CA2000928A1 - Sulfamoylphenyl ureas - Google Patents
Sulfamoylphenyl ureasInfo
- Publication number
- CA2000928A1 CA2000928A1 CA002000928A CA2000928A CA2000928A1 CA 2000928 A1 CA2000928 A1 CA 2000928A1 CA 002000928 A CA002000928 A CA 002000928A CA 2000928 A CA2000928 A CA 2000928A CA 2000928 A1 CA2000928 A1 CA 2000928A1
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- Prior art keywords
- c4alkyl
- phenyl
- substituted
- hydrogen
- chloroacetyl
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/51—Y being a hydrogen or a carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/84—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
- C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D333/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Hydrogenated Pyridines (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catching Or Destruction (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
5-17276/+
Sulfamoylphenylureas Abstract The N-acylsulfamoylphenylureas of formula I below are suitable as counter-agents (antidotes or safeners) for protecting cultivated plants from the phytotoxic action of herbicides. Suitable crops are preferably cereals, soybeans, sorghum, maize and rice, and suitable herbicides are sulfonylureas, chloroacetanilides and aryloxyphenoxypropionic acid derivatives.
The N-acylsulfamoylphenylureas have the formula I
(I) wherein A is a radical selected from the group , , , or , each of R1 and R2, independently of the other, is hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkynyl, C3-C6alkynyl, or C1-C4alkyl substituted by C1-C4alkoxy
Sulfamoylphenylureas Abstract The N-acylsulfamoylphenylureas of formula I below are suitable as counter-agents (antidotes or safeners) for protecting cultivated plants from the phytotoxic action of herbicides. Suitable crops are preferably cereals, soybeans, sorghum, maize and rice, and suitable herbicides are sulfonylureas, chloroacetanilides and aryloxyphenoxypropionic acid derivatives.
The N-acylsulfamoylphenylureas have the formula I
(I) wherein A is a radical selected from the group , , , or , each of R1 and R2, independently of the other, is hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkynyl, C3-C6alkynyl, or C1-C4alkyl substituted by C1-C4alkoxy
Description
2~ 9~3 5-17276/+
Sulfamoylphenylureas The present invention relates to novel N-acylsulfamoylphenylureas that are suitable for protecting cultivated plants from the phytotoxic action of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloro-acetanilide herbicides and aryloxyphenoxypropionic acid herbicides. The invention relates also to the preparation of the novel compounds and to their use for the protection of cultivated plants. The invention relates also to compositions containing the novel active ingredient and to herbicidal compositions that contain a combination of herbicide and counter-agent, and to corresponding methods of weed control. Finally, the invention relates also to the seeds of cultivated plants protected against herbicidal action by treat1nent with N-acylsulfamoylphenylureas.
It is known that herbicides belonging to the classes of the sulfonyl-ureas, haloacetanilides and aryloxyphenoxypropionic acid derivatives, when employed in an effective concentration, occasionally also damage cultivated plants to a certain extent in addition to the weeds that are to be controlled. Overdoses are often applied unintentionally and accidentally when edge zones overlap during stripwise spraying, either as -a result of wind or as a result of incorrect judgement of the effective width of the spraying apparatus. The climatic conditions or the nature of the soi~ may be such that the concentration of herbicide recommended for normal conditions acts as an overdose. The quality of the seeds may also be a factor in the tolerance of the herbicide. To counteract this problem, various substances have already been proposed which are able specifically to antagonise the harmful action of the herbicide on the cultivated plant, i.e. to protect the cultivated plant without noticeably influencing the herbicidal action on the weeds to be controlled. However, it has been found that the proposed counter-agents often have very species-specific activity both with respect to the cultivated plants and with respect to the herbicide and also, in soms cases, contingent on the mode of application, i.e. a specific counter-agent is often suitable only for a specific cultivated plant and a few classes of herbicide.
For example, British Patent Specification 1 277 557 describes the treat-ment of seeds or shoots of wheat and sorghum with certain oxamic acid esters and amides for protection against attack by "ALACHLOR" (N-methoxy-methyl-N-chloroacetyl-2,6-diethylaniline). U.S. Patent 4 618 331 dis-closes benzoxazine derivatives having a protective action against the herbicidal action of haloacetanilides and sulfonylureas. For protection against sulfonylurea herbicides EP-A-122 231 proposes benzoyloxime ether and EP-A-147 365 proposes phenylglyoxylic acid nitrile oxime, naphtha-lenedicarboxylic acid anhydride, a thiazolecarboxylic acid ester and dichloroacetamides as counter-agents. Furthermore, according to DE-OS 2 402 983 maize plants can be effectively protected against damage by chloroacetanilides by adding an N-disubstituted dichloroacetamide to the soil as counter-agent. Such compounds are used according to DE-OS 2 828 265 and 2 828 293 also as antidotes against herbicidal acet-anilides.
It has surprisingly now been found that a group of N-acylsulfamoylphenyl-ureas are eminently suitable for protecting cultivated plants against the damaging eff~ct of sulfonylurea herbicides, chloroacetanilide herbicides or a}yloxyphenoxypropionic acid herbicides. These N-acylsulfamoylphenyl-ureas are therefore referred to in the following text also as "counter-agents", "antidotes" or "safeners".
The novel N-acylsulfamoylphenylureas proposed according to the invention have the general formula I
~a ~ b R ~ 5O2-NH-CO-A (I) - . :
: ~, 9~8 wherein A is a radical selected from the group R ~ R ~.~d.
R ~Rc f~.=N/
e ~
e or R -~ *-\0/ \S/
each of Rl and R2, independently of the other, is hydrogen, C1-Cgalkyl, C 3-C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C ~ alkynyl, or C1-C4alkyl substituted by C1-C4alkoxy RY
.
--~ or by RY
or R1 and R2 toge~her form a C4-C6alkylene bridge, or a C4-C~alkylene bridge interrupted by oxygen, sulEur, SO, SO2, N~l or by -N(Cl-C4alkyl)-, R3 is hydrogen or C1-C4alkyl, each of Ra and Rb, independently oE the other, is hydrogen, halogen, cyano, nitro, trifluoromethyl, C1-C4alkyl, Cl-C4alkoxy, Cl-C4alkylthio, Cl-C4alkylsulfinyl, Cl-C4alkylsulfonyl, -COORi, -CO~R R , -COR , -SO2NR R or -OSO2-C1-CI,alkyl, or R and R
together form a C3-C4alkylene bridge, which can be substituted by halogen or by C1-C4alkyl, or a C3-C4alkenylene bridge, which can be substituted by halogen or by Cl-C4alkyl, or a C4alkadienylene bridge which can be substituted by halogen or by C1-C4alkyl, each of Rg and Rh, independently of the other, is hydrogen, halogen, C1-C4alkyl, trifluoromethyl, methoxy, methylthio or -COORi, wherein R is hydrogen, halogen, C1-C4alkyl or methoxy, R is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4-alkylthio, Cl-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORi or CONR R , R
is hydrogen, halogen~ C1-C4alkyl, -COORJ, trifluoromethyl or methoxy, or Rd and R together form a C3-C4alkylene bridge, Rf is hydrogen, halogen -, ' 2~ 8 or Cl-C4alkyl, each of R and RY, independently of the other, is hydrogen, halogen, C1-CI,alkyl, Cl-C4alkoxy, C1-C4alkylthio, -CooR4, tri-fluoromethyl, nitro or cyano, each of Ri, Rk and R , independently of the others, is hydrogen or C1-C4alkyl, Rk and Rm together form a C4-C6-alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, NH or by -N(C1-C4alkyl)-, and Rn is C1-C4alkyl, phenyl, or phenyl substituted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl.
In the definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, but preferably fluorine, chlorine and bromine, especially chlorine. Alkyl in the definitions is to be under-stood as being straight-chain or branched alkyl, for example methyl, ethyl, n-propyl, isopropyl or the four butyl isomers. Longer chain alkyl groups include the isomers of pentyl, hexyl, heptyl or octyl, the un-branched chains being preferred in each case. Alkoxy is to be understood as being: methoxy, ethoxy, n-propoxy, isopropoxy or the four isomeric butoxy radicals, but especially methoxy, ethoxy or isopropoxy. Alkyl substituted by alkoxy is preferably methoxymethyl, ethoxymethyl, methoxy-ethyl or ethoxyethyl, but especially methoxyethyl. Alkyl substituted by unsubstituted or substituted phenyl is preferably derivatives of phenyl-ethyl or benzyl. C3-C6alkenyl and C3-C6alkynyl radicals in the definition of Rl and R2 are distinguished by being bonded via a saturated carbon atom to the nitrogen atom carrying them. Typical alkenyl and alkynyl radicals are allyl, 2-butenyl, methallyl, 3-butenyl, propargyl, 2-butynyl, 3-butynyl or 2-pentenyl. Examples of cycloalkyl are cyclo-propyl, cyclopentyl, cyclohexyl and cycloheptyl, but preferably cyclo-pentyl and cyclohexyl. Heterocycles that are formed by R1 and R2 or Rs and R6 together with the nitrogen atom carrying them are pyrrolidine, piperidine, pyrazolidine, imidazolidine, oxazolidine, thiazolidine, morpholine, thiomorpholine, piperazine or hexahydroazepine and, in the case of sulfur-containing rings, the oxidation products thereof. In alkylthio, alkylsulfinyl or alkylsulfonyl, alkyl has the specific mean-ings listsd above.
: . :
: - ~ ': ' :, ' 2~0i9~8 When Ra and R together form a C3-C4alkylene bridge, C3-C4alkenylene bridge or C4alkadienylene bridge, each of which can be substituted by halogen or by Cl-C4alkyl, then, together with the phenyl ring to which the bridge is bonded, dinuclear systems are formed, for example 1,2,3,4-tetrahydronaphthalene 9 1-chloro-2-methyl-3,4-dihydronaphthalene, indane, 1,2-dihydronaphthalene, indene, naphthalene, 2-methylnaphthalene, l~n-butylnaphthalene, 2-ethylnaphthalene or l-chloronaphthalene.
When the substituents Rd and Re together form a C3-C4alkylene bridge, then, together with the ring system to which they are bonded, polynuclear systems are formed, for e~ample 2,3-tetramethylenethiophene, 2,3-tri-methylenethiophene, 2,3-tetramethylenefurane, 3,4-tetramethylenepyridine or / \
'!
~,/ \.
Owing to their good activity as herbicide antagonists, special mention should be made of those compounds wherein either a) R is hydrogen, or b) the sulfamoyl group occupies the 4-position of the phenyl ring, or c) R2 and R3 are hydrogen, or d) A is the group Rg 1RC>~R
A preferred group of compounds of formula I comprises those compounds wherein Rb is hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring. Also preferred are those compounds wherein R2, R3 and R
are hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
2~3~1 39~3 Furthermore, of the compounds of sub-group d), preferred compounds are those wherein R2, R3 and Rb are hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
Of the compounds according to the invention, those falling within the scope of sub-formula Ia ~ R
Rl-NH-CO-NH--~ ~--SO2-NH-CO--~ ~ (Ia) =- =- RC
wherein R1, RC, Rg and Rh are as defined under formula I, are worthy of very special interest.
The compounds of formula Ia wherein Rc is hydrogen are further preferred ln respect of their action. A further sub-group worthy of special mention comprises the compounds of formula Ia wherein the radicals R1, Rg and Rh are C1-C4alkyl groups.
