CA1223590A - Pyrazolylsulfonylureas and isoxazolylsulfonylureas - Google Patents
Pyrazolylsulfonylureas and isoxazolylsulfonylureasInfo
- Publication number
- CA1223590A CA1223590A CA000461749A CA461749A CA1223590A CA 1223590 A CA1223590 A CA 1223590A CA 000461749 A CA000461749 A CA 000461749A CA 461749 A CA461749 A CA 461749A CA 1223590 A CA1223590 A CA 1223590A
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- Prior art keywords
- alkyl
- shea
- formula
- compound
- halogen
- Prior art date
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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
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Abstract of the disclosure:
Compounds of the general formula (I)
Compounds of the general formula (I)
Description
35~
Heterocyclically substituted phenylsulfor,ylureas which exhibit herb;cidal or plant growth-regulating pro-parties are known from for example, Netherlands Patent 121,788, German 0-Ffenlegungsschrift 2,715,786 and European 5 Patent 1,485.
However, these exhibit disadvantages in use, for example high persistence or inadequate selectivity There have now been found novel pyrazol-4-yl-sul-fonylureas and isoxazol-4-yl-sulfonylureas which contain 10 a pyrimidine or treason rung as an additional heteroçyc~
fig component. These compounds possess advantageous her bicidal and plant growth-regulating properties Accordingly, the present invention relates to compounds of the general formula (I) ~S02~ COY
where X is oxygen or NR6, Y us OH or nitrogen, R1 and R2 independently of one another are hydra-gent halogen, (C1-C6)alkyl, ~C2-C6)alkenyl or (C2-C6)alkynyl, which are optionally substituted by one to three halogen atoms by ~C1-C4 Y' .,. 'I
35~q~
.
by (C1-C4)alkylsulfenyl, by (C1-Cl)alkylsulfinyl, by (C1-C4)alkylsulfonyl or by (C1-C~)alkoxycar-bony, OH, optionally halogenated (C1-C~)alkoxy, (C2-C4)alkenyloxy~ (C2-C4)alkynyloxy, S -OS02(C1-C4)alkyl, -oCO(C1-C4)alkYl~
~OCoN~(c~l-c4)alkyl~2~ ~ocoNH(c~l-c4)alkyl~
-oso2-c6H4-(4~-cH3, -SNOWSHOE, -coequal, (C1-C4)alkylsulfenyl, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, -S02NH(C1-C4)alkYl, -S02N~(C1-C4)alkylJ2, a phenol radical which is optionally substituted by halogen, CF3, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxycarbonyl~
(C1-C4)alkylsulfenyl~ (C1-C4)alkylsulfinyl or (C1-C4)alkylsulfonyl, benzyl,(C1-C4)alkoxycarbonyl, tC2-C4)alkenyloxycarbonyl, (C2-C4)alkynyloxycarbonyl~
aminocarbonyl, (C1-C4)alkylaminocarbonyl or dir(C1-C4)alkyl~aminocarbonyl, R3 us hydrogen or (C1-C4)alkyl, R4 and R5 independently of one another are hydra-on gent (C1-C4)alkyl or (C1-C4)alkoxy which may optionally be moo-, dip or tri-substituted by halogen or moo- or substituted by (C1-C2)alkoxy, or (C1-C2)alkylthio, halogen, ~C1-C4)alkylthio, (C1-C4)alkylamino or (C1-C4)dialkylamino, 5 and- i f X = NR6, R6 is hydrogen, (C1-C6)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, a phenol radical which is option-ally substituted by halogen, ~C1-C4)alkyl, CF3, (C1-C4)a!koxycarbonyl or N02, -C0(C1-C4)alkyl, I
-COO(C1-C6)alkyl, -CONH(C1-C6)alkyl, -CNr(C1-C4)alkYl~l2~ -C-C6HS' -C~12-CO(c1-c~)alkYl~
-S02(C1-C4)a~kyl or -Sickish - and their non-phytotoxic salts.
The novel compounds of the general formula I can be synthesized from starting materials which are known per so or have been prepared by known processes The processes of preparation comprise a) reacting a compound of the formula (II) R7 ~,02~NH-C No wherein R7 and R8 independently of one another are hydra-gent (C1-C8)alkyl, (C3-C7)cycloalkyl or phenol which is optionally monosubstituted or polysub-stituted by halogen, (C1 Colloquial, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkoxycarbonyl, CF3, N02 or CHIHUAHUAS-, or the radicals R7 and R8 together with the shared nitrogen atom form a 5-membered to 7-membered aliphatic ring, wherein a SHEA group can optionally be replaced by oxygen, NH or N(C1 Cowlick , R9 is hydrogen, (C1-C8)alkyl, (C3-C7)cycloalkyl or phenol, which is optionally monosubs-tituted or polysubstituted by halogen,(C1-C4)alkyl, . .
~235~
(C1-C4)alkoxy, (C1-C4)alkylthio, CF3, N02 or (C1-C4)alkoxycarbonyl, and R2, R3, R4, R5 and X have the same meanings 25 in formula (I), 5 with a compound of the formula (III) H-X-NH (lit) where X has the same meaning as in formula I, or 10 b) where appropriate, converting a compound of the formula I, where X = NH or R2 = OH, into another compound of the formula I by derivatization.
Compounds of the formula I, wherein X = NH, can for example be converted into other compounds of the for-15 mute I in a conventional manner by alkylating or acylatingthe NH group of the porously ring, while compounds of the formula I, where R2 = OH, can be converted into other compounds of the formula (I) by alkylation, acylation or halogenation of the heterocyclic OH group, using convent 20 tonal methods.
Rye a): the reaction of the compounds (II) Andy) is preferably carried out in inert solvents, such as aliphat1c or aromatic hydrocarbons, for example zillion or Tulane, acid nitrites, such as acetonitrile, halogen-25 axed or nitrated aliphatics, such as ethylene chloride chloroform or nitromethane, acid asides, such as dim ethyl-formamide, aliphatic alcohols, such as methanol or eta-Rowley, heterocyclics, such as tetrahydrofuran, or mixtures of these solvents with water, where appropriate with the .
~35~
addition of basic compounds such as alkali metal acetates or carbonates, for example sodium acetate or potassium carbonate, or tertiary organic ammonias such as triethyl~
amine or pardon. The reaction is carried out at tempo-5 natures between 0C and the boiling point of the solvent.
where appropriate, the compounds of the formula ~III) are employed in a twofold to three-fold molar excess relative to (I).
Rye b): the alkylation or acylation is preferably 10 carried out in inert solvents such as dimethylformam;det aceton;triLe, tetrahydrofuran, hydrocarbons such as zillion, or water at temperatures between -20 and the boiling point of the solvent. If appropriate, the react ton us carried out with add ton of basic compounds 15 such as alkali metal hydroxides or alkali metal carbon-ales, for example sodium hydroxide or potassium carbon-ate, or tertiary organic amine, such as triethylamine.
Alkylat;ng gents employed are conventional agents such as methyl sulfate, ethyl bromide or propargyl bromide 20 and assaulting agents employed are conventional corapounds such as acetic android, ethyl chloroform ate, dim ethyl-carbamyl chloride or methyl ;socyanate.
The compounds of the formula (I) can form So its on which the sulfonamide hydrogen atom is replaced by a 25 suitable cation. These salts are in general metal salts, optionally substituted ammon;um salts or organic amine salts. These salts are preferably prepared in inert sol-vents, for example water, methanol or acetone, at tempera lures of 20 - 1000C. Exannples ox suitable bases for 5~6~
the preparation of the salts according to the invention are alkali metal carbonates, such as potassium carbonate, ammonia or tertiary organic amine, such as ethanol amine.
The starting compounds of the formula III are 5 known or can be prepared by processes known on principle.
The compounds of the formula II used as starting materials are the subject of German Patent Application P 33 30 603.6 published 21 March 1985.
The heterocyclic sulfonylurea derivatives accord-10 in to the invention exhibit an excellent herbicidal action, and very good selectivity in important large-scale crops. They are therefore suitable for the selective control of dicotyledonous and grasslike annual and preen-nil weeds especially on agriculturally important crops, 15 for example wheat, barley, rye, rice, maize, su3ar-beet and soybean. It us immaterial whether the substances are applied by prosing, reemergence or post-emergence spraying. If the compounds according to the invention are applied to the soil surface by prosing or pro-20 emergence methods, before germination of the weed plants they do not prevent the emergence of the seedlings. The weeds grow to the cotyledon stage, but then cease to grow and finally dye off completely after 3 - 5 weeks. On application of the active compounds to the green parts 25 of plants by the post-emergence method, a drastic cues-station of growth again occurs very rapidly after the treatment, and the weed plants stop at the growth stage reached at the time of application, or die off entirely after a certain time, so that in this way competition 1~35~1~
.
Rome weeds, which us harmful to the crop plants, us sup-pressed very early and lastingly.
In addition, the substances according to the invention exhibit excellent growth regulating properties 5 on crop plants They have a regulating action on the plant's intrinsic metabolism and accordingly can be em-toyed for influencing, on a controlled manner, substances contained in plants, and for facilitation of harvesting, for example by starting desiccation or repressing growth.
