyl)-piperazine, N,N-di-(C1-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabi-cyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).
Particularly preferred substances are sodium hydroxide and potassium hydroxide, trimethyl-, triethyl-, txipropyl- and tributylamine, N,N-dimethyl-,N,N-diethyl-and N,N-dipropyl-cyclopentylamine, N,N-dimethyl-, N,N-diethyl- and N,N-dipropyl-cyclohexylamine, N-methyl-l N-ethyl- and N-propyl-pyrrolidine, N-methyl-, N-ethyl- and N-propyl-piperidine, N-methyl-, N-ethyl- and N-propyl-morpholine, N,N'-dimethyl-, N,N'-diethyl- and N,N'~
dipropyl-piperazine, N,N-dimethyl-, N,N-diethyl- and N,N-dipropyl-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).
The process accordiny to the invention is carried out in the presence of hydrocarbons as diluents. Diluents which are preferred in the process according to the invention are aromatic, in particular benzoidal Le A 27 329 - 9 -3 2 ~
hydrocarbons, which contain, if appropriate, 1 to 3 alkyl substituents, each of which has 1 to 3 carbon atoms.
Examples of these which may be mentioned are: benzene, toluene, o-, m- and p-xylene, ethylbenzene, propyl-benzene, cumene, 1,2,3-trLmethylbenzene, 1,2,4-trLmethyl-ben~ene and I,3,5-trimethylbenzlene. Toluene is very particularly preferred as a diluent in the process according to the invention.
In the process according to the invention, the reaction temperatures can be varied within a substantial range7 In general, the process is carried out at tempera-~ures between 0C and 100C, preferably at temperatures between 10C and 50C.
In general, the process according to the inven-tion is carried out under atmospheric pre sure. However, it is also possible to carry out the process under increased or reduced pressure.
For carrying out the process according to the invention, between 0.9 and 1.5 moles, preferably between 1.0 and 1.3 moles, of an alkali metal hydroxide or a basic organic nitrogen compound are generally employed per mole of sulphonylurea of the formula (I).
The reactants can be combined in any desired sequence. In a preferred embodiment of the process according to the invention, the sulphonylurea of the formula (I) is first stirred with the hydrocarbon diluent, and an alkali metal hydroxide or a basic organic nitrogen compound is then added. The reaction mixture is stirred until crystallization of the product is virtually complete; the product is subsequently isolated by Le A 27 329 - 10 -~,~332~
filtration with suction.
The active compounds of the formula (I) 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 ~he substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the follow-ing plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, ~rtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsiu~, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the aenera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, FLmbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Le A 27 329 - 11 -J ~ 9~
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 accord-ing to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the 10 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, 15 decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee planta-tions, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop-fields, on lawn, turf and pasture-land, and for the 20 selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the invention are particularly suitable for selectively combating dicotyledon weeds in monocotyledon cultures as a pre-emergence or post-emergence method.
~he 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 Lmpregnated 30 with active compound, and very fine capsules in polymeric Le A 27 329 - 12 -2 ~
substances.