The following individual compounds according to the invention falling within the scope of formula I are preferred:
1-[4-(N-4-methylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1 [4-(N-3-methyl-benzoylsulfamoyl)-phenyl]-3-methylurea~ 1-[4-(N-4-tert.-butylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3-trifluoromethylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-4-nitrobenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-2,3-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3,3-dimethylurea, 1-[4-(N-
Sulfamoylphenylureas The present invention relates to novel N-acylsulfamoylphenylureas that are suitable for protecting cultivated plants from the phytotoxic action of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloro-acetanilide herbicides and aryloxyphenoxypropionic acid herbicides. The invention relates also to the preparation of the novel compounds and to their use for the protection of cultivated plants. The invention relates also to compositions containing the novel active ingredient and to herbicidal compositions that contain a combination of herbicide and counter-agent, and to corresponding methods of weed control. Finally, the invention relates also to the seeds of cultivated plants protected against herbicidal action by treat1nent with N-acylsulfamoylphenylureas.
It is known that herbicides belonging to the classes of the sulfonyl-ureas, haloacetanilides and aryloxyphenoxypropionic acid derivatives, when employed in an effective concentration, occasionally also damage cultivated plants to a certain extent in addition to the weeds that are to be controlled. Overdoses are often applied unintentionally and accidentally when edge zones overlap during stripwise spraying, either as -a result of wind or as a result of incorrect judgement of the effective width of the spraying apparatus. The climatic conditions or the nature of the soi~ may be such that the concentration of herbicide recommended for normal conditions acts as an overdose. The quality of the seeds may also be a factor in the tolerance of the herbicide. To counteract this problem, various substances have already been proposed which are able specifically to antagonise the harmful action of the herbicide on the cultivated plant, i.e. to protect the cultivated plant without noticeably influencing the herbicidal action on the weeds to be controlled. However, it has been found that the proposed counter-agents often have very species-specific activity both with respect to the cultivated plants and with respect to the herbicide and also, in soms cases, contingent on the mode of application, i.e. a specific counter-agent is often suitable only for a specific cultivated plant and a few classes of herbicide.
For example, British Patent Specification 1 277 557 describes the treat-ment of seeds or shoots of wheat and sorghum with certain oxamic acid esters and amides for protection against attack by "ALACHLOR" (N-methoxy-methyl-N-chloroacetyl-2,6-diethylaniline). U.S. Patent 4 618 331 dis-closes benzoxazine derivatives having a protective action against the herbicidal action of haloacetanilides and sulfonylureas. For protection against sulfonylurea herbicides EP-A-122 231 proposes benzoyloxime ether and EP-A-147 365 proposes phenylglyoxylic acid nitrile oxime, naphtha-lenedicarboxylic acid anhydride, a thiazolecarboxylic acid ester and dichloroacetamides as counter-agents. Furthermore, according to DE-OS 2 402 983 maize plants can be effectively protected against damage by chloroacetanilides by adding an N-disubstituted dichloroacetamide to the soil as counter-agent. Such compounds are used according to DE-OS 2 828 265 and 2 828 293 also as antidotes against herbicidal acet-anilides.
It has surprisingly now been found that a group of N-acylsulfamoylphenyl-ureas are eminently suitable for protecting cultivated plants against the damaging eff~ct of sulfonylurea herbicides, chloroacetanilide herbicides or a}yloxyphenoxypropionic acid herbicides. These N-acylsulfamoylphenyl-ureas are therefore referred to in the following text also as "counter-agents", "antidotes" or "safeners".
The novel N-acylsulfamoylphenylureas proposed according to the invention have the general formula I
~a ~ b R ~ 5O2-NH-CO-A (I) - . :
: ~, 9~8 wherein A is a radical selected from the group R ~ R ~.~d.
R ~Rc f~.=N/
e ~
e or R -~ *-\0/ \S/
each of Rl and R2, independently of the other, is hydrogen, C1-Cgalkyl, C 3-C 8 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C ~ alkynyl, or C1-C4alkyl substituted by C1-C4alkoxy RY
.
--~ or by RY
or R1 and R2 toge~her form a C4-C6alkylene bridge, or a C4-C~alkylene bridge interrupted by oxygen, sulEur, SO, SO2, N~l or by -N(Cl-C4alkyl)-, R3 is hydrogen or C1-C4alkyl, each of Ra and Rb, independently oE the other, is hydrogen, halogen, cyano, nitro, trifluoromethyl, C1-C4alkyl, Cl-C4alkoxy, Cl-C4alkylthio, Cl-C4alkylsulfinyl, Cl-C4alkylsulfonyl, -COORi, -CO~R R , -COR , -SO2NR R or -OSO2-C1-CI,alkyl, or R and R
together form a C3-C4alkylene bridge, which can be substituted by halogen or by C1-C4alkyl, or a C3-C4alkenylene bridge, which can be substituted by halogen or by Cl-C4alkyl, or a C4alkadienylene bridge which can be substituted by halogen or by C1-C4alkyl, each of Rg and Rh, independently of the other, is hydrogen, halogen, C1-C4alkyl, trifluoromethyl, methoxy, methylthio or -COORi, wherein R is hydrogen, halogen, C1-C4alkyl or methoxy, R is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4-alkylthio, Cl-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORi or CONR R , R
is hydrogen, halogen~ C1-C4alkyl, -COORJ, trifluoromethyl or methoxy, or Rd and R together form a C3-C4alkylene bridge, Rf is hydrogen, halogen -, ' 2~ 8 or Cl-C4alkyl, each of R and RY, independently of the other, is hydrogen, halogen, C1-CI,alkyl, Cl-C4alkoxy, C1-C4alkylthio, -CooR4, tri-fluoromethyl, nitro or cyano, each of Ri, Rk and R , independently of the others, is hydrogen or C1-C4alkyl, Rk and Rm together form a C4-C6-alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, NH or by -N(C1-C4alkyl)-, and Rn is C1-C4alkyl, phenyl, or phenyl substituted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl.
In the definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, but preferably fluorine, chlorine and bromine, especially chlorine. Alkyl in the definitions is to be under-stood as being straight-chain or branched alkyl, for example methyl, ethyl, n-propyl, isopropyl or the four butyl isomers. Longer chain alkyl groups include the isomers of pentyl, hexyl, heptyl or octyl, the un-branched chains being preferred in each case. Alkoxy is to be understood as being: methoxy, ethoxy, n-propoxy, isopropoxy or the four isomeric butoxy radicals, but especially methoxy, ethoxy or isopropoxy. Alkyl substituted by alkoxy is preferably methoxymethyl, ethoxymethyl, methoxy-ethyl or ethoxyethyl, but especially methoxyethyl. Alkyl substituted by unsubstituted or substituted phenyl is preferably derivatives of phenyl-ethyl or benzyl. C3-C6alkenyl and C3-C6alkynyl radicals in the definition of Rl and R2 are distinguished by being bonded via a saturated carbon atom to the nitrogen atom carrying them. Typical alkenyl and alkynyl radicals are allyl, 2-butenyl, methallyl, 3-butenyl, propargyl, 2-butynyl, 3-butynyl or 2-pentenyl. Examples of cycloalkyl are cyclo-propyl, cyclopentyl, cyclohexyl and cycloheptyl, but preferably cyclo-pentyl and cyclohexyl. Heterocycles that are formed by R1 and R2 or Rs and R6 together with the nitrogen atom carrying them are pyrrolidine, piperidine, pyrazolidine, imidazolidine, oxazolidine, thiazolidine, morpholine, thiomorpholine, piperazine or hexahydroazepine and, in the case of sulfur-containing rings, the oxidation products thereof. In alkylthio, alkylsulfinyl or alkylsulfonyl, alkyl has the specific mean-ings listsd above.
: . :
: - ~ ': ' :, ' 2~0i9~8 When Ra and R together form a C3-C4alkylene bridge, C3-C4alkenylene bridge or C4alkadienylene bridge, each of which can be substituted by halogen or by Cl-C4alkyl, then, together with the phenyl ring to which the bridge is bonded, dinuclear systems are formed, for example 1,2,3,4-tetrahydronaphthalene 9 1-chloro-2-methyl-3,4-dihydronaphthalene, indane, 1,2-dihydronaphthalene, indene, naphthalene, 2-methylnaphthalene, l~n-butylnaphthalene, 2-ethylnaphthalene or l-chloronaphthalene.
When the substituents Rd and Re together form a C3-C4alkylene bridge, then, together with the ring system to which they are bonded, polynuclear systems are formed, for e~ample 2,3-tetramethylenethiophene, 2,3-tri-methylenethiophene, 2,3-tetramethylenefurane, 3,4-tetramethylenepyridine or / \
'!
~,/ \.
Owing to their good activity as herbicide antagonists, special mention should be made of those compounds wherein either a) R is hydrogen, or b) the sulfamoyl group occupies the 4-position of the phenyl ring, or c) R2 and R3 are hydrogen, or d) A is the group Rg 1RC>~R
A preferred group of compounds of formula I comprises those compounds wherein Rb is hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring. Also preferred are those compounds wherein R2, R3 and R
are hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
2~3~1 39~3 Furthermore, of the compounds of sub-group d), preferred compounds are those wherein R2, R3 and Rb are hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
Of the compounds according to the invention, those falling within the scope of sub-formula Ia ~ R
Rl-NH-CO-NH--~ ~--SO2-NH-CO--~ ~ (Ia) =- =- RC
wherein R1, RC, Rg and Rh are as defined under formula I, are worthy of very special interest.
The compounds of formula Ia wherein Rc is hydrogen are further preferred ln respect of their action. A further sub-group worthy of special mention comprises the compounds of formula Ia wherein the radicals R1, Rg and Rh are C1-C4alkyl groups.
The following individual compounds according to the invention falling within the scope of formula I are preferred:
1-[4-(N-4-methylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1 [4-(N-3-methyl-benzoylsulfamoyl)-phenyl]-3-methylurea~ 1-[4-(N-4-tert.-butylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3-trifluoromethylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-4-nitrobenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-2,3-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3,3-dimethylurea, 1-[4-(N-
3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-ethylurea, 1-[4-(N-3,4-dimethyl-benzoylsulfamoyl)-phenyl]-3-allylurea, 1-[4-(N-3,4-dimethylbenzoyl-sulfamoyl)-phenyl]-3-phenylurea, 1-[4-(N-3,5-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dichlorobenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dimethoxybenzoylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3,4-dimethoxybenzoylsulfamoyl~-phenyl]-3,3-dimethylurea, 1-[4-(N-2,4,5-trimethoxybenzoylsulfamoyl)-phenyl]-3-methylurea, l-[4-(N-l-. - ~ . . ..
~:- '" "'' ~: ~' ' 2~928 naphthylcarbonylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-2-furylcarbonyl-sulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea, 1-[4-(N-2-thienylcarbonylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-piperonyloylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3-methylbenzoylsulfamoyl)-phenyl]-3,3-dimethylurea, 1-[4-(N-3-tri-fluoromethylbenzoylsulfamoyl)-phenyl]-3-cyclopropylurea, 1-[3-(N-3,4-di-methylbenzoylsulfamoyl)-phenyl]-3-methylurea, and 1-[3-(N-2-furyl-carbonylsulfamoyl)-phenyl]-3,3-dimethylurea.