10 Moreover, they can be used for the general control and inhibition of undesired vegetative growth without thereby killing the plants. An inhibition of vegetative growth is very important in numerous monocotyledonous and Dakota-loudness crops since lodging can thereby be reduced or 15 completely prevented. Aspects to be particularly singled out are the growth-regulating activity of the compounds as growth inhibitors in cereals, maize, soybean, cotton and lawns, and the ability of the compounds to increase the content of desired constituents, such as carob 20 hydrates and proteins, in crop plants. Finally, the come pounds show a very good improvement in fruit abscission, especially in citrus fruit, or reduce the force with which the fruit is held.
Accordingly, the invention also relates to herb-25 tidal Andre growth-regulating agents which contain a compound of the formula I in combination with conventional formulation auxiliaries and inert substances, and to the use of these agents in agriculture.
The agents according to the invention in general .
- ~'h235~3~
contain 2 - 95% by weight of the active compounds of the formula I. They can be used as wettable powders, emulsi-liable concentrates, spray able solutions, dusting agents or granules, on the customary formulations.
S The wettable powders are preparations which are homogeneously dispersible on water and which on addition to the active compound contain a delineate or inert sub-stance as well us wetting agents, for example polyoxyethy-fated alkylphenols, polyoxyethylated fatty alcohols, 10 alkylsulfonates or alkylphenylsulfonates~ and dispersants, for example sodium lign;nsulfonate~ sodium 2,2'-dinaphthyl-methane~6,6'-disulfonate, sodium dibutylnaphthalenesul-donate or sodium oleylmethyltaurinate.
Emulsifiable concentrates are prepared by disk 15 solving the active compound in an organic solvent, for example buttonhole, cyclohexanone, dimethylformam;de, zillion or higher-boiling aromatics or hydrocarbons, with addition of one or more emulsifiers. Examples of emulsifiers which may be used are: calcium alkylarylsulfonates, such 20 as Cay dodecylbenzenesulfonate, or nonion;c emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/
ethylene oxide condensates, fatty alcohol/propylene oxide/
ethylene oxide condensates, alkyl-polyethers~ sorbitan 25 fatty acid esters, polyoxyethylene-sorbitol fatty acid esters or polyoxyethylene-sorbitol esters.
Dusting agents are obtained by mulling the active compound with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite, ~23~
pyroph;llite or diaton1aceous earth.
Granules can be prepared ether by spraying the active compound onto adsorbent granular inert material or by applying active compound concentrates by means of S adhesives, for example polyvinyl alcohol, sodium polyp acrylate or m;r,eral oils, to the surface ox carriers such as sand, coolants or granular inert material. Suitable - active compounds can also be prepared in the manner con-vent;onally employed for the preparation of fertilizer 10 granules - if desired using a mixture of active compounds with fertilizers.
In herb;cidal agents, the concentrations of the active compounds on the commercial formulations can differ.
In wettable powders, the active compound concern-traction varies for example between about 10% and 80%, the remainder consisting of the forrnulat;on additives men-toned above. In emulsifiable concentrates, the active compound concentration can again be about 10 to 80%.
20 Dust-like formulations contain about 2 - 20%. In grant vies, the active compound content in part depends on whether the active compound is liquid or solid and what granulate no auxiliaries, fullers and the like are used For use as herbicides, the commercial concentrates are diluted, where appropriate, in the customary manner, for example with water in the case of wettable powders and emulsifiable concentrates Dust-like and granular preparations and spray able solutions are not additionally diluted with further inert substances before use. The .
I
amount which requires to be applied varies with external conditions such as temperature, humidity, etc. It us in general between 0.01 and 10 kg/ha, preferably between about 0.1 and 5~0 kg/ha, of active compound.
S For certain application sectors it can be ad van-tageous to use the novel herbicides conjointly Whitehall one or more other herbicides, for example as a tank mixture or ready-to-use formulation in order to achieve add-tonal advantageous effects.
The active compounds according to the invention can be combined with other herbicides, insecticides and fungicides.
Concentrations of between 0~01 and 1.25 kg/ha are suitable for use as growth regulators. preferably, aqueous dispersions of wettable powders or dilutions of ernulsifi able concentrates are used. They are applied by the post emergence method. Preferred crops are maize and tobacco.
Preparation Fxam~les Example 1 1-t3,5 Dimethylisoxazol-4-ylsulfonyl)-3-(4-methoxy~6-methyl-1,3,5-triazin-2-yl~-urea 14.3 9 Tao mole) of N-~(4-methoxy-6-methyl-treason yl)-aminocarbonyl~ methylcarbonyl-2-methylaminoprop-1-en-1 ylsulfonamide Lowry suspended in 150 ml of methanol at 30C~ and 7.2 9 (0.088 mole) of sodium acetate and 6.16 9 (0.08~ mole) of hydroxylarnine hydrochloride were added successively. The mixture was stirred for 18 hours at room temperature, heated for S
minutes to 60C and filtered, the solution was US
. .
concentrated and the residue taken up in water. After acidification with 2 N Hal pi 2-3), 9.8 g (71.7~ of theory) of the desired product were obta;neds Melting point 173C (with decomposition).
Example 2 1-(1,3,5-Tr;methylpyrazol-4-ylsulfonyl~-3-(4,6~dimmethyl-pyrim;d;n-2-yl)-urea 17.1 9 (0.05 mole) of N-C(4,6-d;methylpyrimidin-
Heterocyclically substituted phenylsulfor,ylureas which exhibit herb;cidal or plant growth-regulating pro-parties are known from for example, Netherlands Patent 121,788, German 0-Ffenlegungsschrift 2,715,786 and European 5 Patent 1,485.
However, these exhibit disadvantages in use, for example high persistence or inadequate selectivity There have now been found novel pyrazol-4-yl-sul-fonylureas and isoxazol-4-yl-sulfonylureas which contain 10 a pyrimidine or treason rung as an additional heteroçyc~
fig component. These compounds possess advantageous her bicidal and plant growth-regulating properties Accordingly, the present invention relates to compounds of the general formula (I) ~S02~ COY
where X is oxygen or NR6, Y us OH or nitrogen, R1 and R2 independently of one another are hydra-gent halogen, (C1-C6)alkyl, ~C2-C6)alkenyl or (C2-C6)alkynyl, which are optionally substituted by one to three halogen atoms by ~C1-C4 Y' .,. 'I
35~q~
.
by (C1-C4)alkylsulfenyl, by (C1-Cl)alkylsulfinyl, by (C1-C4)alkylsulfonyl or by (C1-C~)alkoxycar-bony, OH, optionally halogenated (C1-C~)alkoxy, (C2-C4)alkenyloxy~ (C2-C4)alkynyloxy, S -OS02(C1-C4)alkyl, -oCO(C1-C4)alkYl~
~OCoN~(c~l-c4)alkyl~2~ ~ocoNH(c~l-c4)alkyl~
-oso2-c6H4-(4~-cH3, -SNOWSHOE, -coequal, (C1-C4)alkylsulfenyl, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, -S02NH(C1-C4)alkYl, -S02N~(C1-C4)alkylJ2, a phenol radical which is optionally substituted by halogen, CF3, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxycarbonyl~
(C1-C4)alkylsulfenyl~ (C1-C4)alkylsulfinyl or (C1-C4)alkylsulfonyl, benzyl,(C1-C4)alkoxycarbonyl, tC2-C4)alkenyloxycarbonyl, (C2-C4)alkynyloxycarbonyl~
aminocarbonyl, (C1-C4)alkylaminocarbonyl or dir(C1-C4)alkyl~aminocarbonyl, R3 us hydrogen or (C1-C4)alkyl, R4 and R5 independently of one another are hydra-on gent (C1-C4)alkyl or (C1-C4)alkoxy which may optionally be moo-, dip or tri-substituted by halogen or moo- or substituted by (C1-C2)alkoxy, or (C1-C2)alkylthio, halogen, ~C1-C4)alkylthio, (C1-C4)alkylamino or (C1-C4)dialkylamino, 5 and- i f X = NR6, R6 is hydrogen, (C1-C6)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, a phenol radical which is option-ally substituted by halogen, ~C1-C4)alkyl, CF3, (C1-C4)a!koxycarbonyl or N02, -C0(C1-C4)alkyl, I
-COO(C1-C6)alkyl, -CONH(C1-C6)alkyl, -CNr(C1-C4)alkYl~l2~ -C-C6HS' -C~12-CO(c1-c~)alkYl~
-S02(C1-C4)a~kyl or -Sickish - and their non-phytotoxic salts.
The novel compounds of the general formula I can be synthesized from starting materials which are known per so or have been prepared by known processes The processes of preparation comprise a) reacting a compound of the formula (II) R7 ~,02~NH-C No wherein R7 and R8 independently of one another are hydra-gent (C1-C8)alkyl, (C3-C7)cycloalkyl or phenol which is optionally monosubstituted or polysub-stituted by halogen, (C1 Colloquial, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkoxycarbonyl, CF3, N02 or CHIHUAHUAS-, or the radicals R7 and R8 together with the shared nitrogen atom form a 5-membered to 7-membered aliphatic ring, wherein a SHEA group can optionally be replaced by oxygen, NH or N(C1 Cowlick , R9 is hydrogen, (C1-C8)alkyl, (C3-C7)cycloalkyl or phenol, which is optionally monosubs-tituted or polysubstituted by halogen,(C1-C4)alkyl, . .