These formulations are produced in a known manner, for example by mixing th~e 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 foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suit-able in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloro-ethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol-vents, 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, montmo-rillonite or diatomaceous earth, and ground syntheticminerals, 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 Le A 27 329 - 13 -~ g~
organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxy-ethy ene 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 latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phos-pholipids, such as cephalins and lecithins, and syntheticphospholipids, 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 phthalocyanir.e dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds, the active compounds accord-ing to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being Le A 2? 329 - 14 -possible. ~y~
Suitable herbicides for the mixtures are known herbicides, such as, for example, l-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione (AMæTHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethyl-urea (METABENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combatin~ weeds in sugar beet, and 4-amino-6-(l,l~dimethylethyl)-3~methylthio-1,2,4-triazin-5(4H)-one (METRIBUZIN) for combating weeds in soya beans;
furthermore also 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophPnoxy)-butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); N-(methoxy-methyl)-2,6-diethyl-chloroacetanilide (ALACHLOR); 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triaæine (ATRAZINE); 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzo-nitrile (BROMO~YNIL); 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); exo-l-methyl-4-(1-methyl-ethyl)-2-(2-methylphenyl-methoxy)-7-oxabicyclo-(2,2,1)-heptane (CINMETHYLIN); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID); 2-chloro-4-ethylamino-6-t3-cyanoprop-ylamino)-1,3,5-triazine (CYANAZINE); 2-[4-(2,4-dichloro-phenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); S-ethyl N,N-di-n-propylthiocar-bamate (EPTAME); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIQZINE); 2-{4-[(6-chloro-2-benz-Le A 27 3?9 - 15 -~ J~'3 oxazolyl)-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); l-methyl-3-phenyl-5-(3-trifluoromethyl-phenyl)-4-pyridone ( FLURIDONE); [( 4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its l-methyl-heptyl ester ( FLUROXYPYR); 2-~4-[(3-chloro-5-(trifluoro-methyl)-2-pyridinyl)-oxy]-phenoxy}-propanoic acid or its ethyl ester (HALOXYFOP); 3-cyclohexy1-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione (HEXA~INONE); methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-lH-imidazol-2-yl]-4(5)-methylbenzoate(IMAZAMETHABENZ);3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N,N-dimethyl-N'-(4-i~opropylphenyl)-urea (ISOPROTURON); (2-methyl-4-chlorophenoxy)-acetic acid (MCPA); (4-chloro-2-methyl-phenoxy)-propionic acid (MCPP); N-methyl~2-(1,3-benzo-thiazol-2-yloxy)-acetanilide (MEFENACET); 2-chloro-N-(2,6-dimethylphenyl)-N-[(lH)-pyrazol-l-yl-methyl]-acet-amide (NETAZACHLOR); 2-ethyl-6-methyl-N-(l-methyl-2-methoxyethyl)-chloroacetanilide (METOLACHLOR); 2-{[~((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic acid or its methyl ester (METSULFURON); (2-chloro-4-trifluoromethylphenyl)-(3-ethoxy-4-nitro-phenyl) ether (OXYFLUORFEN); N-(l-ethyl-propyl3-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);
2-chloro-N-isopropylacetanilide (PROPACHLOR); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate(QUIZALOFOP-ETHYL);2-chloro-4,6-bis~
(ethylamino)-1,3,5-triazine (SIMAZINE); 2,4-bis-[N-Le A 27 329 - 16 -~3J ~ J ~ ~
ethylamino]-6-methylthio-I~3l5-tria~ine (SIMETR~NE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine lTERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-2~mino]-sulphonyl]-thio-phene-2-carboxylate (THIAMETURON); S-(2,3,3-trichloro-allyl) N,N-diisopropylthiocarbamate (TRI-ALLATE) and 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLUR-ALIN). Surprisingly, some mixtures also show synergistic action.
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 according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between l g and 1000 g of active compound per hectare of soil surface, preferably between 5 g and 500 g per ha.
The preparation and use of the active compounds Le A 27 329 - 17 -~ ~ e~ ~ 3 ~ g according to the invention can be seen from the following examplPs .
Preparation Examples:
Examplel ~S 2 ~ N - C O - N~ N
Na CH3 OCH3 4.4 g (O.010 mol) of 3-(4,6-dimethoxy-s-triazin-2-yl)-3-methyl-1-(2-trifluoromethoxy-phenylsulphonyl)-urea are stirred with 15 ml of toluene, and 0.5 g (O.0125 mol) of sodium hydroxide powder are then added.
The reaction mixture is stirred for 60 minutes at 20C to 25C, which results in the formation of a viscous crys-talline paste which i~ kept stirrable by adding a total of 30 ml of toluene. When the reaction is complete, the crystalline product is isolated by filtration with suction.
4.0 g (87 % of theory) of the sodium salt of 3-(4,6-dimethoxy-s-triaæin-2-yl)-3-methyl-1-(2-trifluoro-methoxy-phenylsulphonyl)-llrea are obtained; melting point 224C.