The compounds of formula I wherein R1 is as defined under formula I with the exception of hydrogen and R2 is hydrogen, are prepared by reacting a sulfamoylaniline of formula V
~a b ~ R (V) R3 =-~ S02-NH-CO-A
wherein A, R3, Ra and Rb are as defined under formula I, with an iso-cyanate of formula VI
Rl-N=C=0 (VI) wherein R1 is as defined under formula I with the exception of hydrogen.
By reaction with alkylating reagents of formula Lg - R2 wherein Lg is a leaving group such as halogen, tosyl, C6Hs-SO3- or CH30S03- and R2 is as defined under formula I with the exception of hydrogen, it is possible to prepare those compounds of formula I wherein R2 is other than hydrogen. The reaction of the aniline derivatives of formula V with the isocyanate of formula VI can be carried out either without a solvent or in the presence of an aprotic inert organic solvent.
The reactions are advantageously carried out in a solvent. Suitable sol-vents are hydrocarbons such as ben2~ene, toluene, xylene or cyclohexane, 9~3 carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetra-hydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidi-none. The reaction temperatures are preferably from -20 to +120C. The reactions occurring in the coupling processes are generally slightly exothermic and can be carried out at room temperature. In order to reduce the reaction time or also to initiate the reaction, it is expedient to heat the reaction mixture for a short time up to boiling point. The reaction times can also be reduced by the addition of a few drops of base as catalyst. Suitable bases are especially tertiary amines such as tri-methylamine, triethylamine, quinuclidine, N,N-dimethylaminopyridine, pyridine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene. The end products of formula I can either be isolated directly as a crystallisate or by concentration and/or evaporation of the solvent and puriEied by recrystallisation or tritura-tion of the solid residue in solvents in which they are not readily soluble.
In accordance with a second process, the compounds of formula I are obtained by acylating a sulfamoylphenylurea of formula VII
Ra b wherein R1, R2, R3, Ra and R are as defined under formula I, with a carboxylic acid halide of formula VIII
Hal-C0-A (VIII) wherein A is as defined under formula I and Hal is chlorine or bromine.
The reaction of the sulfamoylphenylurea of formula VII with the acylating reagent of formula VIII is advantageously carried out in the presence of an acid-binding agent in an inert organic solvent. Suitable solvents are : , ' 9;;~8 g hydrocarbons such as benzene, toluene, xylene or cyclohexane, carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, ethylene glycol dlmethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from -20 to +120C. The reactions occurring in the coupling processes are generally slightly exothermic and can be carried out at room temperature. In order to reduce the reaction time or also to initiate the reaction, it is expedient to heat the reac-tion mixture for a short time up to boiling point. The reaction times can also be reducsd by the addition of a few drops oE base as catalyst. Suit-able bases are especially tertiary amines such as trimethylamine, tri-ethylamine, quinuclidine, N,N-dimethylaminopyridine, pyridine, 1,4-diaza-bicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,ô-diazabi-cyclo[5.4.0]undec-7-ene. It is also possible, however, to use as bases inorganic bases such as hydrides, such as sodium and calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or hydrogen carbonates such as potassium and sodium hydrogen carbonate. These bases can be used simultaneously as acid-binding agents. The end products of formula I can either be isolated directly as a crystallisate or by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble.
.
The starting compounds of formulae ~, VI, VII and VIII are generally known. Some of the compounds of formulae VI and VII are commercially available. Compounds of formulae V and VIII, for which no specific pre-paration processes have as yet been described in the literature, can be prepared in accordance with the following reaction schemes under the conditions customary for the individual reaction steps:
' :
%~ 2~
Scheme 1 ~ R
OzN~ + Hal-CO-A
¦ Base ~ R
02N--~ ~
¦ catalytic hydLogenation ~ R
Scheme 2 ~a Rb H~ + Cl-CO-O--~ ~-¦ Base ,R
~ O-CO-~
¦ NH/
\R2 R2~
.. : . :
. :' . .: : ' ~:0~ 8 Scheme 3 R~ Cl-~-OH
' I
\N-CO-~
¦ NH~
\N-CO-~
50z-NH2 The compounds of formula I are stable substances under normal laboratory conditions. They do not decompose when stored at room temperature.
A counter-agent or antidote of formula I can be used, according to thepurpose of use, for pre-treating seeds of the cultivated plant (dressing oE seeds or cuttings) or for application to the soil before or after sowlng. It may, however, be applied on its own or together with the herbicide, before or after emergence of the plants. Treatment of the plants or the`seed with the antidote can therefore be carried out in principle independently of the time of application of the herbicide.
Treatment of the plants may, however, also be carried out by simultaneous application of the herbicide and the counter-agent (tank mix). Pre-emergence treatment includes both treatment of the cultivation area before sowing (ppi = pre plant incorporation) and treatment of the sown cultivation area before emergence of the crop.
The amount of counter-agent applied in relation to the herbicide depends to a large extent on the mode of application. In the case of field treat-ment in which the herbicide and the counter-agent are applied either simultaneously (tank mix) or separately, the ratio of the amounts of ~. , , :
Z~9~
counter-agent to herbicide is in the range of from 1:100 to 5:1. As a rule, full protective action is achieved with a ratio of counter-agent to herbicide of from 5:1 to 1:50. With seed dressing and similar selective protective measures, however, far smaller quantities of counter-agent are required in relation to the quantities of herbicide subsequently applied per hectare of cultivation area. In general, in the case of seed dress-ing, from 0.1 to 10 g of counter-agent are required per kg of seed. As a rule, full protective action is achieved with from 0.1 to 5 kg of counter-agent per kg of seed. If the counter-agent is to be applied by soaking the seed shortly before sowing, it is advantageous to use solutions of the counter-agent that contain the active ingredient in a concentration of from 1 to 10,000 ppm. As a rule, full protective action is achieved with counter-agent concentrations of from 100 to 1,000 ppm.
As a rule, there is a relatively long time lapse between protective measures, such as seed dressing and treatment of cuttings with a counter-agent of formula I, and the possible later field treatment with herbicides. In agriculture, horticulture and forestry, pre-treated seeds and plant material may subsequently come into contact with a variety of chemicals. The invention therefore relates also to protective composi-tions for cultivated plants that contain, as actlve ingredient, a counter-agent of formula I together with customary carriers. Such compo-sitions may optionally contain, in addition, those herbicides from whose effects the cultivated plants are to be protected. The invention relates also to propagation material from cultivated plants, such as seeds, plantlets and cuttings, that has been pretreated with compounds of for-mula I. The compounds of formula I are especially suitable for the treat-ment of seeds of cereals, soybeans and preferably sorghum, maize and rice.
Cultivated plants within the scope of the present invention are, for example, all types of cereal, such as wheat, rye, barley and oats, and also, especially, rice, cultivated sorghum, maize and soybeans. The com-pounds of formula I are preferably used to protect sorghum, maize and .
' ' : ..
, ,~
- ~ .
X~''3%~3 ~
rice against the action of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxypropionic acid herbicides.
Outstanding protective action against acylcyclohexanedione herbicides, sulfonylurea herbicides, aryloxyphenoxypropionic acid herbicides and chloroacetanilide herbicides is to be observed when the antidotes of formula I are used in maize, sorghum and rice. In particular, special mention should be made of the advantageous effect of the compound 1-[4-(N-3,4-dimethylbenzoylsulfamoyl~-phenyl]-3-methylurea.
Sulfonylurea herbicides, whose damaging effect on cultivated plants canbe eliminated with the aid of the N-acylsulfamoylphenylureas of for-mula I, have recently become known in great number. Of the many publica-tions devoted to the disclosure of herbicidally active sulfonylurea derivatives there may be mentioned by way of example US Patent 4,127,405 and published European Patent Applications EP-A-7687, EP-A-30142, EP-A-44807, EP-A-44808, EP-A-51466, EP-A-70802, EP-A-84020, EP-A-87780, EP-A-102925, EP-A-108708, EP-A-120814, EP-A-13606:L, EP-A-184385, EP-A-20699S and EP-A-237292.
Typical examples of herbicidal sulfonylurea derivatives are encompassedby formula II
E-(C~ ~ -50z-~N-CO-~ Y
9~
wherein E is a group /Rs \ - / ' \ -N/ ' \S/
R~
/
or ~\
1~.3 n is O or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, Cl-C4haloalkoxy, C1-C4haloalkylthio, C2-C4haloalkenyl, chlorine or Cl-C4-alkoxycarbonyl, Rs is trifluoromethyl or di(Cl-C4alkyl)carbamoyl, R6 is Cl-C4alkoxycarbonyl, R7 is C1-C4alkoxycarbonyl, and R~ is C1-C4alkyl.
The following individual herbicidally active substances fall within thescope of formula II:
N-(3-trifluoromethylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(3-dimethylcarbamoylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(1-methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea~ N-(2-methoxycarbonylthien-3-yl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxy-carbonylbenzylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-ethoxy-6-methyl-amino-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-ethoxycarbonylphenyl-sulfonyl)-N'-(4-chloro-6-methoxypyrimidin-2-yl)-urea, N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea and N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-tria7in-2-yl)-urea.
, . . .
,~ : ~; :
. . ..
Haloacetanilides, whose damaging effect on cultivated plants can be eliminated with the aid of the N-acylsulfamoylphenylureas of formula I, are already known in great numbsr. Such haloacetanilides can be described by the following general formula III:
N/ (III) R~ CO-CH 2 Cl wherein L is a C1-C4alkylene bridge, each of R9 7 R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1~C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-Csalkoxyalkyl or C2-Csalkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyrrolyl, unsubsti-tuted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxadi-azol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, unsubsti-tuted or substituted 1,2,4-triazol-3-yl, unsubstituted or substituted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or sub-stituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetrahydro-furyl.
The following herbicidal chloroacetanilide derivatives especially fall within the scope of formula III:
N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chlo~oacetyl-N-methoxymethyl-2,6-diethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(methoxy-ethyl)-2,6-diethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methyl-aniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline, N-chloro-acetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline, N-(2-ethoxy-' ~ .. . .
:
2~ 9i~8 ethyl)-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-(2-n-propoxy-ethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methyl-aniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline, N-chloroacetyl-N-(2,2-di-ethoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methyl-ethyl)-2,3-dimethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-methyl-aniline, N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline, N-chloro-acetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline, N-(2-ethoxy-2-methylethyl)-N-chloroacatyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(l-ethyl-l-methoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-.
methoxyethyl)-2-methoxy-6-methylaniline, N-n-butoxymethyl-N-chloroace~yl-2-tert.-butylaniline, N-(2-ethoxyethyl-2-methylethyl)-2,6-dimethyl-aniline, N-chloroacetyl-N-(2- methoxyethyl)-2-chloro-6-methylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline, N-(2-ethoxy-ethyl)-N-chloroacetyl-2,3,6-trimethylaniline, N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline, N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-dimethyl-aniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methyl-aniline, N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methyl-aniline, N-chloroacetyl-N-(2-furylmethyl)-2,6-dimethylaniline, N-chloro-acetyl-N-(2-furylmethyl)-2-ethyl-6-methylaniline~ N-chloroacetyl-N-(2-tetrahydrofurvlmethyl)-2,6-dimethylaniline, N-ch:Loroacetyl-N-(N,N-di-methylcarbamoylmethyl)-2,6-dimethylaniline, N-(n-butoxymethyl)-N-chloro-acetyl-2,6-diethylaniline, N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-di-ethylaniline, N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-di-methylaniline, N-chloroacetyl-N-isopropyl-2,3-dimethylaniline, N-chloro-acetyl-N-isopropyl-2-chloroaniline, N-chloroacetyl-N-(lH-pyrazol-1-yl-methyl)-2,6-dimethylaniline, N-chloroacetyl-N-(lH-pyrazol-l-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylani`Line~ N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline, N-chloroacetyl-39~:~
N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert.-butylaniline, N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline and N-chloroacetyl-N-(l-methyl-5-methylthio-l,3,.4-triazol-2-ylmethyl)-2,6-diethylaniline.