~235~
(C1-C4)alkoxy, (C1-C4)alkylthio, CF3, N02 or (C1-C4)alkoxycarbonyl, and R2, R3, R4, R5 and X have the same meanings 25 in formula (I), 5 with a compound of the formula (III) H-X-NH (lit) where X has the same meaning as in formula I, or 10 b) where appropriate, converting a compound of the formula I, where X = NH or R2 = OH, into another compound of the formula I by derivatization.
Compounds of the formula I, wherein X = NH, can for example be converted into other compounds of the for-15 mute I in a conventional manner by alkylating or acylatingthe NH group of the porously ring, while compounds of the formula I, where R2 = OH, can be converted into other compounds of the formula (I) by alkylation, acylation or halogenation of the heterocyclic OH group, using convent 20 tonal methods.
Rye a): the reaction of the compounds (II) Andy) is preferably carried out in inert solvents, such as aliphat1c or aromatic hydrocarbons, for example zillion or Tulane, acid nitrites, such as acetonitrile, halogen-25 axed or nitrated aliphatics, such as ethylene chloride chloroform or nitromethane, acid asides, such as dim ethyl-formamide, aliphatic alcohols, such as methanol or eta-Rowley, heterocyclics, such as tetrahydrofuran, or mixtures of these solvents with water, where appropriate with the .
~35~
addition of basic compounds such as alkali metal acetates or carbonates, for example sodium acetate or potassium carbonate, or tertiary organic ammonias such as triethyl~
amine or pardon. The reaction is carried out at tempo-5 natures between 0C and the boiling point of the solvent.
where appropriate, the compounds of the formula ~III) are employed in a twofold to three-fold molar excess relative to (I).
Rye b): the alkylation or acylation is preferably 10 carried out in inert solvents such as dimethylformam;det aceton;triLe, tetrahydrofuran, hydrocarbons such as zillion, or water at temperatures between -20 and the boiling point of the solvent. If appropriate, the react ton us carried out with add ton of basic compounds 15 such as alkali metal hydroxides or alkali metal carbon-ales, for example sodium hydroxide or potassium carbon-ate, or tertiary organic amine, such as triethylamine.
Alkylat;ng gents employed are conventional agents such as methyl sulfate, ethyl bromide or propargyl bromide 20 and assaulting agents employed are conventional corapounds such as acetic android, ethyl chloroform ate, dim ethyl-carbamyl chloride or methyl ;socyanate.
The compounds of the formula (I) can form So its on which the sulfonamide hydrogen atom is replaced by a 25 suitable cation. These salts are in general metal salts, optionally substituted ammon;um salts or organic amine salts. These salts are preferably prepared in inert sol-vents, for example water, methanol or acetone, at tempera lures of 20 - 1000C. Exannples ox suitable bases for 5~6~
the preparation of the salts according to the invention are alkali metal carbonates, such as potassium carbonate, ammonia or tertiary organic amine, such as ethanol amine.
The starting compounds of the formula III are 5 known or can be prepared by processes known on principle.
The compounds of the formula II used as starting materials are the subject of German Patent Application P 33 30 603.6 published 21 March 1985.
The heterocyclic sulfonylurea derivatives accord-10 in to the invention exhibit an excellent herbicidal action, and very good selectivity in important large-scale crops. They are therefore suitable for the selective control of dicotyledonous and grasslike annual and preen-nil weeds especially on agriculturally important crops, 15 for example wheat, barley, rye, rice, maize, su3ar-beet and soybean. It us immaterial whether the substances are applied by prosing, reemergence or post-emergence spraying. If the compounds according to the invention are applied to the soil surface by prosing or pro-20 emergence methods, before germination of the weed plants they do not prevent the emergence of the seedlings. The weeds grow to the cotyledon stage, but then cease to grow and finally dye off completely after 3 - 5 weeks. On application of the active compounds to the green parts 25 of plants by the post-emergence method, a drastic cues-station of growth again occurs very rapidly after the treatment, and the weed plants stop at the growth stage reached at the time of application, or die off entirely after a certain time, so that in this way competition 1~35~1~
.
Rome weeds, which us harmful to the crop plants, us sup-pressed very early and lastingly.
In addition, the substances according to the invention exhibit excellent growth regulating properties 5 on crop plants They have a regulating action on the plant's intrinsic metabolism and accordingly can be em-toyed for influencing, on a controlled manner, substances contained in plants, and for facilitation of harvesting, for example by starting desiccation or repressing growth.
10 Moreover, they can be used for the general control and inhibition of undesired vegetative growth without thereby killing the plants. An inhibition of vegetative growth is very important in numerous monocotyledonous and Dakota-loudness crops since lodging can thereby be reduced or 15 completely prevented. Aspects to be particularly singled out are the growth-regulating activity of the compounds as growth inhibitors in cereals, maize, soybean, cotton and lawns, and the ability of the compounds to increase the content of desired constituents, such as carob 20 hydrates and proteins, in crop plants. Finally, the come pounds show a very good improvement in fruit abscission, especially in citrus fruit, or reduce the force with which the fruit is held.
Accordingly, the invention also relates to herb-25 tidal Andre growth-regulating agents which contain a compound of the formula I in combination with conventional formulation auxiliaries and inert substances, and to the use of these agents in agriculture.
The agents according to the invention in general .
- ~'h235~3~
contain 2 - 95% by weight of the active compounds of the formula I. They can be used as wettable powders, emulsi-liable concentrates, spray able solutions, dusting agents or granules, on the customary formulations.
S The wettable powders are preparations which are homogeneously dispersible on water and which on addition to the active compound contain a delineate or inert sub-stance as well us wetting agents, for example polyoxyethy-fated alkylphenols, polyoxyethylated fatty alcohols, 10 alkylsulfonates or alkylphenylsulfonates~ and dispersants, for example sodium lign;nsulfonate~ sodium 2,2'-dinaphthyl-methane~6,6'-disulfonate, sodium dibutylnaphthalenesul-donate or sodium oleylmethyltaurinate.
Emulsifiable concentrates are prepared by disk 15 solving the active compound in an organic solvent, for example buttonhole, cyclohexanone, dimethylformam;de, zillion or higher-boiling aromatics or hydrocarbons, with addition of one or more emulsifiers. Examples of emulsifiers which may be used are: calcium alkylarylsulfonates, such 20 as Cay dodecylbenzenesulfonate, or nonion;c emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/
ethylene oxide condensates, fatty alcohol/propylene oxide/
ethylene oxide condensates, alkyl-polyethers~ sorbitan 25 fatty acid esters, polyoxyethylene-sorbitol fatty acid esters or polyoxyethylene-sorbitol esters.
Dusting agents are obtained by mulling the active compound with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite, ~23~
pyroph;llite or diaton1aceous earth.
Granules can be prepared ether by spraying the active compound onto adsorbent granular inert material or by applying active compound concentrates by means of S adhesives, for example polyvinyl alcohol, sodium polyp acrylate or m;r,eral oils, to the surface ox carriers such as sand, coolants or granular inert material. Suitable - active compounds can also be prepared in the manner con-vent;onally employed for the preparation of fertilizer 10 granules - if desired using a mixture of active compounds with fertilizers.
In herb;cidal agents, the concentrations of the active compounds on the commercial formulations can differ.
In wettable powders, the active compound concern-traction varies for example between about 10% and 80%, the remainder consisting of the forrnulat;on additives men-toned above. In emulsifiable concentrates, the active compound concentration can again be about 10 to 80%.
20 Dust-like formulations contain about 2 - 20%. In grant vies, the active compound content in part depends on whether the active compound is liquid or solid and what granulate no auxiliaries, fullers and the like are used For use as herbicides, the commercial concentrates are diluted, where appropriate, in the customary manner, for example with water in the case of wettable powders and emulsifiable concentrates Dust-like and granular preparations and spray able solutions are not additionally diluted with further inert substances before use. The .
I
amount which requires to be applied varies with external conditions such as temperature, humidity, etc. It us in general between 0.01 and 10 kg/ha, preferably between about 0.1 and 5~0 kg/ha, of active compound.
S For certain application sectors it can be ad van-tageous to use the novel herbicides conjointly Whitehall one or more other herbicides, for example as a tank mixture or ready-to-use formulation in order to achieve add-tonal advantageous effects.
The active compounds according to the invention can be combined with other herbicides, insecticides and fungicides.
Concentrations of between 0~01 and 1.25 kg/ha are suitable for use as growth regulators. preferably, aqueous dispersions of wettable powders or dilutions of ernulsifi able concentrates are used. They are applied by the post emergence method. Preferred crops are maize and tobacco.
Preparation Fxam~les Example 1 1-t3,5 Dimethylisoxazol-4-ylsulfonyl)-3-(4-methoxy~6-methyl-1,3,5-triazin-2-yl~-urea 14.3 9 Tao mole) of N-~(4-methoxy-6-methyl-treason yl)-aminocarbonyl~ methylcarbonyl-2-methylaminoprop-1-en-1 ylsulfonamide Lowry suspended in 150 ml of methanol at 30C~ and 7.2 9 (0.088 mole) of sodium acetate and 6.16 9 (0.08~ mole) of hydroxylarnine hydrochloride were added successively. The mixture was stirred for 18 hours at room temperature, heated for S
minutes to 60C and filtered, the solution was US
. .
concentrated and the residue taken up in water. After acidification with 2 N Hal pi 2-3), 9.8 g (71.7~ of theory) of the desired product were obta;neds Melting point 173C (with decomposition).