Example 2 6~ 7~<
K CH3 oc~3 Le A 27 329 - 18 -r~ l^J ~ ~ ~
4.4 g (0.010 mol) of 3-(4,6-dimethoxy s-triazin-2-yl)-3-methyl-1-(2-trifluoromethoxy-phenylsulphonyl)-urea are stirred with 50 ml of toluene, and 0.8 g of 80 %
potassium hydroxide powder (0.0114 mol of KOH) is then added. The reaction mixture is stirred for 15 hours at 20C to 25C, and the product which is obtained as crystals is isolated by filtration with suction.
4.1 g (86 % of theory) of the potassium salt of 3-(4,6-dimethoxy-s-triazin-2-yl)-3-methyl-1-(2-trifluoro-methoxy-phenylsulphonyl)-urea are obtained; melting point 193~C (decomposition).
Other examples which can be prepared analogously are the compounds of the formula (I) listed in Table 2 below.
~ 5O2-N-CO- ~ ~2 (I) Le A 27 329 - 19 -~3239~
t, _ CJ~ o C -- ~o ~, E N E O` N c~
C 1:~` N
O C~
Z
~ N ~ r 1 ~ Z
:~: Z Z ~-) Z Z _ ~
H
E ~r U o O u U ~ ~
U O O O O O O O
O~`~ ~ ~ U ~ U
C
,~ Z Z Z Z Z Z Z
O
Z Z Z ~ Z Z :Z ~
o N ~ 'q 5 St~
.~ ~ ~ O U O O O O
1~ ~ U ~ 5 ~ 51:~
N N
.. ~ ~ k ~ ~ L h CJ
E~~ O r~ O
Le A 27 329 - 20 -~i.S~3~3~
c -~ N N ~
~ y ~) 1~5 t~ tr~
_I
6 o o O o O
.C
~ ~ Z Z Z Z
o X Z Z Z Z
c O ~ X r~
~I; O O
O
I~; U
E
X
~ IL ~ IL
.. o ~ U
CJ ¦ --~
E~ I X o Le A27 329 - 21 -~ ~ é~
For example, the compound given in Table 2 as Example 5 can be prepared as follows:
-~-CO-N~
( C2H5 ) 3NH CH3 OCH3 8.8 g (0.02 mol) of 3-(4,6~dimethoxy-S-triazin-2-yl)-3-methyl-l-(2-trifluoromethoxy-phenylsulphonyl)-urea are dissolved in 88 ml of toluene by heating to approximately 40C; 2.2 g (0.021 mol) of triethylamine are subsequently added at 35C to 40~C. The product starts to crystallize after a few minutes. The mixture is stirred for another approximately 15 hours at 20C, and the crystalline product is then isolated by filtration with suction.
8.8 g (82 ~ of theory) of the triethylammonium salt of 3-(4,6-dLmethoxy-s-triazin-2-yl)-3-methyl-1-(2-trifluoromethoxy-phenylsulphonyl)-urea are obtained;
melting point: 125DC (decomposition).
Le A 27 329 - 22 -2~ 8 Use Examples:
ExamPle A
Post-emergence test Solvent: 5 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Additive: 0.1 % Renex-36 (= polyoxyethylene(5) tridecyl ether; wetting agent) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier and additive is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 15 cm are sprayed with the preparation of active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is 80 chosen that the particular amounts of active compound desired are applied in 1,000 1 of water/ha. After three weeks, the degree of damage to the plants i8 rated in ~ damage in comparison to the develop-ment of the untreated control. The figures denote:
0~ = no action (like untreated control) 100% = total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 4, 5, 8, 9, 10, 11 and 12 have a very powerful action against weeds combined with a very good tolerance by wheat, barley and maize.
Le A 27 329 - 23 -~ é,~ J
Example ~
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound i8 mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of watex per unit area. The concentration of the active compound in the preparation is of no impor-tance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in com-parison to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 4 and 5 have a very powerful action against weeds combined with a very good tolerance by wheat, barley and maize.