Aryloxyphenoxypropionic acid herbicides, whose damaging effect on culti-vated plants can be eliminated with the aid of the N-acylsulfamoylphenyl-ureas of formula I, are known in great number. Such aryloxyphenoxyprop-ionic acid derivatives can be described by the following general formula IV:
Q-O ~ O-CH-CO-T (IV) wherein Q is a radical \ =. =N Rl4/ ~-/ \O/
~ or \~
Rl 4 / ~-/ \S/ ~./ N~
and T is -NRlsRls, -N(CN)Rl7, -ORls, SRls or -o-N=CRl9RZ0, wherein Rl3 is halogen or trifluoromethyl, R1 4 is hydrogen or halogen, each of R1s and R15, independently of the other, is hydrogen, Cl-C8alkoxy, C1-Cgalk`yl, phenyl or benzyl, R1s and R15 together with the nitrogen atom carrying them form a 5- or 6-membered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, Rl3 is hydrogen or the equiv-alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary Cl-C4alkylammonium or Cl-C4hydroxyalkylammonium radical; a Cl-C9alkyl radical that is unsubstituted or mono- or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, Cl-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR2l, -COSR2l, -CONH2, -CON(Cl-C 4 alkoxy)-Cl-C 4 alkyl, -CO-N-di-Cl-C 4 alkyl, CONH-Cl-C 4 alkyl, -N(Cl-C4alkoxy)-Cl-C4alkyl or by di-Cl-C4alkylamino; a C3-Cgalkenyl radical that is unsubstituted or substituted by halogen or by Cl-C4-2Cii~9Z~
alkoxy; a C3-Cgalkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-Cgcycloalky].; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1-C4alkoxy, acetyl, -COOR21, COSRZ17 -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4alkyl, or together they form a 3- to 6-membered alkylene chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3-C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
The following herbicidal aryloxyphenoxypropionic acid derivatives especially fall within the scope of formula IV:
2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)~phenoxy]-thioprop-ionic acid propargyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid methyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, 2-[4-(5-trifluoromethyl-pyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, 2-[4-(5-trifluoro-methylpyridin-2-yloxy)-phenoxy]-propionic acid methyl ester, 2-[4-(6-chloroquinoxalin-2-yloxy)-phenoxy]-propionic acid ethyl ester and 2-[4-(6-chlorobenzoxazolin-2-yloxy)-phenoxy]-propionic acid ethyl ester.
Acylcyclohexanedione derivatives, whose damaging effect on cultivated plants can be eliminated with the aid of the N-acylsulfamoylphenylureas of formula I, are described, for example, in published European Patent Application No. O 243 313. Such acylcyclohexanedione derivatives can be described by the following general formula IX
R ~f' R22-S(O~ (C )l l~ (IX) wherein A' is a 2- ~o 7-membered alkylene bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n' is O, 1 or 2, R22 is C1-C4alkyl or benzyl, R23 is Cl-C6alkyl unsubstituted or sub-stituted by halogen, C~-C4alkoxy or by C1-C4alkylthio; C3-C6cycloalkyl;
'', ' , ~ -9~8 phenyl, benzyl or phenylethyl wherein the phenyl ring Gan be substituted by halogen, C1-C4alkyl, C~-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C1-CI,haloalkoxy, cyano or by nitro, X' is oxygen or a radical -NORz4~ and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or 3 -C 6 alkynyl.
The following herbicidal acylcyclohexanedione derivatives especially fall within the scope of formula IX:
5-(1-Methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-cyclopropylcarbonylcyclohexane-1,3-dione, S-(1-methylthiocyclobutan-1-yl)-2-(2,3-dichlorobenzoyl)-cyclo-hexane-1,3-dione, 5-(1-methylsulfonylcyclobutan-1-yl)-2-n-butyrylcyclo-hexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-propionylcyclo-hexane-1,3-dione, 5-(1-ethylthiocyclopropan-1-yl)-2-propionylcyclo-hexane-1,3-dione and 5--(1-methylthiocyclopropan-1-yl)-2-n-butyrylcyclo-hexane 1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclohexan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthio-cyclobutan-1-yl)-2-(1-allyloxyimino-n-butyryl)-cyclohexane-1,3-dione and 5-(1-methylthiocyclopentan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxy-imino)-n-butyryl]-cyclohexane 1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(cis-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione and 5-(1-ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione.
The antidotes of formula I are most especially suitable for protecting cultivated plants from the herbicidal action of herbicides of formulae II, III and IV.
Agrochemical compositions that contain in a common formulation togetherwith the antidote of formula I a sulfonylurea herbicida, a chloroacet-anilide herbicide or an aryloxyphenoxypropionic acid herbicide are :. :
:
:
9~
suitable for use as selective herbicides in crops of useful plants. The herbicidal compositions of the invention preferably contain, in addition to an antidote of formula I, a sulfonylurea of formula II, a chloro-acetanilide of formula III, an acylcyclohexanedione derivative of formula IX or an aryloxyphenoxypropionic acid derivativs of formula IY.
Unless used for dressing seed, the amount of counter-agent applied varies between about 0.01 and about 5 parts by weight per part by weight of herbicide. In practice, the most suitable ratio with regard to the optimum effect on the specific cultivated plant is determined from case to case, that is to say depending upon the type of herbicide used.
The invention relates also to a method of selectively controlling weedsin crops of cultivated plants, in which the crops of cultivated plants, parts of the cultivated plants or the cultivation areas of the cultivated plants are treated with a herbicide and a compound of formula I or with a composition containing that combination. The present invention relates also to the compositions containing the combination of herbicide and antidote.
The weeds to be controlled may be either monocotyledonous or di-cotyledonous weeds.
Various methods and techniques are suitable for employing the compoundsof formula I or compositions containing them for the protection of culti-vated plants from the damaging effects oE agrochemicals. Examples of these methods and techniques are:
i) Seed dressing a) dressing the seed with an active ingredient formulated as a wettable powder~ by shaking in a vessel until uniform distribution over the surface of the seed is achieved (dry dressing). In this procedure, about 10 to 500 g of active ingredient of formula I (40 g to 2 kg of wettable powder in the case of a 25 % strength formulation) are used per 100 kg of seed.
g~
b) dressing the seed with an emulsifiable concentrate of the active ingredient or with an aqueous solution of a wettable powder formulation of the active ingredient of formula I by method a) (wet dressing).
c) dressing by immersing the seed in a liquor containing from 50 to 3,200 ppm of an active ingredient of formula I for from 1 to 72 hours and, if desired, subsequently drying the seed (immersion dressing, seed soaking).
Dressing the seed or treating the sprouted seedling are, of course, thepreferred methods of application since the treatment with the active ingredient is directed entirely towards the target crop. As a rule, from 10 g to 500 g, preferably from 50 to ~00 g, of active ingredient are used per 100 kg of seed, and, depending upon-the method employed, which also allows other active ingredients or micronutrients to be added, it is possible to exceed or use less than the concentration limits indicated (repeat dressing).
ii) Application from a tank mix A liquid formulation of a mixture of counter-agent and herbicide (ratio of the one to the other from 10:1 to 1:30~ is used, the application rate of herbicide being from 0.001 to lO kg per hectare: A tank mix of this type is preferably applied before or after sowing or is worked 5 to 10 cm deep into the soil before sowing.
iii~ Application to the seed furrow The counter-agent is introduced in the form of an emulsifiable concen-trate, wettable powder, or granulate into the open, sown seed furrow and then, after the seed furrow has been covered, the herbicide is applied in the normal manner according to the pre-emergence method.
: .
:
~ 2~2~8 iv) Controlled release of active ingredient A solution of the active ingredient is adsorbed onto mineral granulate carriers or polymerised granules (urea/formaldehyde) and is allowed to dry. If desired, it is possible to apply a coating (coated granulate) which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of for-mulation and are therefore formulated e.g. into emulsifiable concen-trates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsula-tions. As with the nature of the compositions, the methods of applica-tion, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures con-taining the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, sur-face-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, di-methyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil;
or water.
, The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, mont-morillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite;
and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
The term "surfactants" will also be understood as comprising mixtures oE
surfactants.
Both so-called water-soluble soaps and also water--soluble synthetic sur-face-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-c22)7 e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyl-taurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C2 z-alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligno-sulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sul-;
:
92~3 fates obtained f}om natural fatty acids. These com,oounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediaminopoly-propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpoly-ethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenolpolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
- ~ :'. ,' ~ : ' .
: , .
'I ' ~ I . :'. ' I
.: ~ :
. ~ .
~o~9~
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C~-C2z-alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described inter alia in the following publications:
"198; International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ, USA, 1985, H. Stache~ "Tensid-Taschenbuch", 2nd Edition, C. Hanser Verlag Munich, Vienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemic~l Publishing Co., New York, 1980-1981.
The agrochemical compositions usually contain 0.1 to 95 %, preferably 0.1 to 80 Yo~ of a compound of formula I, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
Preferred formulations are composed especially of the following constitu-ents tthroughout percentages are by weight):
Emulsifiable concentrates:
active ingredient mixture: 1 to 20 %, preferably 5 to 10 %
surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier: 50 to 94 %, preferably 70 to 85 %
Dusts:
active ingredient mixture:0.1 to 10 %, preferably 0.1 to 1 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient mixture: 5 to 75 %, preferably 10 to 50 %
water:94 to 25 %, preferably 88 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %
...
,. ~.
., ': .:
9~8 Wettable powders:
active ingredient mixture: 0.5 to 90 ~/0, preferably I to 80 %
surfactant: 0.5 to 20 %, preferably 1 to 15 %
solid carrier:5 to 95 %, preferably 15 to 90 %
_anulates:
active ingredient mixture:0.5 to 30 %, preferably 3 to 15 %
solid carrier:99.5 to 70 %, preferably 97 to 85 %
Whereas commercial products will preferably be formulated as concen-trates, the end user will normally employ dilute formulations. The for-mulations may be diluted down to a concentration of 0.001 % active in-gredient. The rates of application are normally from 0.01 to 10 kg a.i.tactive ingredient)/ha, preferably from 0.25 to 5 kg a.i./ha.
The compositions may also contain further auxiliaries such as stabi-lisers, antifoams, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtain-ing special effects.
The following Examples serve to illustrate the invention. They do not limit the invention.
Preparation Examples:
Example_Pl: 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl] 3-methylurea H3C-NH-C0-NH-~ -SO2-NH-CO~ -CH3 : ' :.,~,',; - :
- ':' . ' : ~ `
a) N-(4-sulfamoylphenyl)-0-phenylcarbamate.
176 g of sulfanilamide are suspended in 750 ml of dioxane, and 79 g of pyridine are added thereto. 160 g of chloroformic acid phenyl ester are then added dropwise to that mixture at 15C. The reaction suspension is stirred at 50C for l hour, cooled and stirred into 2 litres of water.
The precipitated product is separated off and dried, yielding 277 g of N-(4-sulfamoylphenyl)-0-phenylcarbamate, m.p. 220-223C.
b) l-(4-sulfamoylphenyl)-3-methylurea.