Example 2 1-(1,3,5-Tr;methylpyrazol-4-ylsulfonyl~-3-(4,6~dimmethyl-pyrim;d;n-2-yl)-urea 17.1 9 (0.05 mole) of N-C(4,6-d;methylpyrimidin-
2-yl)-aminocarbonyl]-1-methylcarbonyl-Z-methylaminno prop 1-en-1-ylsulfonamide were suspended on 150 ml of Matthew-not, and 5006 g (0.11 mole) of methylhydrazine were added at 0C. The mixture was sired for a further 18 hours at room temperature and worked up as under Example 1. 14.3 9 (85% of theory) of try methylpyrazol-4 ylsulfonyl)-3-(4,6 dimethylpyrimidin-yowler were obtained. Melting point 216-220C
with decompos;t;on).
Example 3 1-(1,3-D;methyl-5-hydroxypyrazol-4-ylsulfonyl)-3-((4,6-dimethylpyr;mid;n-2-yl)-urea 18~55 9 (Owe mole) of ethyl 2-C3-~4~6-dimethyl-pyrim;d;n-2-yl)-ureidosulfonyl]-3-methylaminobut-22-enoate were suspended in 150 ml of methanol, and 5.06 g (0.11 mole) of methylhydrazine were added at 0C. After 18 hours' stirring at room temperature, the mixture was worked up as under Example 1. 14.7 g (86.4% of theory) of 1-(1,3-dimethyl-5-hydroxypyrazol-~-ylsulfonyl)-3-(4,6-d;methylpyrimidin-2-yl)-urea were obtained. Melt-in point 175 OKAY with decomposition).
~L2~3~
.
The compounds listed in Tables 1 and 2 below can be prepared as described on Examples 1 - I
~Z3~
Table 1 . Isoxa~ol-4- ye sùlfonylureasA~
No ~S~)2N~1CON <
Jo Us N
R2 Pi c o m I US I R4 1 by I Y ¦ M e l t i n g p o u n d . C
N o . I__. _ Jo __ __ SHEA SHEA H OUCH;; It N 173 8 SHEA ('1 H OUCH Ohs OH
C 1 Ohs H OUCH C~T3 OH
SHEA OUCH H OUCH Ouches C H
11 SHEA, OCHF2 If CCH3 CCH3 N
14 SHEA OX ON H OHS C2 Ho OH
SHEA OSSEOUS H SHEA CHIHUAHUAS N
16 SHEA OOZE N~H3S H SHEA SHEA N
17 C2 Ho C2 Ho H Of C~3 OH
.
- .
Table 1 (cont;nuat;on) .
pound I ¦ R2 R5 R4 R5 ¦MP~lotct~g , _ __ . _ _ _ _ 19 COUCH SHEA . H OUCH C~3 OH
Crib COUCH H OUCH OUCH N
21 C6H5 SHEA H SHEA Chihuahuas OH 166~169 2 2 cluck SHEA H OUCH SHEA OH
2 3 -F-C6~ SHEA H OUCH SHEA N
.
24 Lyle SHEA H SHEA SHEA OH
,4-C1-C-Il - SHEA SHEA OUCH OUCH N
. CC~H
27 SHEA -6~I5 H OUCH SHEA OH
.
28 SHEA cluck H - H N(CH5 Jo SHEA OH
29 SHEA C2 Ho H OUCH SHEA N
.
p o u n d Al ¦ R2 I R4 R6 Y M e l i n g _ _ __ - SHEA --I----30` C2 Ho c2 Ho C2 H Of NHCH, N
SHEA
~;~ OH,, OH,, H SHEA OH;, I OUCH N
'. ':
32 SHEA SHEA H CH(SCH3)2 SHEA OH
with decompos;t;on).
Example 3 1-(1,3-D;methyl-5-hydroxypyrazol-4-ylsulfonyl)-3-((4,6-dimethylpyr;mid;n-2-yl)-urea 18~55 9 (Owe mole) of ethyl 2-C3-~4~6-dimethyl-pyrim;d;n-2-yl)-ureidosulfonyl]-3-methylaminobut-22-enoate were suspended in 150 ml of methanol, and 5.06 g (0.11 mole) of methylhydrazine were added at 0C. After 18 hours' stirring at room temperature, the mixture was worked up as under Example 1. 14.7 g (86.4% of theory) of 1-(1,3-dimethyl-5-hydroxypyrazol-~-ylsulfonyl)-3-(4,6-d;methylpyrimidin-2-yl)-urea were obtained. Melt-in point 175 OKAY with decomposition).
~L2~3~
.
The compounds listed in Tables 1 and 2 below can be prepared as described on Examples 1 - I
~Z3~
Table 1 . Isoxa~ol-4- ye sùlfonylureasA~
No ~S~)2N~1CON <
Jo Us N
R2 Pi c o m I US I R4 1 by I Y ¦ M e l t i n g p o u n d . C
N o . I__. _ Jo __ __ SHEA SHEA H OUCH;; It N 173 8 SHEA ('1 H OUCH Ohs OH
C 1 Ohs H OUCH C~T3 OH
SHEA OUCH H OUCH Ouches C H
11 SHEA, OCHF2 If CCH3 CCH3 N
14 SHEA OX ON H OHS C2 Ho OH
SHEA OSSEOUS H SHEA CHIHUAHUAS N
16 SHEA OOZE N~H3S H SHEA SHEA N
17 C2 Ho C2 Ho H Of C~3 OH
.
- .
Table 1 (cont;nuat;on) .
pound I ¦ R2 R5 R4 R5 ¦MP~lotct~g , _ __ . _ _ _ _ 19 COUCH SHEA . H OUCH C~3 OH
Crib COUCH H OUCH OUCH N
21 C6H5 SHEA H SHEA Chihuahuas OH 166~169 2 2 cluck SHEA H OUCH SHEA OH
2 3 -F-C6~ SHEA H OUCH SHEA N
.
24 Lyle SHEA H SHEA SHEA OH
,4-C1-C-Il - SHEA SHEA OUCH OUCH N
. CC~H
27 SHEA -6~I5 H OUCH SHEA OH
.
28 SHEA cluck H - H N(CH5 Jo SHEA OH
29 SHEA C2 Ho H OUCH SHEA N
.
p o u n d Al ¦ R2 I R4 R6 Y M e l i n g _ _ __ - SHEA --I----30` C2 Ho c2 Ho C2 H Of NHCH, N
SHEA
~;~ OH,, OH,, H SHEA OH;, I OUCH N
'. ':
32 SHEA SHEA H CH(SCH3)2 SHEA OH
3 3 SHEA SHEA H COOK ) 2 SHEA OH
34 CCl3 SHEA H OHS OUCH OH
Shekel SHEA H NHCH3 OUCH N
36 SHEA Of SHEA H Of OUCH . N
37 OH SHEA H SHEA Ohs OH 1~8 39 Of Ho OH, ¦ OUCH ¦ H, ¦ N
US -come I R2 R3 R4 R5 y Me l t i no pound pot nut Lo .__ ___ _ _ __ __ on_ Jo OUCH CH-CH2 SHEA H OUCH SHEA OH
42 Chihuahuas SHEA H OUCH c~3 N
. OOZE SHEA SHEA H OUCH SHEA OH
46 OOZE No SHEA H SHEA SHEA OH
34 CCl3 SHEA H OHS OUCH OH
Shekel SHEA H NHCH3 OUCH N
36 SHEA Of SHEA H Of OUCH . N
37 OH SHEA H SHEA Ohs OH 1~8 39 Of Ho OH, ¦ OUCH ¦ H, ¦ N
US -come I R2 R3 R4 R5 y Me l t i no pound pot nut Lo .__ ___ _ _ __ __ on_ Jo OUCH CH-CH2 SHEA H OUCH SHEA OH
42 Chihuahuas SHEA H OUCH c~3 N
. OOZE SHEA SHEA H OUCH SHEA OH
46 OOZE No SHEA H SHEA SHEA OH
4~3 SHEA SHEA H SHEA SHEA N
52 SHEA Ouches SHEA H SHEA SHEA OH
54 Ibsyl Ohs H SHEA SHEA OH
.
235~
Table 2 Pyrazol-4-yl-su.lfon~lureas pa N R4 SUE NHCON
I ( R3 N Us p o u n d Al R2 R3 Rq Us R6 M e L t i n g --I _ __ __ SHEA SHEA, H SHEA SHEA C2 I OH ll9 56 SHEA SHEA H SHEA SHEA C3 Ho OH 184-1~7 57 SHEA SHEA H SHEA SHEA OH CCHt~CH3 OH 214- 217 58 SHEA SHEA H SHEA SHEA OH OH' OH 2 Of- 2 03 61 SHEA SHEA H OHS Ohs SHEA OH
62 SHEA SHEA H OUCH SHEA C2 Ho OH 1 5 2 -1 5 4 63 Ohs SHEA H OHS SHEA Us Ho KIWI OH 1 6 4 -1 6 7 64 Ohs SHEA H OUCH SHEA OH ~CHCH OH 186 owe Ohs SHEA H GCH3 SHEA OH OH' 3 OH 1 3 6 -1 3 9 66 OHS SHEA H OUCH ooze H OH
67 SHEA SHEA H OUCH OOZE Ohs OH
69 SHEA Ohs H OUCH OUCH SHEA N
.