Le A 27 329 - 24 -
2-chloro-N-isopropylacetanilide (PROPACHLOR); 0-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbamate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate(QUIZALOFOP-ETHYL);2-chloro-4,6-bis~
(ethylamino)-1,3,5-triazine (SIMAZINE); 2,4-bis-[N-Le A 27 329 - 16 -~3J ~ J ~ ~
ethylamino]-6-methylthio-I~3l5-tria~ine (SIMETR~NE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine lTERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-2~mino]-sulphonyl]-thio-phene-2-carboxylate (THIAMETURON); S-(2,3,3-trichloro-allyl) N,N-diisopropylthiocarbamate (TRI-ALLATE) and 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLUR-ALIN). Surprisingly, some mixtures also show synergistic action.
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 according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between l g and 1000 g of active compound per hectare of soil surface, preferably between 5 g and 500 g per ha.
The preparation and use of the active compounds Le A 27 329 - 17 -~ ~ e~ ~ 3 ~ g according to the invention can be seen from the following examplPs .
Preparation Examples:
Examplel ~S 2 ~ N - C O - N~ N
Na CH3 OCH3 4.4 g (O.010 mol) of 3-(4,6-dimethoxy-s-triazin-2-yl)-3-methyl-1-(2-trifluoromethoxy-phenylsulphonyl)-urea are stirred with 15 ml of toluene, and 0.5 g (O.0125 mol) of sodium hydroxide powder are then added.
The reaction mixture is stirred for 60 minutes at 20C to 25C, which results in the formation of a viscous crys-talline paste which i~ kept stirrable by adding a total of 30 ml of toluene. When the reaction is complete, the crystalline product is isolated by filtration with suction.
4.0 g (87 % of theory) of the sodium salt of 3-(4,6-dimethoxy-s-triaæin-2-yl)-3-methyl-1-(2-trifluoro-methoxy-phenylsulphonyl)-llrea are obtained; melting point 224C.
Example 2 6~ 7~<
K CH3 oc~3 Le A 27 329 - 18 -r~ l^J ~ ~ ~
4.4 g (0.010 mol) of 3-(4,6-dimethoxy s-triazin-2-yl)-3-methyl-1-(2-trifluoromethoxy-phenylsulphonyl)-urea are stirred with 50 ml of toluene, and 0.8 g of 80 %
potassium hydroxide powder (0.0114 mol of KOH) is then added. The reaction mixture is stirred for 15 hours at 20C to 25C, and the product which is obtained as crystals is isolated by filtration with suction.
4.1 g (86 % of theory) of the potassium salt of 3-(4,6-dimethoxy-s-triazin-2-yl)-3-methyl-1-(2-trifluoro-methoxy-phenylsulphonyl)-urea are obtained; melting point 193~C (decomposition).
Other examples which can be prepared analogously are the compounds of the formula (I) listed in Table 2 below.
~ 5O2-N-CO- ~ ~2 (I) Le A 27 329 - 19 -~3239~
t, _ CJ~ o C -- ~o ~, E N E O` N c~
C 1:~` N
O C~
Z
~ N ~ r 1 ~ Z
:~: Z Z ~-) Z Z _ ~
H
E ~r U o O u U ~ ~
U O O O O O O O
O~`~ ~ ~ U ~ U
C
,~ Z Z Z Z Z Z Z
O
Z Z Z ~ Z Z :Z ~
o N ~ 'q 5 St~
.~ ~ ~ O U O O O O
1~ ~ U ~ 5 ~ 51:~
N N
.. ~ ~ k ~ ~ L h CJ
E~~ O r~ O
Le A 27 329 - 20 -~i.S~3~3~
c -~ N N ~
~ y ~) 1~5 t~ tr~
_I
6 o o O o O
.C
~ ~ Z Z Z Z
o X Z Z Z Z
c O ~ X r~
~I; O O
O
I~; U
E
X
~ IL ~ IL
.. o ~ U
CJ ¦ --~
E~ I X o Le A27 329 - 21 -~ ~ é~
For example, the compound given in Table 2 as Example 5 can be prepared as follows:
-~-CO-N~
( C2H5 ) 3NH CH3 OCH3 8.8 g (0.02 mol) of 3-(4,6~dimethoxy-S-triazin-2-yl)-3-methyl-l-(2-trifluoromethoxy-phenylsulphonyl)-urea are dissolved in 88 ml of toluene by heating to approximately 40C; 2.2 g (0.021 mol) of triethylamine are subsequently added at 35C to 40~C. The product starts to crystallize after a few minutes. The mixture is stirred for another approximately 15 hours at 20C, and the crystalline product is then isolated by filtration with suction.