330 ml of a 33 % ethanolic methylamine solution are added dropwise at 30C to a suspension of 350 g of N-(4-sulfamoylphenyl)-0-phenylcarbamate in 1500 ml of ethanol. The product crystallises out of the initially clear solution within a period of 1.5 hours. After the reaction mixture has cooled, the precipitate is separated off and dried, yielding 256 g of 1-(4-sulfamoylphenyl)-3-methylurea, m.p. 211-213C.
c) 56.7 g of 3,4-dimethylbenzoyl chloride and 3.9 g of 4-dimethylamino-pyridine are added to a suspension of 73.3 g of 1-(4-sulfamoylphenyl)-3-methylurea in 600 ml of acetonitrile. 98.1 g of triethylamine are added dropwise to that mixture, during which the temperature of the mixture rises from room temperature to 45C and the disperse constituents enter into solution. After a short time crystallisation begins. After a further 2.5 hours, the mixture is stirred into 2.5 litres of ice-water and 200 ml of 2N sulfuric acid. The precipitated product is separated off, washed with ether and dried, yielding 114.4 g of 1-[4-(N-3,4-dimethylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, m.p. 236-230C (with decomposition).
xample P2: 1-[3-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea /N-C0-NH~
H3C \.=.- S02-NH-C0 \0 - :
~, :
.: :
':: ~' . , ~ ~ "
.L i .
. :. . .
Z~ 9~8 a) N-(3-sulfamoylphenyl)-0-phenylcarbamate.
113 g of chloroformic acid phenyl ester are added dropwise at 15C to a suspenSion of 125 g of 3-aminobenzenesulfonamide and 57.9 g of pyridine in 500 ml of dioxane. The mixture is stirred for one hour at room tem-perature and for one hour at 50C and then stirred into 2 litres of water. The precipitated product is separated off and dried, yielding 201 g of N-(3-sulfamoylphenyl)-0-phenylcarbamate, m.p. 184-186C ~with decompos',.tion).
b) 1-(3-sulfamoylphellyl)-3,3-dimethylurea.
A mixture of 205 g of N-(3-sulfamoylphenyl)-0-phenylcarbamate and 158 g of a 40 % aqueous solution of dimethylamine is heated at reflux in 500 ml of ethanol for 3 hours. The solvent is distilled off under reduced pressure. Water is added to the residue and the phenol that is formed is driven off with steam. After the distillation flask has cooled, the crystalline residue is separated off, washed with cold methanol and dried, yielding 136 g of 1-(3-sulfamoylphenyl)-3,3-dimethylurea, m.p.
193-19~C.
c) 6.1 g of 2-furancarboxylic acid chloride and 0.1 g of 4-dimethylamino-pyridine are added to a suspension of 10.1 g of 1-t3-sulfamoylphenyl)-3,3-dimethylurea in 60 ml of acetonitrile. 9.5 g of triethylamine are added dropwise to that mixture at room temperature. The reaction mixture is stirred ~or 15 hours at room temperature and for one hour at 60C.
After the mixture has cooled, 4.5 g of methanesulfonic acid are added dropwise thereto and the mixture is taken up in 1 litre of water. The oil that separates out crystallises after a short time. The crystals are separated off, washed with methanol and dried, yielding 11.3 g of 1-[3-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea, m.p.
216-217C (with decomposition).
~xample P3: 1-[4-(N-3t4-dimethylbenzoylsulfamoyl)-phenYl]-3-allylurea /CH~
H2C=CH-CH2-NH-C0-NH-~ -S02-NH-C0--~ ~--CH3 :
~:- '" "'' ~: ~' ' 2~928 naphthylcarbonylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-2-furylcarbonyl-sulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea, 1-[4-(N-2-thienylcarbonylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-piperonyloylsulfamoyl)-phenyl]-3-methylurea, 1-[4-(N-3-methylbenzoylsulfamoyl)-phenyl]-3,3-dimethylurea, 1-[4-(N-3-tri-fluoromethylbenzoylsulfamoyl)-phenyl]-3-cyclopropylurea, 1-[3-(N-3,4-di-methylbenzoylsulfamoyl)-phenyl]-3-methylurea, and 1-[3-(N-2-furyl-carbonylsulfamoyl)-phenyl]-3,3-dimethylurea.
The compounds of formula I wherein R1 is as defined under formula I with the exception of hydrogen and R2 is hydrogen, are prepared by reacting a sulfamoylaniline of formula V
~a b ~ R (V) R3 =-~ S02-NH-CO-A
wherein A, R3, Ra and Rb are as defined under formula I, with an iso-cyanate of formula VI
Rl-N=C=0 (VI) wherein R1 is as defined under formula I with the exception of hydrogen.
By reaction with alkylating reagents of formula Lg - R2 wherein Lg is a leaving group such as halogen, tosyl, C6Hs-SO3- or CH30S03- and R2 is as defined under formula I with the exception of hydrogen, it is possible to prepare those compounds of formula I wherein R2 is other than hydrogen. The reaction of the aniline derivatives of formula V with the isocyanate of formula VI can be carried out either without a solvent or in the presence of an aprotic inert organic solvent.
The reactions are advantageously carried out in a solvent. Suitable sol-vents are hydrocarbons such as ben2~ene, toluene, xylene or cyclohexane, 9~3 carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetra-hydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidi-none. The reaction temperatures are preferably from -20 to +120C. The reactions occurring in the coupling processes are generally slightly exothermic and can be carried out at room temperature. In order to reduce the reaction time or also to initiate the reaction, it is expedient to heat the reaction mixture for a short time up to boiling point. The reaction times can also be reduced by the addition of a few drops of base as catalyst. Suitable bases are especially tertiary amines such as tri-methylamine, triethylamine, quinuclidine, N,N-dimethylaminopyridine, pyridine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene. The end products of formula I can either be isolated directly as a crystallisate or by concentration and/or evaporation of the solvent and puriEied by recrystallisation or tritura-tion of the solid residue in solvents in which they are not readily soluble.
In accordance with a second process, the compounds of formula I are obtained by acylating a sulfamoylphenylurea of formula VII
Ra b wherein R1, R2, R3, Ra and R are as defined under formula I, with a carboxylic acid halide of formula VIII
Hal-C0-A (VIII) wherein A is as defined under formula I and Hal is chlorine or bromine.
The reaction of the sulfamoylphenylurea of formula VII with the acylating reagent of formula VIII is advantageously carried out in the presence of an acid-binding agent in an inert organic solvent. Suitable solvents are : , ' 9;;~8 g hydrocarbons such as benzene, toluene, xylene or cyclohexane, carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, ethylene glycol dlmethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from -20 to +120C. The reactions occurring in the coupling processes are generally slightly exothermic and can be carried out at room temperature. In order to reduce the reaction time or also to initiate the reaction, it is expedient to heat the reac-tion mixture for a short time up to boiling point. The reaction times can also be reducsd by the addition of a few drops oE base as catalyst. Suit-able bases are especially tertiary amines such as trimethylamine, tri-ethylamine, quinuclidine, N,N-dimethylaminopyridine, pyridine, 1,4-diaza-bicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,ô-diazabi-cyclo[5.4.0]undec-7-ene. It is also possible, however, to use as bases inorganic bases such as hydrides, such as sodium and calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or hydrogen carbonates such as potassium and sodium hydrogen carbonate. These bases can be used simultaneously as acid-binding agents. The end products of formula I can either be isolated directly as a crystallisate or by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble.
.
The starting compounds of formulae ~, VI, VII and VIII are generally known. Some of the compounds of formulae VI and VII are commercially available. Compounds of formulae V and VIII, for which no specific pre-paration processes have as yet been described in the literature, can be prepared in accordance with the following reaction schemes under the conditions customary for the individual reaction steps:
' :
%~ 2~
Scheme 1 ~ R
OzN~ + Hal-CO-A
¦ Base ~ R
02N--~ ~
¦ catalytic hydLogenation ~ R
Scheme 2 ~a Rb H~ + Cl-CO-O--~ ~-¦ Base ,R
~ O-CO-~
¦ NH/
\R2 R2~
.. : . :
. :' . .: : ' ~:0~ 8 Scheme 3 R~ Cl-~-OH
' I
\N-CO-~
¦ NH~
\N-CO-~
50z-NH2 The compounds of formula I are stable substances under normal laboratory conditions. They do not decompose when stored at room temperature.
A counter-agent or antidote of formula I can be used, according to thepurpose of use, for pre-treating seeds of the cultivated plant (dressing oE seeds or cuttings) or for application to the soil before or after sowlng. It may, however, be applied on its own or together with the herbicide, before or after emergence of the plants. Treatment of the plants or the`seed with the antidote can therefore be carried out in principle independently of the time of application of the herbicide.
Treatment of the plants may, however, also be carried out by simultaneous application of the herbicide and the counter-agent (tank mix). Pre-emergence treatment includes both treatment of the cultivation area before sowing (ppi = pre plant incorporation) and treatment of the sown cultivation area before emergence of the crop.
The amount of counter-agent applied in relation to the herbicide depends to a large extent on the mode of application. In the case of field treat-ment in which the herbicide and the counter-agent are applied either simultaneously (tank mix) or separately, the ratio of the amounts of ~. , , :
Z~9~
counter-agent to herbicide is in the range of from 1:100 to 5:1. As a rule, full protective action is achieved with a ratio of counter-agent to herbicide of from 5:1 to 1:50. With seed dressing and similar selective protective measures, however, far smaller quantities of counter-agent are required in relation to the quantities of herbicide subsequently applied per hectare of cultivation area. In general, in the case of seed dress-ing, from 0.1 to 10 g of counter-agent are required per kg of seed. As a rule, full protective action is achieved with from 0.1 to 5 kg of counter-agent per kg of seed. If the counter-agent is to be applied by soaking the seed shortly before sowing, it is advantageous to use solutions of the counter-agent that contain the active ingredient in a concentration of from 1 to 10,000 ppm. As a rule, full protective action is achieved with counter-agent concentrations of from 100 to 1,000 ppm.
As a rule, there is a relatively long time lapse between protective measures, such as seed dressing and treatment of cuttings with a counter-agent of formula I, and the possible later field treatment with herbicides. In agriculture, horticulture and forestry, pre-treated seeds and plant material may subsequently come into contact with a variety of chemicals. The invention therefore relates also to protective composi-tions for cultivated plants that contain, as actlve ingredient, a counter-agent of formula I together with customary carriers. Such compo-sitions may optionally contain, in addition, those herbicides from whose effects the cultivated plants are to be protected. The invention relates also to propagation material from cultivated plants, such as seeds, plantlets and cuttings, that has been pretreated with compounds of for-mula I. The compounds of formula I are especially suitable for the treat-ment of seeds of cereals, soybeans and preferably sorghum, maize and rice.
Cultivated plants within the scope of the present invention are, for example, all types of cereal, such as wheat, rye, barley and oats, and also, especially, rice, cultivated sorghum, maize and soybeans. The com-pounds of formula I are preferably used to protect sorghum, maize and .
' ' : ..
, ,~
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X~''3%~3 ~
rice against the action of acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxypropionic acid herbicides.
Outstanding protective action against acylcyclohexanedione herbicides, sulfonylurea herbicides, aryloxyphenoxypropionic acid herbicides and chloroacetanilide herbicides is to be observed when the antidotes of formula I are used in maize, sorghum and rice. In particular, special mention should be made of the advantageous effect of the compound 1-[4-(N-3,4-dimethylbenzoylsulfamoyl~-phenyl]-3-methylurea.