Table 2 (continuation) , Come . Melting pound R1 R2 R3 R4 R5 I Y pro i nut no. r c~
__ __ _ . _. _ _ _ 7 SHEA SHEA H OUCH SHEA H It 72 SHEA CXs H OUCH SHEA C3 Ho N
73 SHEA SHEA H SCHICK I C~3 SHEA OH 182-184 74 SHEA C~13 H OH ( C2 Ho I SHEA SHEA OH
SHEA KIWI H Of SHEA SHEA OH
78 SHEA SHEA H N(CII~ I SHEA SHEA N
79 C~3 SHEA H SHEA SHEA OUCH SHEA N
SHEA C~3 H SHEA S2 SHEA OUCH SHEA N
81 Ohs SHEA H SHEA SHEA OUCH SHEA OH
82 Ohs SHEA H SHEA OUCH SHEA SHEA OH
83 SHEA Ohs H SHEA SHEA C OUCH OH
SHEA SHEA H SHEA SHEA CACHE SHEA
87 SHEA Ohs H OH SHEA CON H3)2 OH
88 OH, Ohs H SHEA SHEA ¦ COUCH OH
KIWI
Table 2 (continuation) p o u n d Al I l R5 R4 L Jo 11 e l t 1 n g - _ I _ SHEA SHEA H OUCH SHEA SHEA COUCH;; N
9 SHEA SHEA H SHEA SHEA SO C~13 OH
91 SHEA Ohs HI SHEA SHEA C6H5 OH 17 6 92 SHEA SHEA H OUCH c~3 cluck H - OH
93 SHEA SHEA H OUCH CEIL 3-c~-C6H4- OH
94 . SHEA cTH~ H OX Ho SHEA 4 -Cluck- N
- 95 SHEA, SHEA To OUCH SHEA 3-CF -C EYE- OH
96 SHEA SHEA H SHEA SHEA oilily OH
97 H H H OUCH C~3 SHEA OH
98 Ohs H H OUCH SHEA Chihuahuas N
loo H Of H OUCH KIWI SHEA N
lo Of H H OUCH SHEA SHEA N .
Z35~
table 2 (continuation) -p o u n d Al R2 R3 I ¦ R5 I Y p ,~tC
o. __ __~ _ __ __ I_ 102 SHEA Of H SHEA SHEA SHEA OH 2 2 0 - 2 3 0 103 C2 Ho C2 Ho H SHEA SHEA c~3 OH
104 CF3 SHEA H SHEA ohs Chihuahuas OH
105 CF5 Of H OUCH SHEA SHEA N
108 OUCH SHEA H SHEA SHEA Us OH
10~ SHEA OUCH H OUCH SHEA SHEA N
111 SHEA SWISH H OUCH SHEA C~3 OH
112 SHEA SO Ohs H OOZE C~.3 SHEA OH
113 Ho Ho CH=CH2 H OUCH KIWI KIWI OH
115 CH3o932CH3 H SHEA Ohs SHEA OH
116 . OH, OKAY H ; Of SHEA H OH
118 CH3CCO~r~ H OUCH SHEA SHEA OH
so Table 2 continuation) C Melting pound R1 R2 R3 R4 I R6 y point -- SHEA __ Jo _ _ 119 SHEA OSQ2 N~CH3 H SHEA SHEA C~3 OH
' . .
i22 SHEA SHEA SO SHEA H OUCH Ohs SHEA OH
123 SHEA SHEA CGOCH3 H SHEA SHEA SHEA OH .
124 SHEA -C6H5 H SHEA Ohs KIWI OH 130 12 6 OHS 2~1-C6H4- H OUCH Ohs SHEA N
127 SHEA E~Tolyl H OUCH SHEA eye OH
. . .
129 SHEA 2{~F3-C6H4- H OUCH C~3 Ohs OH
o Table 2 (continuation) R2 R3 I Us R6 Y ill e l t i n g p o u n d _ I_ I_ . __ _ . . . p o i n t C OKAY
130 C~3 SO Ohs H SHEA . SHEA , OH
131 H Jo H SHEA SHEA SHEA OH
132 C6H5 H . H OUCH C~3 I
lo C6H5 H H SHEA SHEA SHEA OH
1~4 cluck 4 SHEA H Ho SHEA SHEA OH
SHEA H SHEA SHEA KIWI N
1~6 SHEA H OUCH, SHEA SHEA OH
. SHEA SHEA SHEA SHEA H C .
138 Of Of H OUCH SHEA I OH .
1~9: SHEA ¦ By H OUCH C~;5 SHEA OH
140 c~3 OSSIFY H H OUCH SHEA SHEA N
141 H OSSIFY H OUCH C Ho SHEA OH
43 SHEA CCF2CHF2.H OUCH SHEA ÇH3 I
144 Ho OCF2CHClE H OUCH OUCH H OH
~35i~
, - 23 a -Table 2 (continuation) , Come Melting pound R1 R2 R3 R4 R5 6 point ---152 Of OCHF2 WHOOSH SHEA SHEA OH
15 3 OCHF2 Of 3 3 3 N
154 SHEA . 3 C 3 SO 3 155 SHEA Of WHOOSH SHEA COUCH OH
156 SHEA Of WHOOSH SHEA COOK N
.
160 H Of WHOOSH OUCH S2CH3 OH
I
- I -I. Herbicidal action The present compounds according to the invention exhibit excellent herbicidal activity against a broad spectrum of economically important monocotyledonous
52 SHEA Ouches SHEA H SHEA SHEA OH
54 Ibsyl Ohs H SHEA SHEA OH
.
235~
Table 2 Pyrazol-4-yl-su.lfon~lureas pa N R4 SUE NHCON
I ( R3 N Us p o u n d Al R2 R3 Rq Us R6 M e L t i n g --I _ __ __ SHEA SHEA, H SHEA SHEA C2 I OH ll9 56 SHEA SHEA H SHEA SHEA C3 Ho OH 184-1~7 57 SHEA SHEA H SHEA SHEA OH CCHt~CH3 OH 214- 217 58 SHEA SHEA H SHEA SHEA OH OH' OH 2 Of- 2 03 61 SHEA SHEA H OHS Ohs SHEA OH
62 SHEA SHEA H OUCH SHEA C2 Ho OH 1 5 2 -1 5 4 63 Ohs SHEA H OHS SHEA Us Ho KIWI OH 1 6 4 -1 6 7 64 Ohs SHEA H OUCH SHEA OH ~CHCH OH 186 owe Ohs SHEA H GCH3 SHEA OH OH' 3 OH 1 3 6 -1 3 9 66 OHS SHEA H OUCH ooze H OH
67 SHEA SHEA H OUCH OOZE Ohs OH
69 SHEA Ohs H OUCH OUCH SHEA N
.
Table 2 (continuation) , Come . Melting pound R1 R2 R3 R4 R5 I Y pro i nut no. r c~
__ __ _ . _. _ _ _ 7 SHEA SHEA H OUCH SHEA H It 72 SHEA CXs H OUCH SHEA C3 Ho N
73 SHEA SHEA H SCHICK I C~3 SHEA OH 182-184 74 SHEA C~13 H OH ( C2 Ho I SHEA SHEA OH
SHEA KIWI H Of SHEA SHEA OH
78 SHEA SHEA H N(CII~ I SHEA SHEA N
79 C~3 SHEA H SHEA SHEA OUCH SHEA N
SHEA C~3 H SHEA S2 SHEA OUCH SHEA N
81 Ohs SHEA H SHEA SHEA OUCH SHEA OH
82 Ohs SHEA H SHEA OUCH SHEA SHEA OH
83 SHEA Ohs H SHEA SHEA C OUCH OH
SHEA SHEA H SHEA SHEA CACHE SHEA
87 SHEA Ohs H OH SHEA CON H3)2 OH
88 OH, Ohs H SHEA SHEA ¦ COUCH OH
KIWI
Table 2 (continuation) p o u n d Al I l R5 R4 L Jo 11 e l t 1 n g - _ I _ SHEA SHEA H OUCH SHEA SHEA COUCH;; N
9 SHEA SHEA H SHEA SHEA SO C~13 OH
91 SHEA Ohs HI SHEA SHEA C6H5 OH 17 6 92 SHEA SHEA H OUCH c~3 cluck H - OH
93 SHEA SHEA H OUCH CEIL 3-c~-C6H4- OH
94 . SHEA cTH~ H OX Ho SHEA 4 -Cluck- N
- 95 SHEA, SHEA To OUCH SHEA 3-CF -C EYE- OH
96 SHEA SHEA H SHEA SHEA oilily OH
97 H H H OUCH C~3 SHEA OH
98 Ohs H H OUCH SHEA Chihuahuas N
loo H Of H OUCH KIWI SHEA N
lo Of H H OUCH SHEA SHEA N .