8.8 g (82 ~ of theory) of the triethylammonium salt of 3-(4,6-dLmethoxy-s-triazin-2-yl)-3-methyl-1-(2-trifluoromethoxy-phenylsulphonyl)-urea are obtained;
melting point: 125DC (decomposition).
Le A 27 329 - 22 -2~ 8 Use Examples:
ExamPle A
Post-emergence test Solvent: 5 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether Additive: 0.1 % Renex-36 (= polyoxyethylene(5) tridecyl ether; wetting agent) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier and additive is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 15 cm are sprayed with the preparation of active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is 80 chosen that the particular amounts of active compound desired are applied in 1,000 1 of water/ha. After three weeks, the degree of damage to the plants i8 rated in ~ damage in comparison to the develop-ment of the untreated control. The figures denote:
0~ = no action (like untreated control) 100% = total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 4, 5, 8, 9, 10, 11 and 12 have a very powerful action against weeds combined with a very good tolerance by wheat, barley and maize.
Le A 27 329 - 23 -~ é,~ J
Example ~
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound i8 mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of watex per unit area. The concentration of the active compound in the preparation is of no impor-tance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in com-parison to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 4 and 5 have a very powerful action against weeds combined with a very good tolerance by wheat, barley and maize.
Le A 27 329 - 24 -
Claims (18)
1. A process for preparing a sulphonylurea salt of the formula (I) in which M? represents an alkali metal ion or the counterion, formed by protonation, of a basic organic nitrogen compound, R represents halogenoalkyl, R1 represents optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl or aral-kyl, R2 represents hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkyl-thio, amino, alkylamino or dialkylamino, X represents nitrogen or a -CH group, Y represents nitrogen or a -CR3 group where R3 represents hydrogen, halogen, cyano, alkyl, formyl, alkyl-carbonyl or alkoxy-carbonyl, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, Le A 27 329 - 25 -which comprises reacting a sulphonylurea of the formula (III) wherein R, R1, R2, X and Y are as defined above, with an alkali metal hydroxide or with a basic organic nitrogen compound in the presence of a hydrocarbon as diluent at a temperature from about 0 to 100°C.
2. The process according to Claim 1, in which M? represents a lithium, sodium or potassium ion, a tri-(C1-C4-alkyl)-ammonium ion, a N-(C3-C6-cyclo-alkyl)-N,N-di-(C1-C4-alkyl)-ammonium ion or in each case the counterion, formed by protonation, of N-(C1-C4-alkyl)-pyrrolidine, N-(C1-C4-alkyl)-piperidine, N-(C1-C4-alkyl)-morpholine, N,N'-di-(C1-C4-alkyl)-piperazine, N,N-di-(C1-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabi-cyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-[2.2.2]-octane [DABCO], R represents halogeno-C1-C4-alkyl, R1 represents C1-C6-alkyl (which is optionally substi-tuted by fluorine, cyano, C1-C4-alkoxy or C1-C4-Le A 27 329 - 26 -alkylthio), or represents C3-C6-alkenyl and C3-C6-alkynyl (which are optionally substituted by fluor-ine or chlorine), or represents phenyl-C1-C2-alkyl (which is optionally substituted in the phenyl moiety by fluorine, chlorine, nitro, cyano, methyl, methoxy or C1-C2-alkoxycarbonyl), R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethyl-amino, X represents nitrogen or a -CH group, Y represents nitrogen or a -CR3 group where R3 represents hydrogen, fluorine, chlorine, bromine, methyl, formyl, acetyl, methoxy-carbonyl or ethoxycarbonyl, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino.