Sulfonylurea herbicides, whose damaging effect on cultivated plants canbe eliminated with the aid of the N-acylsulfamoylphenylureas of for-mula I, have recently become known in great number. Of the many publica-tions devoted to the disclosure of herbicidally active sulfonylurea derivatives there may be mentioned by way of example US Patent 4,127,405 and published European Patent Applications EP-A-7687, EP-A-30142, EP-A-44807, EP-A-44808, EP-A-51466, EP-A-70802, EP-A-84020, EP-A-87780, EP-A-102925, EP-A-108708, EP-A-120814, EP-A-13606:L, EP-A-184385, EP-A-20699S and EP-A-237292.
Typical examples of herbicidal sulfonylurea derivatives are encompassedby formula II
E-(C~ ~ -50z-~N-CO-~ Y
9~
wherein E is a group /Rs \ - / ' \ -N/ ' \S/
R~
/
or ~\
1~.3 n is O or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, Cl-C4haloalkoxy, C1-C4haloalkylthio, C2-C4haloalkenyl, chlorine or Cl-C4-alkoxycarbonyl, Rs is trifluoromethyl or di(Cl-C4alkyl)carbamoyl, R6 is Cl-C4alkoxycarbonyl, R7 is C1-C4alkoxycarbonyl, and R~ is C1-C4alkyl.
The following individual herbicidally active substances fall within thescope of formula II:
N-(3-trifluoromethylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(3-dimethylcarbamoylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(1-methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea~ N-(2-methoxycarbonylthien-3-yl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxy-carbonylbenzylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-ethoxy-6-methyl-amino-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-ethoxycarbonylphenyl-sulfonyl)-N'-(4-chloro-6-methoxypyrimidin-2-yl)-urea, N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea and N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-tria7in-2-yl)-urea.
, . . .
,~ : ~; :
. . ..
Haloacetanilides, whose damaging effect on cultivated plants can be eliminated with the aid of the N-acylsulfamoylphenylureas of formula I, are already known in great numbsr. Such haloacetanilides can be described by the following general formula III:
N/ (III) R~ CO-CH 2 Cl wherein L is a C1-C4alkylene bridge, each of R9 7 R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1~C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-Csalkoxyalkyl or C2-Csalkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyrrolyl, unsubsti-tuted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxadi-azol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, unsubsti-tuted or substituted 1,2,4-triazol-3-yl, unsubstituted or substituted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or sub-stituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetrahydro-furyl.
The following herbicidal chloroacetanilide derivatives especially fall within the scope of formula III:
N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chlo~oacetyl-N-methoxymethyl-2,6-diethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(methoxy-ethyl)-2,6-diethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methyl-aniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline, N-chloro-acetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline, N-(2-ethoxy-' ~ .. . .
:
2~ 9i~8 ethyl)-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-(2-n-propoxy-ethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methyl-aniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline, N-chloroacetyl-N-(2,2-di-ethoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methyl-ethyl)-2,3-dimethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-methyl-aniline, N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline, N-chloro-acetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline, N-(2-ethoxy-2-methylethyl)-N-chloroacatyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(l-ethyl-l-methoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-.
methoxyethyl)-2-methoxy-6-methylaniline, N-n-butoxymethyl-N-chloroace~yl-2-tert.-butylaniline, N-(2-ethoxyethyl-2-methylethyl)-2,6-dimethyl-aniline, N-chloroacetyl-N-(2- methoxyethyl)-2-chloro-6-methylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline, N-(2-ethoxy-ethyl)-N-chloroacetyl-2,3,6-trimethylaniline, N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline, N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-dimethyl-aniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methyl-aniline, N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methyl-aniline, N-chloroacetyl-N-(2-furylmethyl)-2,6-dimethylaniline, N-chloro-acetyl-N-(2-furylmethyl)-2-ethyl-6-methylaniline~ N-chloroacetyl-N-(2-tetrahydrofurvlmethyl)-2,6-dimethylaniline, N-ch:Loroacetyl-N-(N,N-di-methylcarbamoylmethyl)-2,6-dimethylaniline, N-(n-butoxymethyl)-N-chloro-acetyl-2,6-diethylaniline, N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-di-ethylaniline, N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-di-methylaniline, N-chloroacetyl-N-isopropyl-2,3-dimethylaniline, N-chloro-acetyl-N-isopropyl-2-chloroaniline, N-chloroacetyl-N-(lH-pyrazol-1-yl-methyl)-2,6-dimethylaniline, N-chloroacetyl-N-(lH-pyrazol-l-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylani`Line~ N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline, N-chloroacetyl-39~:~
N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert.-butylaniline, N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline and N-chloroacetyl-N-(l-methyl-5-methylthio-l,3,.4-triazol-2-ylmethyl)-2,6-diethylaniline.
Aryloxyphenoxypropionic acid herbicides, whose damaging effect on culti-vated plants can be eliminated with the aid of the N-acylsulfamoylphenyl-ureas of formula I, are known in great number. Such aryloxyphenoxyprop-ionic acid derivatives can be described by the following general formula IV:
Q-O ~ O-CH-CO-T (IV) wherein Q is a radical \ =. =N Rl4/ ~-/ \O/
~ or \~
Rl 4 / ~-/ \S/ ~./ N~
and T is -NRlsRls, -N(CN)Rl7, -ORls, SRls or -o-N=CRl9RZ0, wherein Rl3 is halogen or trifluoromethyl, R1 4 is hydrogen or halogen, each of R1s and R15, independently of the other, is hydrogen, Cl-C8alkoxy, C1-Cgalk`yl, phenyl or benzyl, R1s and R15 together with the nitrogen atom carrying them form a 5- or 6-membered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, Rl3 is hydrogen or the equiv-alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary Cl-C4alkylammonium or Cl-C4hydroxyalkylammonium radical; a Cl-C9alkyl radical that is unsubstituted or mono- or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, Cl-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR2l, -COSR2l, -CONH2, -CON(Cl-C 4 alkoxy)-Cl-C 4 alkyl, -CO-N-di-Cl-C 4 alkyl, CONH-Cl-C 4 alkyl, -N(Cl-C4alkoxy)-Cl-C4alkyl or by di-Cl-C4alkylamino; a C3-Cgalkenyl radical that is unsubstituted or substituted by halogen or by Cl-C4-2Cii~9Z~
alkoxy; a C3-Cgalkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-Cgcycloalky].; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1-C4alkoxy, acetyl, -COOR21, COSRZ17 -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4alkyl, or together they form a 3- to 6-membered alkylene chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3-C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
The following herbicidal aryloxyphenoxypropionic acid derivatives especially fall within the scope of formula IV:
2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)~phenoxy]-thioprop-ionic acid propargyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid methyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, 2-[4-(5-trifluoromethyl-pyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, 2-[4-(5-trifluoro-methylpyridin-2-yloxy)-phenoxy]-propionic acid methyl ester, 2-[4-(6-chloroquinoxalin-2-yloxy)-phenoxy]-propionic acid ethyl ester and 2-[4-(6-chlorobenzoxazolin-2-yloxy)-phenoxy]-propionic acid ethyl ester.
Acylcyclohexanedione derivatives, whose damaging effect on cultivated plants can be eliminated with the aid of the N-acylsulfamoylphenylureas of formula I, are described, for example, in published European Patent Application No. O 243 313. Such acylcyclohexanedione derivatives can be described by the following general formula IX
R ~f' R22-S(O~ (C )l l~ (IX) wherein A' is a 2- ~o 7-membered alkylene bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n' is O, 1 or 2, R22 is C1-C4alkyl or benzyl, R23 is Cl-C6alkyl unsubstituted or sub-stituted by halogen, C~-C4alkoxy or by C1-C4alkylthio; C3-C6cycloalkyl;
'', ' , ~ -9~8 phenyl, benzyl or phenylethyl wherein the phenyl ring Gan be substituted by halogen, C1-C4alkyl, C~-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C1-CI,haloalkoxy, cyano or by nitro, X' is oxygen or a radical -NORz4~ and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or 3 -C 6 alkynyl.
The following herbicidal acylcyclohexanedione derivatives especially fall within the scope of formula IX:
5-(1-Methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-cyclopropylcarbonylcyclohexane-1,3-dione, S-(1-methylthiocyclobutan-1-yl)-2-(2,3-dichlorobenzoyl)-cyclo-hexane-1,3-dione, 5-(1-methylsulfonylcyclobutan-1-yl)-2-n-butyrylcyclo-hexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-propionylcyclo-hexane-1,3-dione, 5-(1-ethylthiocyclopropan-1-yl)-2-propionylcyclo-hexane-1,3-dione and 5--(1-methylthiocyclopropan-1-yl)-2-n-butyrylcyclo-hexane 1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclohexan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthio-cyclobutan-1-yl)-2-(1-allyloxyimino-n-butyryl)-cyclohexane-1,3-dione and 5-(1-methylthiocyclopentan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxy-imino)-n-butyryl]-cyclohexane 1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(cis-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione and 5-(1-ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione.
The antidotes of formula I are most especially suitable for protecting cultivated plants from the herbicidal action of herbicides of formulae II, III and IV.
Agrochemical compositions that contain in a common formulation togetherwith the antidote of formula I a sulfonylurea herbicida, a chloroacet-anilide herbicide or an aryloxyphenoxypropionic acid herbicide are :. :
:
:
9~
suitable for use as selective herbicides in crops of useful plants. The herbicidal compositions of the invention preferably contain, in addition to an antidote of formula I, a sulfonylurea of formula II, a chloro-acetanilide of formula III, an acylcyclohexanedione derivative of formula IX or an aryloxyphenoxypropionic acid derivativs of formula IY.
Unless used for dressing seed, the amount of counter-agent applied varies between about 0.01 and about 5 parts by weight per part by weight of herbicide. In practice, the most suitable ratio with regard to the optimum effect on the specific cultivated plant is determined from case to case, that is to say depending upon the type of herbicide used.
The invention relates also to a method of selectively controlling weedsin crops of cultivated plants, in which the crops of cultivated plants, parts of the cultivated plants or the cultivation areas of the cultivated plants are treated with a herbicide and a compound of formula I or with a composition containing that combination. The present invention relates also to the compositions containing the combination of herbicide and antidote.
The weeds to be controlled may be either monocotyledonous or di-cotyledonous weeds.
Various methods and techniques are suitable for employing the compoundsof formula I or compositions containing them for the protection of culti-vated plants from the damaging effects oE agrochemicals. Examples of these methods and techniques are:
i) Seed dressing a) dressing the seed with an active ingredient formulated as a wettable powder~ by shaking in a vessel until uniform distribution over the surface of the seed is achieved (dry dressing). In this procedure, about 10 to 500 g of active ingredient of formula I (40 g to 2 kg of wettable powder in the case of a 25 % strength formulation) are used per 100 kg of seed.
g~
b) dressing the seed with an emulsifiable concentrate of the active ingredient or with an aqueous solution of a wettable powder formulation of the active ingredient of formula I by method a) (wet dressing).
c) dressing by immersing the seed in a liquor containing from 50 to 3,200 ppm of an active ingredient of formula I for from 1 to 72 hours and, if desired, subsequently drying the seed (immersion dressing, seed soaking).