Z35~
table 2 (continuation) -p o u n d Al R2 R3 I ¦ R5 I Y p ,~tC
o. __ __~ _ __ __ I_ 102 SHEA Of H SHEA SHEA SHEA OH 2 2 0 - 2 3 0 103 C2 Ho C2 Ho H SHEA SHEA c~3 OH
104 CF3 SHEA H SHEA ohs Chihuahuas OH
105 CF5 Of H OUCH SHEA SHEA N
108 OUCH SHEA H SHEA SHEA Us OH
10~ SHEA OUCH H OUCH SHEA SHEA N
111 SHEA SWISH H OUCH SHEA C~3 OH
112 SHEA SO Ohs H OOZE C~.3 SHEA OH
113 Ho Ho CH=CH2 H OUCH KIWI KIWI OH
115 CH3o932CH3 H SHEA Ohs SHEA OH
116 . OH, OKAY H ; Of SHEA H OH
118 CH3CCO~r~ H OUCH SHEA SHEA OH
so Table 2 continuation) C Melting pound R1 R2 R3 R4 I R6 y point -- SHEA __ Jo _ _ 119 SHEA OSQ2 N~CH3 H SHEA SHEA C~3 OH
' . .
i22 SHEA SHEA SO SHEA H OUCH Ohs SHEA OH
123 SHEA SHEA CGOCH3 H SHEA SHEA SHEA OH .
124 SHEA -C6H5 H SHEA Ohs KIWI OH 130 12 6 OHS 2~1-C6H4- H OUCH Ohs SHEA N
127 SHEA E~Tolyl H OUCH SHEA eye OH
. . .
129 SHEA 2{~F3-C6H4- H OUCH C~3 Ohs OH
o Table 2 (continuation) R2 R3 I Us R6 Y ill e l t i n g p o u n d _ I_ I_ . __ _ . . . p o i n t C OKAY
130 C~3 SO Ohs H SHEA . SHEA , OH
131 H Jo H SHEA SHEA SHEA OH
132 C6H5 H . H OUCH C~3 I
lo C6H5 H H SHEA SHEA SHEA OH
1~4 cluck 4 SHEA H Ho SHEA SHEA OH
SHEA H SHEA SHEA KIWI N
1~6 SHEA H OUCH, SHEA SHEA OH
. SHEA SHEA SHEA SHEA H C .
138 Of Of H OUCH SHEA I OH .
1~9: SHEA ¦ By H OUCH C~;5 SHEA OH
140 c~3 OSSIFY H H OUCH SHEA SHEA N
141 H OSSIFY H OUCH C Ho SHEA OH
43 SHEA CCF2CHF2.H OUCH SHEA ÇH3 I
144 Ho OCF2CHClE H OUCH OUCH H OH
~35i~
, - 23 a -Table 2 (continuation) , Come Melting pound R1 R2 R3 R4 R5 6 point ---152 Of OCHF2 WHOOSH SHEA SHEA OH
15 3 OCHF2 Of 3 3 3 N
154 SHEA . 3 C 3 SO 3 155 SHEA Of WHOOSH SHEA COUCH OH
156 SHEA Of WHOOSH SHEA COOK N
.
160 H Of WHOOSH OUCH S2CH3 OH
I
- I -I. Herbicidal action The present compounds according to the invention exhibit excellent herbicidal activity against a broad spectrum of economically important monocotyledonous
5 and dicotyledonous harmful plants. The active compounds also deal well with perennial root-propagated weeds which are dill-faculty to combat It is immaterial whether the sub-stances are applied by prosing, reemergence or post-emergence spraying. If the compounds according to the invention are applied to the soil surface by the prosing or pre-emer~ence method before germination of the weed plants, they do not prevent the emergence of the seedlings. The weeds grow to the cotyledon stage, but then cease to grow and finally die off completely after 3 - 5 weeks.
On application of the active compounds to the green parts of plants by the post-emer0ence method, a drastic cessation of growth again occurs very rapidly after the treatment, and the weed plants stop at the growth stage reached at the time of application, or die off entirely after a certain time, so that in this way competition from weeds, which us harmful to the crop plants, is suppressed very early and lastingly by the use of the novel agents according to the invention.
Though the compounds according to the invention possess an excellent herbicidal activity against moo-cotyledons and dicotyledonous weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, maize, susar-beet, cotton and ~35~
soybean are damaged only insignificantly, i-f at ail.
For these reasons the present compounds are very suit-able for combating undesired plant growth on agricul-tubal crops.
The damage to the weed plants and toleration by the crop plants were rated on a scale of O - I ;
On this scale the figures have the following meaning:, 0 = no action (damaged) 1 = O - 20% action 2 = 20 - YO-YO action 3 = 40 - 60% action 4 - 60 - 80% action 5 = 80 100% action 1. Reemergence method Seeds or pieces of rhizome of monocotyledonous and dicotyledonous weeds were set out in loam in plastic pots (diameter 9 cm) and covered with soil. The come pounds according to the invention, formulated as wet-table powders or as emulsion concentrates, were applied the form of aqueous suspensions or emulsions to the soul surface. The amount of water used per pot eon-responded, when converted, to 600 - 800 litres/hectare.
After the treatment the test pots wore set up in a greenhouse and the test plants cultivated under good conditions for-growth temperature: Z3 1C; relative atmospheric humidity 60 - yo-yo After about 3 weeks, - the damage to the plants was assessed visually. Us-treated controls were used for comparison - I
As may be seen from the values in Table 3, the compounds according to the invention, used in the pro-emergence meti~Gd,in part show- an excellent herbicidal activity against economically irilportant monocotyledo-S noun and dicotyledonous harmful plants.
2. Post-emergence method Seeds of monocotyledonous and dicotyledonous weeds were sown in pots and grown in a greenhouse under good conditions for growth. 3 weeks after sowing, the test plants were treated while in the trifoliate stage.
The preparations according to the invention, formulated as wettable powders or as emulsion concentrates, were sprayed in various doses onto the green parts of the - plant sand after the plants had stood for about weeks in a it greenhouse under optimum growth conditions (temperature:
23 1C; relative atmospheric humidity 60 - 80%) the effect of the preparations was assessed visually in comparison to untreated controls. The agents according to the invention showed goad herbicidal anti-I viny against a broad spectrum of economically important broadleaf and grimness weeds table 4).
owe -Table 3: Herbicidal action of the compounds according to the invention used in the pro emergence method .
En- Dose Herbicidal activity ample ient/hectare SPA Ski LOWE COG
1 2~5 4 5 4 3 3 2.5 1 2 2 4 2.5 S 4 4 4 2~5 5 5 5 4 21 2~5 3 5 37 2.5 1 2 1 2 56 2.5 5 5 5 5 57 2.5 4 4 4 SO 2.5 2 1 2 2 So 2.5 5 5 5 5 61 2,5 5 5 5 5 62 2.5 5 S 5 5 63 2.5 4 1 4 64 2.5 5 5 5 5 2,5 5 5 5 5 ` 71 2.5 5 5 5 5 73 2.5 5 5 5 5 91 2.5 5 4 4 124 2.5 5 5 4 5 125 2.5 5 3 4 3 161 2.5 5 5 5 S
Table 4: Herbicidal action of the compounds according to the invention used in the post-emergence method .-En- Dose Herbicidal activity ample kg of active inured-ient/hectare SIX So Lo HOG
1 2~5 4 4 1 2 2 2,5 5 5 5 5 3 2.5 3 2 2 4 2,5 5 3 4 2.5 5 5 4 3 21 I 5 4 2 ` 3 37 2,5 1 2 1 0 56 2,5 5 5 5 57 2,5 3 3 4 2 58 2!5 3 3 3 59 2,5 5 5 5 5 it 2,5 4 3 4 2 I 2.5 5 5 5 4 63 2,5 4 3 4 2 64 2,5 4 3 3 3 2,5 5 2 3 4 71 2~5 5 5 5 5 73 2~5 5 5 4 5 91 2~5 3 3 3 124 2.5 4 3 S 4 125 2.5 4 3 5 3 161 2.5 5 5 5 5 Abbreviations: as for Table 3 ~35~
.
II. Growth-regulating activity 1. Stimulation of liberation of ethylene Calamondin oranges were dipped for 2 minutes in solutions containing 2,000 Pam of the-active compound.
The ethylene formed by the fruit was then determined daily by gas chromatography over 5 days.
The results of Table 5 represent a mean of a total of 3 series of experiments.
Table 5:
10 Compound according Ethylene production to Example (relative units) Total for sty - Thea day Control 2.0 Glyoxime 4.1 4 14.6 62 16.2 The compounds claimed show, as may be seen in Table 1, a substantially higher initial action and last-in action in respect of ethylene liberation than that shown by the comparative agent glyoxime~ The total amount of ethylene formed also markedly exceeds that obtained with the comparative agent. Since ethylene, which is also formed by the plant, is a determining factor in the process of ripening and absciss;on, the experiment serves to prove the accelerated and compare-pensive formation of separation tissue, and hence the induction of the abscission process, brought about by the compounds according to the present appl;cat;on.
I
2. Abscission act-ion in citrus plants Pieces of orange tree branches bearing at least 20 fruit were sprayed with active compound solutions shortly before -the harvest.
After 7 days, the results were evaluated by measuring the force with which the fruit was held.
Table 6 - Preparation No. Dosage Holding force (Pam) (pounds) Control 16 Comparative agent 5-chloro-3-methyl-1û 4-nitropyrazoLe owe 3~5 4 1,000 1.9 62 1,000 2.1 .
` .