3. The process according to Claim 1, in which M? represents a sodium ion or a potassium ion, or represents a trimethyl-, triethyl-, tripropyl- or tributylammonium ion, or a N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclopentylammonium ion, a Le A 27 329 - 27 -N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclo-hexylammonium ion, or in each case the counterion, formed by protonation, of N-methyl-, N-ethyl- or N-propyl-pyrrolidine, N-methyl-, N-ethyl- or N-propyl-piperidine, N-methyl-, N-ethyl- or N-propyl-mor-pholine, N,N'-dimethyl-, N,N'-diethyl- or N,N'-dipropyl-piperazine, N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-[2.2.2]-octane (DABCO), R represents difluoromethyl or trifluoromethyl, R1 represents methyl, R2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen, Y represents nitrogen or a CH group, and Z represents a C-R4 group where R4 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl,methoxy, ethoxy, difluorometh-oxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
4. A sulphonylurea salt of the formula (I) Le A 27 329 in which M? represents an alkali metal ion or the counterion, formed by protonation, of a basic organic nitrogen compound, R represents halogenoalkyl, R1 represents optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl or aral-kyl, R2 represents hydrogen, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkyl-thio, amino, alkylamino or dialkylamino, X represents nitrogen or a -CH group, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino.
5. A sulphonylurea salt according to Claim 4, in which M? represents a lithium, sodium or potassium ion, a tri-(C1-C4-alkyl)-ammonium ion, a N-(C3-C6-cyclo-alkyl)-N,N-di-(C1-C4-alkyl)-ammonium ion or in each case the counterion, formed by protonation, of N-(C1-C4-alkyl)-pyrrolidine, N-(C1-C4-alkyl)-piperidine, N-(C1-C4-alkyl)-morpholine, N,N'-di-(C1-C4-alkyl)-piperazine, N,N-di-(C1-C4-alkyl)-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabi-cyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-Le A 27 329 - 29 -[2.2.2]-octane [DABCO], R represents halogeno-C1-C4-alkyl, R1 represents C1-C6-alkyl (which is optionally substi-tuted by fluorine, cyano, C1-C4-alkoxy or C1-C4-alkylthio), or represents C3-C6-alkenyl and C3-C6-alkinyl (which are optionally substituted by fluor-ine or chlorine), or represents phenyl-C1-C2-alkyl (which is optionally substituted in the phenyl moiety by fluorine, chlorine, nitro, cyano, methyl, methoxy or C1-C2-alkoxycarbonyl), R2 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethyl-amino, X represents nitrogen or a -CH group, and Z represents nitrogen or a -CR4 group where R4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino.
6. A sulphonylurea salt according to Claim 4, in which M? represents a sodium ion or a potassium ion, or xepresents a trimethyl-, triethyl-, tripropyl- or tributyl-ammonium ion, or a N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclopentylammonium ion, a Le A 27 329 -30-N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-cyclo-hexylammonium ion, or in each case the counterion, formed by protonation, of N-methyl-, N-ethyl- or N-propyl-pyrrolidine, N-methyl-, N-ethyl- or N-propyl-piperidine, N-methyl-, N-ethyl- or N-propyl-morpholine, N,N'-dimethyl-, N,N'-diethyl- or N,N'-dipropyl-piperazine, N,N-dimethyl-, N,N-diethyl- or N,N-dipropyl-benzylamine, 1,5-diazabicyclo-[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) or 1,4-diazabicyclo-[2.2.2]-octane (DABCO), R represents difluoromethyl or trifluoromethyl, R1 represents methyl, R2 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, X represents nitrogen, and Z represents a C-R4 group where R4 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoro-methoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino.
7. A sulphonylurea salt according to claim 4, of the formula in which M? represents Na?, K? or (C2H5)3NH?.
Le A 27 329 - 31 -
Le A 27 329 - 31 -
8. A sulphonylurea salt according to claim 4, of the formula
9. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 4 to 8 in admixture with a suitable carrier or diluent.
10. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 4 to 8 in admixture with a solid diluent or carrier, a liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.
11. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 4 to 8.
12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 4 to 8 in admixture with a suitable carrier or diluent.
13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 4 to 8 in admixture with a suitable carrier or diluent.
14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90% by weight of a compound according to any one of claims 4 to 8 in admixture with a suitable carrier or diluent.
15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 4 to 8 wherein the compound is applied as a pre-emergence herbicide.
16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 4 to 8 wherein the compound is applied as a post-emergence herbicide.
17. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 4 to 8 wherein the compound is applied to an area of cultivation at a rate of between 1 and 1000 g/ha.
18. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 4 to 8 wherein the compound is applied to an area of cultivation at a rate of between 5 and 500 g/ha.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3941790.5 | 1989-12-19 | ||
| DE3941790 | 1989-12-19 | ||
| DEP4018349.1 | 1990-06-08 | ||
| DE4018349A DE4018349A1 (en) | 1989-12-19 | 1990-06-08 | METHOD FOR PRODUCING SULFONYL URINE SALTS, NEW SULFONYL URINE SALTS AND THEIR USE AS HERBICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2032398A1 true CA2032398A1 (en) | 1991-06-20 |
Family
ID=25888121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002032398A Abandoned CA2032398A1 (en) | 1989-12-19 | 1990-12-17 | Process for preparing sulphonylurea salts, new sulphonylurea salts, and their use as herbicides |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0433779B1 (en) |
| JP (1) | JPH03271281A (en) |
| AU (1) | AU638296B2 (en) |
| BR (1) | BR9006439A (en) |
| CA (1) | CA2032398A1 (en) |
| DE (2) | DE4018349A1 (en) |
| ES (1) | ES2068317T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886176A (en) * | 1992-03-05 | 1999-03-23 | Bayer Aktiengesellschaft | Process for preparing sulphonylurea salts |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4440355A1 (en) * | 1994-11-11 | 1996-05-15 | Hoechst Schering Agrevo Gmbh | Acylaminophenylsulfonylurea salts, process for their preparation and use as herbicides and plant growth regulators |
| DE19530768A1 (en) * | 1995-08-22 | 1997-02-27 | Bayer Ag | Salts of N- (2-cyclopropylcarbonylphenylaminosulfonyl) -N '- (4,6-dimethoxy-2-pyrimidinyl) urea |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| OA05625A (en) * | 1976-04-07 | 1981-04-30 | Du Pont | N- (heterocyclic aminocarbonyl) aryl sulfonamides herbicides, compositions containing them and methods using them. |
| DE3621320A1 (en) * | 1986-06-26 | 1988-01-07 | Bayer Ag | 3-SUBSTITUTED 1- (2-HALOGENALKOXY-BENZOLSULFONYL) -3-HETEROARYL- (THIO) UREA |
| DE3609700A1 (en) * | 1986-03-20 | 1987-09-24 | Schering Ag | Salts of substituted sulphonylureas, processes for their preparation, and herbicides and plant growth regulators containing them |
| WO1989001477A1 (en) * | 1987-08-19 | 1989-02-23 | E.I. Du Pont De Nemours And Company | Process for preparing sulfonylurea salts |
-
1990
- 1990-06-08 DE DE4018349A patent/DE4018349A1/en not_active Withdrawn
- 1990-12-05 AU AU67784/90A patent/AU638296B2/en not_active Ceased
- 1990-12-06 ES ES90123370T patent/ES2068317T3/en not_active Expired - Lifetime
- 1990-12-06 DE DE59008523T patent/DE59008523D1/en not_active Expired - Fee Related
- 1990-12-06 EP EP90123370A patent/EP0433779B1/en not_active Expired - Lifetime
- 1990-12-17 CA CA002032398A patent/CA2032398A1/en not_active Abandoned
- 1990-12-18 BR BR909006439A patent/BR9006439A/en not_active Application Discontinuation
- 1990-12-19 JP JP2411668A patent/JPH03271281A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886176A (en) * | 1992-03-05 | 1999-03-23 | Bayer Aktiengesellschaft | Process for preparing sulphonylurea salts |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9006439A (en) | 1991-10-01 |
| DE4018349A1 (en) | 1991-06-20 |
| AU638296B2 (en) | 1993-06-24 |
| EP0433779B1 (en) | 1995-02-22 |
| EP0433779A3 (en) | 1991-11-21 |
| JPH03271281A (en) | 1991-12-03 |
| EP0433779A2 (en) | 1991-06-26 |
| DE59008523D1 (en) | 1995-03-30 |
| AU6778490A (en) | 1991-06-27 |
| ES2068317T3 (en) | 1995-04-16 |
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