Dressing the seed or treating the sprouted seedling are, of course, thepreferred methods of application since the treatment with the active ingredient is directed entirely towards the target crop. As a rule, from 10 g to 500 g, preferably from 50 to ~00 g, of active ingredient are used per 100 kg of seed, and, depending upon-the method employed, which also allows other active ingredients or micronutrients to be added, it is possible to exceed or use less than the concentration limits indicated (repeat dressing).
ii) Application from a tank mix A liquid formulation of a mixture of counter-agent and herbicide (ratio of the one to the other from 10:1 to 1:30~ is used, the application rate of herbicide being from 0.001 to lO kg per hectare: A tank mix of this type is preferably applied before or after sowing or is worked 5 to 10 cm deep into the soil before sowing.
iii~ Application to the seed furrow The counter-agent is introduced in the form of an emulsifiable concen-trate, wettable powder, or granulate into the open, sown seed furrow and then, after the seed furrow has been covered, the herbicide is applied in the normal manner according to the pre-emergence method.
: .
:
~ 2~2~8 iv) Controlled release of active ingredient A solution of the active ingredient is adsorbed onto mineral granulate carriers or polymerised granules (urea/formaldehyde) and is allowed to dry. If desired, it is possible to apply a coating (coated granulate) which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of for-mulation and are therefore formulated e.g. into emulsifiable concen-trates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsula-tions. As with the nature of the compositions, the methods of applica-tion, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures con-taining the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, sur-face-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, di-methyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil;
or water.
, The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, mont-morillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite;
and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
The term "surfactants" will also be understood as comprising mixtures oE
surfactants.
Both so-called water-soluble soaps and also water--soluble synthetic sur-face-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-c22)7 e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyl-taurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C2 z-alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of ligno-sulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sul-;
:
92~3 fates obtained f}om natural fatty acids. These com,oounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediaminopoly-propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenolpoly-ethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenolpolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
- ~ :'. ,' ~ : ' .
: , .
'I ' ~ I . :'. ' I
.: ~ :
. ~ .
~o~9~
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C~-C2z-alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of formulation are described inter alia in the following publications:
"198; International McCutcheon's Emulsifiers & Detergents", Glen Rock NJ, USA, 1985, H. Stache~ "Tensid-Taschenbuch", 2nd Edition, C. Hanser Verlag Munich, Vienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemic~l Publishing Co., New York, 1980-1981.
The agrochemical compositions usually contain 0.1 to 95 %, preferably 0.1 to 80 Yo~ of a compound of formula I, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
Preferred formulations are composed especially of the following constitu-ents tthroughout percentages are by weight):
Emulsifiable concentrates:
active ingredient mixture: 1 to 20 %, preferably 5 to 10 %
surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier: 50 to 94 %, preferably 70 to 85 %
Dusts:
active ingredient mixture:0.1 to 10 %, preferably 0.1 to 1 %
solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient mixture: 5 to 75 %, preferably 10 to 50 %
water:94 to 25 %, preferably 88 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %
...
,. ~.
., ': .:
9~8 Wettable powders:
active ingredient mixture: 0.5 to 90 ~/0, preferably I to 80 %
surfactant: 0.5 to 20 %, preferably 1 to 15 %
solid carrier:5 to 95 %, preferably 15 to 90 %
_anulates:
active ingredient mixture:0.5 to 30 %, preferably 3 to 15 %
solid carrier:99.5 to 70 %, preferably 97 to 85 %
Whereas commercial products will preferably be formulated as concen-trates, the end user will normally employ dilute formulations. The for-mulations may be diluted down to a concentration of 0.001 % active in-gredient. The rates of application are normally from 0.01 to 10 kg a.i.tactive ingredient)/ha, preferably from 0.25 to 5 kg a.i./ha.
The compositions may also contain further auxiliaries such as stabi-lisers, antifoams, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtain-ing special effects.
The following Examples serve to illustrate the invention. They do not limit the invention.
Preparation Examples:
Example_Pl: 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl] 3-methylurea H3C-NH-C0-NH-~ -SO2-NH-CO~ -CH3 : ' :.,~,',; - :
- ':' . ' : ~ `
a) N-(4-sulfamoylphenyl)-0-phenylcarbamate.
176 g of sulfanilamide are suspended in 750 ml of dioxane, and 79 g of pyridine are added thereto. 160 g of chloroformic acid phenyl ester are then added dropwise to that mixture at 15C. The reaction suspension is stirred at 50C for l hour, cooled and stirred into 2 litres of water.
The precipitated product is separated off and dried, yielding 277 g of N-(4-sulfamoylphenyl)-0-phenylcarbamate, m.p. 220-223C.
b) l-(4-sulfamoylphenyl)-3-methylurea.
330 ml of a 33 % ethanolic methylamine solution are added dropwise at 30C to a suspension of 350 g of N-(4-sulfamoylphenyl)-0-phenylcarbamate in 1500 ml of ethanol. The product crystallises out of the initially clear solution within a period of 1.5 hours. After the reaction mixture has cooled, the precipitate is separated off and dried, yielding 256 g of 1-(4-sulfamoylphenyl)-3-methylurea, m.p. 211-213C.
c) 56.7 g of 3,4-dimethylbenzoyl chloride and 3.9 g of 4-dimethylamino-pyridine are added to a suspension of 73.3 g of 1-(4-sulfamoylphenyl)-3-methylurea in 600 ml of acetonitrile. 98.1 g of triethylamine are added dropwise to that mixture, during which the temperature of the mixture rises from room temperature to 45C and the disperse constituents enter into solution. After a short time crystallisation begins. After a further 2.5 hours, the mixture is stirred into 2.5 litres of ice-water and 200 ml of 2N sulfuric acid. The precipitated product is separated off, washed with ether and dried, yielding 114.4 g of 1-[4-(N-3,4-dimethylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, m.p. 236-230C (with decomposition).
xample P2: 1-[3-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea /N-C0-NH~
H3C \.=.- S02-NH-C0 \0 - :
~, :
.: :
':: ~' . , ~ ~ "
.L i .
. :. . .
Z~ 9~8 a) N-(3-sulfamoylphenyl)-0-phenylcarbamate.
113 g of chloroformic acid phenyl ester are added dropwise at 15C to a suspenSion of 125 g of 3-aminobenzenesulfonamide and 57.9 g of pyridine in 500 ml of dioxane. The mixture is stirred for one hour at room tem-perature and for one hour at 50C and then stirred into 2 litres of water. The precipitated product is separated off and dried, yielding 201 g of N-(3-sulfamoylphenyl)-0-phenylcarbamate, m.p. 184-186C ~with decompos',.tion).
b) 1-(3-sulfamoylphellyl)-3,3-dimethylurea.
A mixture of 205 g of N-(3-sulfamoylphenyl)-0-phenylcarbamate and 158 g of a 40 % aqueous solution of dimethylamine is heated at reflux in 500 ml of ethanol for 3 hours. The solvent is distilled off under reduced pressure. Water is added to the residue and the phenol that is formed is driven off with steam. After the distillation flask has cooled, the crystalline residue is separated off, washed with cold methanol and dried, yielding 136 g of 1-(3-sulfamoylphenyl)-3,3-dimethylurea, m.p.
193-19~C.
c) 6.1 g of 2-furancarboxylic acid chloride and 0.1 g of 4-dimethylamino-pyridine are added to a suspension of 10.1 g of 1-t3-sulfamoylphenyl)-3,3-dimethylurea in 60 ml of acetonitrile. 9.5 g of triethylamine are added dropwise to that mixture at room temperature. The reaction mixture is stirred ~or 15 hours at room temperature and for one hour at 60C.
After the mixture has cooled, 4.5 g of methanesulfonic acid are added dropwise thereto and the mixture is taken up in 1 litre of water. The oil that separates out crystallises after a short time. The crystals are separated off, washed with methanol and dried, yielding 11.3 g of 1-[3-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea, m.p.
216-217C (with decomposition).
~xample P3: 1-[4-(N-3t4-dimethylbenzoylsulfamoyl)-phenYl]-3-allylurea /CH~
H2C=CH-CH2-NH-C0-NH-~ -S02-NH-C0--~ ~--CH3 :
4.1 g of triethylamine are added dropwise to a suspension of 12.2 g of 4-(N-3,4-dimethylbenzoylsulfamoyl)-aniline in 20 ml of acetonitrile.
Initially a clear solution is formed from which a salt precipitates.
After the addition of 4.6 g of allyl isocyanate the mixture is stirred for 2 hours at room temperature and then for 2 hours at 70C. When the mixture has cooled, it is taken up in a mixture of 1 litre of ice-water and 4.5 g of concentrated sulfuric acid. The resulting precipitate is separated off, washed with ether and dried, yielding 15.1 g of 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-allylurea, m.p. 194-201C (with decomposition).
~xample P4: 1-[4-(N-2,3-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea H3C-NH-C0-NH--~ ~--S02-NH-C0--~ ~-C~3 \CH3 2.8 g of triethylamine are added to a suspension of 6.1 g of 4-(N-2,3-di-methylbenzoylsulfamoyl)-aniline in 50 ml of acetonitrile. 1.3 ml of methyl isocyanate are added dropwise to that mixture. The reaction mixture is stirred for 2 hours at room temperature and then for 6 hours at 50C. After cooling to room temperature, the mi~ture is taken up in 200 ml of ice-water and 15 ml of 2N sulfuric acid. The precipitated pro-duct is separated off and dried, yielding 1-[4-(N-2,3-dimethylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, m.p. 242-244C.
The intermediates and end products listed in the following Tables are obtained in analogous manner.
,:
. ~
9~
Table 1: R~
/N-C0-NH--~ ~--SO2-NH-CO-A
RZ .=.
Comp. No. RlRZN- A m.p. [C]
1.001 Amino Phenyl 1.002 Methylamino Phenyl 237-238 (decomp.) 1.003 Dimethylamino Phenyl 1.004 Methylamino 2-Tolyl 234-236 (decomp.) 1.005 Methylamino 3-Tolyl 216-218 1.006 Methylamino 4-Tolyl 247-249 (decomp.) 1.007 Methylamino 4-Ethyl-phenyl 1.008 Methylamino 4-n-Propyl-phenyl 1.009 Methylamino 4-i-Propyl-phenyl 1.010 Methylamino 4-n-Butyl-phenyl 1.011 Methylamino 4-tert-Buty]-phenyl250-252 (decomp.) 1.012 Methylamino 2-Chlorophenyl 239-241 .(decomp.) 1.013 Methylamino 3-Chlorophenyl 222-224 (decomp.) 1.014 Methylamino 4-Chlorophenyl 246-247 (decomp.) 1.015 Methylamino 2-Fluorophenyl 227-229 (decomp.) 1.016 Methylamino 3-Fluorophenyl 234-235 (decomp.) 1.017 Methylamino 4-Fluorophenyl 1.018 Methylamino 2-Bromophenyl 244-245a (decomp.) 1.019 Methylamino 3-Bromophenyl 1.020 Methylamino 4-Bromophenyl 1.021 Methylamino 2-Iodophenyl 1.022 Methylamino 3-Iodophenyl .
~: . ~- :, ~ ,,. - . .. :
~. , .