On application of the active compounds to the green parts of plants by the post-emer0ence method, a drastic cessation of growth again occurs very rapidly after the treatment, and the weed plants stop at the growth stage reached at the time of application, or die off entirely after a certain time, so that in this way competition from weeds, which us harmful to the crop plants, is suppressed very early and lastingly by the use of the novel agents according to the invention.
Though the compounds according to the invention possess an excellent herbicidal activity against moo-cotyledons and dicotyledonous weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, maize, susar-beet, cotton and ~35~
soybean are damaged only insignificantly, i-f at ail.
For these reasons the present compounds are very suit-able for combating undesired plant growth on agricul-tubal crops.
The damage to the weed plants and toleration by the crop plants were rated on a scale of O - I ;
On this scale the figures have the following meaning:, 0 = no action (damaged) 1 = O - 20% action 2 = 20 - YO-YO action 3 = 40 - 60% action 4 - 60 - 80% action 5 = 80 100% action 1. Reemergence method Seeds or pieces of rhizome of monocotyledonous and dicotyledonous weeds were set out in loam in plastic pots (diameter 9 cm) and covered with soil. The come pounds according to the invention, formulated as wet-table powders or as emulsion concentrates, were applied the form of aqueous suspensions or emulsions to the soul surface. The amount of water used per pot eon-responded, when converted, to 600 - 800 litres/hectare.
After the treatment the test pots wore set up in a greenhouse and the test plants cultivated under good conditions for-growth temperature: Z3 1C; relative atmospheric humidity 60 - yo-yo After about 3 weeks, - the damage to the plants was assessed visually. Us-treated controls were used for comparison - I
As may be seen from the values in Table 3, the compounds according to the invention, used in the pro-emergence meti~Gd,in part show- an excellent herbicidal activity against economically irilportant monocotyledo-S noun and dicotyledonous harmful plants.
2. Post-emergence method Seeds of monocotyledonous and dicotyledonous weeds were sown in pots and grown in a greenhouse under good conditions for growth. 3 weeks after sowing, the test plants were treated while in the trifoliate stage.
The preparations according to the invention, formulated as wettable powders or as emulsion concentrates, were sprayed in various doses onto the green parts of the - plant sand after the plants had stood for about weeks in a it greenhouse under optimum growth conditions (temperature:
23 1C; relative atmospheric humidity 60 - 80%) the effect of the preparations was assessed visually in comparison to untreated controls. The agents according to the invention showed goad herbicidal anti-I viny against a broad spectrum of economically important broadleaf and grimness weeds table 4).
owe -Table 3: Herbicidal action of the compounds according to the invention used in the pro emergence method .
En- Dose Herbicidal activity ample ient/hectare SPA Ski LOWE COG
1 2~5 4 5 4 3 3 2.5 1 2 2 4 2.5 S 4 4 4 2~5 5 5 5 4 21 2~5 3 5 37 2.5 1 2 1 2 56 2.5 5 5 5 5 57 2.5 4 4 4 SO 2.5 2 1 2 2 So 2.5 5 5 5 5 61 2,5 5 5 5 5 62 2.5 5 S 5 5 63 2.5 4 1 4 64 2.5 5 5 5 5 2,5 5 5 5 5 ` 71 2.5 5 5 5 5 73 2.5 5 5 5 5 91 2.5 5 4 4 124 2.5 5 5 4 5 125 2.5 5 3 4 3 161 2.5 5 5 5 S
Table 4: Herbicidal action of the compounds according to the invention used in the post-emergence method .-En- Dose Herbicidal activity ample kg of active inured-ient/hectare SIX So Lo HOG
1 2~5 4 4 1 2 2 2,5 5 5 5 5 3 2.5 3 2 2 4 2,5 5 3 4 2.5 5 5 4 3 21 I 5 4 2 ` 3 37 2,5 1 2 1 0 56 2,5 5 5 5 57 2,5 3 3 4 2 58 2!5 3 3 3 59 2,5 5 5 5 5 it 2,5 4 3 4 2 I 2.5 5 5 5 4 63 2,5 4 3 4 2 64 2,5 4 3 3 3 2,5 5 2 3 4 71 2~5 5 5 5 5 73 2~5 5 5 4 5 91 2~5 3 3 3 124 2.5 4 3 S 4 125 2.5 4 3 5 3 161 2.5 5 5 5 5 Abbreviations: as for Table 3 ~35~
.
II. Growth-regulating activity 1. Stimulation of liberation of ethylene Calamondin oranges were dipped for 2 minutes in solutions containing 2,000 Pam of the-active compound.
The ethylene formed by the fruit was then determined daily by gas chromatography over 5 days.
The results of Table 5 represent a mean of a total of 3 series of experiments.
Table 5:
10 Compound according Ethylene production to Example (relative units) Total for sty - Thea day Control 2.0 Glyoxime 4.1 4 14.6 62 16.2 The compounds claimed show, as may be seen in Table 1, a substantially higher initial action and last-in action in respect of ethylene liberation than that shown by the comparative agent glyoxime~ The total amount of ethylene formed also markedly exceeds that obtained with the comparative agent. Since ethylene, which is also formed by the plant, is a determining factor in the process of ripening and absciss;on, the experiment serves to prove the accelerated and compare-pensive formation of separation tissue, and hence the induction of the abscission process, brought about by the compounds according to the present appl;cat;on.
I
2. Abscission act-ion in citrus plants Pieces of orange tree branches bearing at least 20 fruit were sprayed with active compound solutions shortly before -the harvest.
After 7 days, the results were evaluated by measuring the force with which the fruit was held.
Table 6 - Preparation No. Dosage Holding force (Pam) (pounds) Control 16 Comparative agent 5-chloro-3-methyl-1û 4-nitropyrazoLe owe 3~5 4 1,000 1.9 62 1,000 2.1 .
` .
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula I
(I) where X is oxygen or NR6, Y is CH or nitrogen, R1 and R2 independently of one another are hydrogen, halogen, (C1-C6)-alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, which are optionally substituted by one to three halogen atoms, by (C1-C4)alkoxy, by (C1-C4)alkylsulfenyl, by (C1-C4)alkylsulfinyl, by (C1-C4)alkylsulfonyl or by (C1-C4)alkoxycarbonyl, OH, (C1-C4)alkoxy, (C2-C4)alkenyloxy, (C2-C4)alkynyloxy, -OSO2(C1-C4)alkyl, -OCO(C1-C4)alkyl, -OCON[(C1-C4)alkyl]2, -OCONH(C1-C4)alkyl, -OSO2-C6H4-(4)-CH3, -OSO2N(CH3)2, -OCO-C6H5, (C1-C4)alkylsulfenyl, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, -SO2NH(C1-C4)alkyl, -SO2N[(C1-C4)alkyl]2, a phenyl radical which is optionally substituted by halogen, CF3, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxycarbonyl, (C1-C4)alkylsulfenyl, (C1-C4)alkylsulfinyl or (C1-C4)alkylsulfonyl, benzyl, (C1-C4)alkoxycarbonyl, (C2-C4)alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, aminocarbonyl, (C1-C4)alkylaminocarbonyl or di[(C1-C4)alkyl]aminocarbonyl, R3 is hydrogen or (C1-C4)alkyl, R4 and R5 independently of one another are hydrogen, (C1-C4)alkyl or (C1-C4)alkoxy which may optionally be mono-, di-or tri-substituted by halogen or mono- or di-substituted by (C1-C2)alkoxy, or (C1-C2)alkylthio, halogen, (C1-C4)alkylthio, (C1-C4)alkylamino or (C1-C4)dialkylamino, and if X = NR6, R6 is hydrogen, (C1-C6)alkyl, (C2-C4)alkenyl, (C2-C4)-alkynyl, a phenyl radical which is optionally substituted by halogen, (C1-C4)alkyl, CF3, (C1-C4)alkoxycarbonyl or NO2, -CO(C1-C4)alkyl, -COO(C1-C6)alkyl, -CONH(C1-C6)alkyl, -CON[(C1-C4)-alkyl]2, -CO-C6H5, -CH2-COO(C1-C4)alkyl, -SO2(C1-C4)alkyl or -SO2-C6H4-(4)CH3, and its non-phytotoxic salts.
(I) where X is oxygen or NR6, Y is CH or nitrogen, R1 and R2 independently of one another are hydrogen, halogen, (C1-C6)-alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, which are optionally substituted by one to three halogen atoms, by (C1-C4)alkoxy, by (C1-C4)alkylsulfenyl, by (C1-C4)alkylsulfinyl, by (C1-C4)alkylsulfonyl or by (C1-C4)alkoxycarbonyl, OH, (C1-C4)alkoxy, (C2-C4)alkenyloxy, (C2-C4)alkynyloxy, -OSO2(C1-C4)alkyl, -OCO(C1-C4)alkyl, -OCON[(C1-C4)alkyl]2, -OCONH(C1-C4)alkyl, -OSO2-C6H4-(4)-CH3, -OSO2N(CH3)2, -OCO-C6H5, (C1-C4)alkylsulfenyl, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, -SO2NH(C1-C4)alkyl, -SO2N[(C1-C4)alkyl]2, a phenyl radical which is optionally substituted by halogen, CF3, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxycarbonyl, (C1-C4)alkylsulfenyl, (C1-C4)alkylsulfinyl or (C1-C4)alkylsulfonyl, benzyl, (C1-C4)alkoxycarbonyl, (C2-C4)alkenyloxycarbonyl, (C2-C4)-alkynyloxycarbonyl, aminocarbonyl, (C1-C4)alkylaminocarbonyl or di[(C1-C4)alkyl]aminocarbonyl, R3 is hydrogen or (C1-C4)alkyl, R4 and R5 independently of one another are hydrogen, (C1-C4)alkyl or (C1-C4)alkoxy which may optionally be mono-, di-or tri-substituted by halogen or mono- or di-substituted by (C1-C2)alkoxy, or (C1-C2)alkylthio, halogen, (C1-C4)alkylthio, (C1-C4)alkylamino or (C1-C4)dialkylamino, and if X = NR6, R6 is hydrogen, (C1-C6)alkyl, (C2-C4)alkenyl, (C2-C4)-alkynyl, a phenyl radical which is optionally substituted by halogen, (C1-C4)alkyl, CF3, (C1-C4)alkoxycarbonyl or NO2, -CO(C1-C4)alkyl, -COO(C1-C6)alkyl, -CONH(C1-C6)alkyl, -CON[(C1-C4)-alkyl]2, -CO-C6H5, -CH2-COO(C1-C4)alkyl, -SO2(C1-C4)alkyl or -SO2-C6H4-(4)CH3, and its non-phytotoxic salts.
2. A compound of the formula I as defined in claim 1 wherein X is NR6, Y is CH or nitrogen, R1 is methyl or hydrogen, R2 is methyl, halogen, CF3, difluoromethoxy, methoxycarbonyl, methoxy-sulfonyl, methoxysulfinyl, methoxysulfinyloxy, methoxycarbonyloxy, R3 is hydrogen, R4 and R5 independently of one another are methoxy or methyl and R6 is methyl.
3. A compound of the formula I as defined in claim 1 wherein X is NR6 and R6 is -CO(C1-C4)alkyl, -CH2COO(C1-C4)alkyl, -SO2(C1-C4) alkyl or -SO2-C6H4(4)CH3.
4. Process for the preparation of a compound of the formula I, which comprises a) reacting a compound of the formula (II) II
wherein R7 and R8 independently of one another are hydrogen, (C1-C8)alkyl, (C3-C7)cycloalkyl or phenyl which is optionally monosubstituted or polysubstituted by halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkoxycarbonyl, CF3, NO2 or CH3SO2-, or the radicals R7 and R8 together with the shared nitrogen atom form a 5-membered to 7-membered aliphatic ring, wherein a CH2 group can optionally be replaced by oxygen, NH or N(C1-C4)alkyl, R9 is hydrogen, (C1-C8)alkyl, (C3-C7)cycloalkyl or phenyl, which is optionally monosubstituted or polysubstituted by halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, CF3, NO2 or (C1-C4)alkoxycarbonyl, and R2, R3, R4, R5 and X have the same meanings as in formula (I), with a compound of the formula (III) H-X-NH2 (III) where X has the same meaning as in formula I, or b) converting a compound of the formula I, where X = NR6 and R6 = H, into another compound of the formula I by alkylating or acylating the NH group of the pyrazole ring, or c) converting a compound of the formula I, where R2 = OH, into another compound of the formula (I) by alkylating or acylating or halogenating the heterocyclic OH group.
wherein R7 and R8 independently of one another are hydrogen, (C1-C8)alkyl, (C3-C7)cycloalkyl or phenyl which is optionally monosubstituted or polysubstituted by halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkoxycarbonyl, CF3, NO2 or CH3SO2-, or the radicals R7 and R8 together with the shared nitrogen atom form a 5-membered to 7-membered aliphatic ring, wherein a CH2 group can optionally be replaced by oxygen, NH or N(C1-C4)alkyl, R9 is hydrogen, (C1-C8)alkyl, (C3-C7)cycloalkyl or phenyl, which is optionally monosubstituted or polysubstituted by halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, CF3, NO2 or (C1-C4)alkoxycarbonyl, and R2, R3, R4, R5 and X have the same meanings as in formula (I), with a compound of the formula (III) H-X-NH2 (III) where X has the same meaning as in formula I, or b) converting a compound of the formula I, where X = NR6 and R6 = H, into another compound of the formula I by alkylating or acylating the NH group of the pyrazole ring, or c) converting a compound of the formula I, where R2 = OH, into another compound of the formula (I) by alkylating or acylating or halogenating the heterocyclic OH group.
5. A method for control of undesired plant growth and/or for growth regulation, which comprises applying an effective amount of a compound of the formula I as claimed in claim 1 onto the plants to be treated or onto the cultivation area.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3330602.8 | 1983-08-25 | ||
| DE19833330602 DE3330602A1 (en) | 1983-08-25 | 1983-08-25 | NEW PYRAZOLYL AND ISOXAZOLYL SULFONYL URINS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1223590A true CA1223590A (en) | 1987-06-30 |
Family
ID=6207371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000461749A Expired CA1223590A (en) | 1983-08-25 | 1984-08-24 | Pyrazolylsulfonylureas and isoxazolylsulfonylureas |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0142629A1 (en) |
| JP (1) | JPS6067479A (en) |
| AU (1) | AU3239384A (en) |
| BR (1) | BR8404225A (en) |
| CA (1) | CA1223590A (en) |
| DD (1) | DD228160A5 (en) |
| DE (1) | DE3330602A1 (en) |
| DK (1) | DK405984A (en) |
| ES (1) | ES535373A0 (en) |
| HU (1) | HUT35480A (en) |
| IL (1) | IL72755A0 (en) |
| ZA (1) | ZA846610B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4954164A (en) * | 1982-02-27 | 1990-09-04 | Nissan Chemical Industries, Ltd. | Pyrazolesulfonylurea derivatives, preparation thereof, herbicide containing said derivative as active ingredient and herbicidal method by use thereof |
| AU578307B2 (en) * | 1984-09-17 | 1988-10-20 | E.I. Du Pont De Nemours And Company | Herbicidal pyrazolesulfonamides |
| CA1232273A (en) * | 1984-12-11 | 1988-02-02 | James V. Hay | Herbicidal sulfonamides |
| US4790869A (en) * | 1986-02-07 | 1988-12-13 | Ishihara Sangyo Kaisha Ltd. | Sulfonamide compounds and salts thereof, herbicidal compositions containing them |
| US4946963A (en) * | 1987-11-13 | 1990-08-07 | The University Of North Carolina At Chapel Hill | Compounds for the control of hyperlipidemia using N-substituted isoxazolidine-3,5-diones |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3131489A1 (en) * | 1981-08-08 | 1983-02-24 | Hoechst Ag, 6000 Frankfurt | HETEROCYCLICALLY SUBSTITUTED SULFONYL UREAS, METHOD FOR THEIR PRODUCTION AND THEIR USE IN AGRICULTURE |
| JPS5846071A (en) * | 1981-09-16 | 1983-03-17 | Nippon Tokushu Noyaku Seizo Kk | Substituted phenylsulfonylurea derivative, its intermediate, their preparation, and herbicide |
| US4954164A (en) * | 1982-02-27 | 1990-09-04 | Nissan Chemical Industries, Ltd. | Pyrazolesulfonylurea derivatives, preparation thereof, herbicide containing said derivative as active ingredient and herbicidal method by use thereof |
| EP0096003B2 (en) * | 1982-05-28 | 1994-06-15 | Ciba-Geigy Ag | Sulfonyl(thio)ureas, process for their preparation and their use as herbicides and/or growth regulating agents |
-
1983
- 1983-08-25 DE DE19833330602 patent/DE3330602A1/en not_active Withdrawn
-
1984
- 1984-08-14 EP EP84109650A patent/EP0142629A1/en not_active Withdrawn
- 1984-08-21 HU HU843143A patent/HUT35480A/en unknown
- 1984-08-23 DD DD84266561A patent/DD228160A5/en unknown
- 1984-08-23 JP JP59174210A patent/JPS6067479A/en active Pending
- 1984-08-23 ES ES535373A patent/ES535373A0/en active Granted
- 1984-08-23 IL IL72755A patent/IL72755A0/en unknown
- 1984-08-24 BR BR8404225A patent/BR8404225A/en unknown
- 1984-08-24 AU AU32393/84A patent/AU3239384A/en not_active Abandoned
- 1984-08-24 CA CA000461749A patent/CA1223590A/en not_active Expired
- 1984-08-24 DK DK405984A patent/DK405984A/en not_active Application Discontinuation
- 1984-08-24 ZA ZA846610A patent/ZA846610B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8504780A1 (en) | 1985-05-16 |
| EP0142629A1 (en) | 1985-05-29 |
| AU3239384A (en) | 1985-02-28 |
| DK405984A (en) | 1985-02-26 |
| DD228160A5 (en) | 1985-10-09 |
| IL72755A0 (en) | 1984-11-30 |
| DE3330602A1 (en) | 1985-03-21 |
| JPS6067479A (en) | 1985-04-17 |
| BR8404225A (en) | 1985-07-23 |
| DK405984D0 (en) | 1984-08-24 |
| ZA846610B (en) | 1985-04-24 |
| ES535373A0 (en) | 1985-05-16 |
| HUT35480A (en) | 1985-07-29 |
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