2~ 28 - 31 ~
ble 1: continued Comp. No. R1R2N- A m.p. [C]
1.023 Methylamino 4-Iodophenyl 1.024 Methylamino 3-Chloromethyl-phenyl 1.025 Methylamino 2-Trifluoromethyl-phenyl 1.026 Methylamino 3-Trifluormethyl-phenyl 231-233 .(decomp.) 1.027 Methylamino 4-Trifluoromethyl-phenyl 1.028 Methylamino 2-Methoxy-phenyl197-198 (decomp.) 1.029 Methylamino 3-Methoxy-phenyl 1.030 Methylamino 4-Methoxy-phenyl 1.031 Methylamino 2-Ethoxy-phenyl 1.032 Methylamino 3-Ethoxy-phenyl 1.033 Methylamino 4-Ethoxy-phenyl 1.034 Methylamino 2-Methylmercapto-phenyl 1.035 Methylamino 2-Methylsulfonyl-phenyl 1.036 Methylamino 2-Methoxycarbonyl-phenyl 1.037 Methylamino 4-Methoxycarbonyl-phenyl 1.038 Methylamino 2-Nitro-phenyl 1.039 Methylamino 3-Nitro-phenyl 1.040 Methylamino 4-Nitro-phenyl 237-238 (dec omp . ) 1.041 Methylamino 2-Acetyl-phenyl 1.042 Methylamino 4-Acetyl-phenyl 1.043 Methylamino 3-Cyanophenyl 1.044 Methylamino 4-Cyanophenyl 1.045 Methylamino 2,3-Dimethyl-phenyl 242-244 1.046 Methylamino 2,4-Dimethyl-phenyl 239-241 (decomp.) 1.047 Methylamino 2,5-Dimethyl-phenyl 223-224 (decomp.) 1.048 Methylamino 2,6-Dimethyl-phenyl 1.049 Amino 3,4-Dimethyl-phenyl 151-153 (decomp.
2~
Table 1: continued Comp. No. RlR2N- A m.p. ¦C~
1.050 Methylamino 3,4-Dimethyl-phenyl 236-238 (decomp.) 1.051 Dimethylamino 3,4-Dimethyl-phenyl 233-235 (decomp.) 1.052 Ethylamino 3,4-Dimethyl-phenyl > 230 (decomp.) 1.053 Propylamino 3,4-Dimethyl-phenyl 211-213 (decomp.) 1.054 Isopropylamino 3,4-Dimethyl-phenyl 235-236 (decomp.) 1.055 Cyclopropylamino 3,4-Dimethyl-phenyl 229-231 1.056 Butylamino 3,4-Dimethyl-phenyl 200-202 (decomp.
1.057 Isobutylamino 3,4-Dimethyl-phenyl 222-223 (decomp.) 1.058 sec.-~utylamino 3,4-Dimethyl-phenyl 215-218 (decomp.) 1.059 tert.-Butylamino 3,4-Dimethy:L-phenyl 223-225 (decomp.) 1.060 Allylamino 3,4-Dimcthyl-phenyl 194-201 (decomp.) 1.061 Propargylamino 3,4-Dimethyl-phenyl 231-233 (decomp.) 1.062 Cycloheylamino 3,4-Dimethyl-phenyl 1.063 Phenylamino 3,4-Dimethyl-phenyl 230-231 (decomp.) 1.064 2-Methoxy-ethylamino 3,4-Dimethyl-phenyl 166-169 (decomp.) 1.065 Benzylamino 3,4-Dimethyl-phenyl 234-236 (decomp.) 1.066 Pyrrolidinyl 3,4-Dimethyl-phenyl 1.067 Piperidinyl 3,4-Dimethyl-phenyl 1.068 Hexahydroazepinyl 3,4-Dimethy;L-phenyl 1.069 Morpholinyl 3,4-Dimethyl-phenyl 1.070 2-Methyl-piperidinyl 3,4-Dimethyl-phenyl 1.071 3-Methyl-piperidinyl 3,4-Dimethyl-phenyl . _ - . ~
' '` : ;' ' ' "
' ~ ~
32~3 Table 1: continued Comp. No. RlR2N- A m.p. [C
1.0724-Methyl-piperidinyl 3,4-Dimethyl-phenyl 1.073 2,6-Dimethyl-piperidinyl 3,4-Dimethyl-phenyl 1.074 N-Methyl-piperazinyl 3,4-Dimethyl-phenyl 1.075 Thiomorpholinyl 3,4-Dimethyl-phenyl 1.076 Methylamino 3,5-Dimethyl-phenyl 240-242 (decomp.) 1.077 Methylamino 2,3-Dichlorophenyl 1.078 Methylamino 2,4-Dichlorophenyl 1.079 Methylamino 2,5-Dichlorophenyl 1.080 Methylamino 2,6-Dichlorophenyl 1.081 Methylamino 3,4-Dichlorophenyl 240-241 1.382 Methylamino 3,5-Dichlorophenyl 1.083 Methylamino 2,3-Difluorophenyl 1.084 Methylamino 2,4-Difluorophenyl 1.085 Methylamino 2,5-Difluorophenyl 1.086 Methylamino 2,6-Difluorophenyl 1.087 Methylami.no 3,4-Difluorophenyl 1.088 Methylamino 3,5-Difluorophenyl 1.089 Methylamino 3,5-Dimethoxy-phenyl 1.090 Methylamino 2,4-Dimethoxy-phenyl 1.091 Methylamino 2,5-Dimethoxy-phenyl 1.092 Methylamino 2,6-Dimethoxy-phenyl 1.093 Methylamino 3,4-Dimethoxy-phenyl (decomp ) 1.09~ Dimethylamino 3,4-Dimethoxy-phenyl 203-207 . (decomp.) 1.095 Methylamino 3,5-Dimethoxy-phenyl 1.096 Methylamino 3,4-Dinitro-phenyl 1.097 Methylamino 3,5-Dinitro-phenyl 1.098 Methylamino 2-Chloro-3-nitro-phenyl 1.099 Methylamino 2-Chloro-4-nitro-phenyl 1.100 Methylamino 2-Chloro-5-nitro-phenyl ' ' . ':: .
: ::
Table 1: continued Comp. No. R1R2N- A m.p. [C]
_ _ 1.101 Methylamino 3-Chloro-2-nitro-phenyl 1.102 Methylamino 4-Chloro-2-nitro-phenyl 1.103 Methylamino 3-Chloro-3-nitro-phenyl 1.104 Methylamino 5-Chloro-2-nitro-phenyl l.lO5 Methylamino 2-Methyl-3-nitro-phenyl (decomp ) 1.106 Methylamino 2-Methyl-5-nitro-phenyl 1.107 Methylamino 2-Methyl-6-nitro-phenyl 1.108 Methylamino 3-Methyl-2-nitro-phenyl 1.109 Methylamino 3-Methyl-4-nitro-phenyl 1.110 Methylamino 4-Methyl-3-nitro-phenyl 1.111 Methylamino 5-Methyl-2-nitro-phenyl 1.112 Methylamino 4-Fluoro-3-n:Ltro-phenyl ~
1.113 Methylamino 5-Chloro-2-methoxy-pheny: -¦
1.114 Methylamino 4-Chloro-2-methoxy-pheny:
1.115 Methylamino 4-Chloro-6-fluoro-phenyl 1.116 Methylamino 4-Chloro-2-fluoro-phenyl 1.117 Methylamino 2,4,6-Trimethyl-phenyl 1.118 Methylamino 2,4,5-Trimethoxy-phenyl 1.119 Methylamino 3,4,5-Trimethoxy-phenyl 238-239 1.120 Methylamino 1-Naphthyl 240-242 (decomp.) 1.121 Methylamino 2-Naphthyl 234-235 (decomp.) 1.122 Methylamino 2-Furyl 245-246 (decomp.) 1.123 Dimethylamino 2-Furyl 246-247 (decomp.) 1.124 Methylamino 3-Furyl ~ ' ' , 9Z~
Table 1: continued Comp. No. RlR2N- A m.p. [C]
1.125 Methylamino 2-Thienyl 245-247 (decomp.) 1.126 Methylamino 2-Chloropyridinyl 1.127 Methylamino 2,6-Dichloropyridinyl 138-139 (decomp.) 1.128 Methylamino 2,6-Dibromopyridinyl 1.129 Methylamino Piperonyl 268-270 (decomp.) 1.130 Dimethylamino 3-Tolyl 204-207 (decomp.) 1.131 Cyclopropylamino 3-Trifluoromethyl-phenyl 246-247 1.132 i-Propylamino 3-Tolyl 217-220 (decomp.) 1.133 Dimethylamino 3-Trifluoromethylphenyl 229-230 (decomp.) 1.134 Amino 4-Chloro 226-228 (decomp.) 1.135 Methylamino 2-Carboxyphonyl (decomp.) 1.136 i-Propylamino 2-Tolyl (decomp.) 1.137 Methylamino 3-Bromo-4-Methylphenyl 244-245 (decomp.) 1.138 i-Propylamino l-Naphthyl 235-237 -(decomp.) 1.139 Allylamino 1-Naphthyl 218-219 1.140 Allylamino 2-Tolyl 195-198 1.141 3-Tolylamino 2-Tolyl 197-199 (decomp.) ' :-9~8 Table 1: continued Comp. No. R1R2N- m.p.
1.142 tert.-Butylamino 2-Tolyl (decomp ) 1.143 tert.-Butylamino 2,4-Dimethylphenyl 226-227 (decomp.) 1.144 Propargylamino 1-Naphthyl 149-151 (decomp.) 1.145 sec. Butylamino 2,4-Dimethylphenyl 230-232 (decomp.) 1.146 Propargylamino 2,4-Dimethylphenyl 191-192 (decomp.) 1.147 Methylamino 2-Biphenyl 262-264D
(decomp.) 1.148 sec. Butylamino 2,5-Dimethylphenyl 208-210 (decomp.) 1.149 Dimethylamino 2,4-Dimethylphenyl 206-209 (decomp.) 1.150 Dimethylamino l-Naphthyl >250 (decomp.) 1.151 Dimethylamino 2-Tolyl 236-240 (decomp.) 1.152 Propargylamino 2,5-Dimethyl-phenyl 198-200 1.153 Methylamino 4-Chloromethyl-phenyl 228-229 (decomp.) 1.154 Methylamino 3 (2,3-Tetramethylane)-thienyl >250 1.155 Methylamino 3-(2,3-Tetramethylene)-furyl 1.156 Methylamino 3-(4,5-Dimethyl)-thienyl 238-239 - , .
.
2~ 9~
Table 2:
/N-CO-NH~
R2 \~ SO2-NH-CO-A
j Comp. No. R1R2N- A m.p. [C~
2.001 Amino Phenyl 2.002 Methylamino Phenyl 2.003 Dimethylamino Phenyl 2.004 Methylamino 2-Tolyl 2.005 Methylamino 3-Tolyl 2.006 Methylamino 4-Tolyl 2.007 Methylamino 2-Chlorophenyl 2.008 Methylamino 4-Chlorophenyl 2.009 Methylamino 3-Trifluoromethyl-phenyl 2.010 Methylamino 2,3-Dimethyl-phenyl 2.011 Methylamino 3,4-Dimethyl-phenyl 147-152 2.012 Methylamino 1-Naphthyl 2.013 Methylamino 2-Naphthyl 2.014 Dimethylamino 2-Furyl 216-217 (decomp.) _ .
.: ~
9~3 Table 3:
~R
~ .
H3C-NH-CO-NH--~ S0z-NH-CO--A
Comp. No. A Ra m.p. [C]
3.001 Phenyl 2-Fluoro 3.002 Phenyl 3-Fluoro 3.003 4-Tolyl 2-Fluoro 258-260 (decomp.) 3.004 4-Tolyl 3-Fluoro ca. 270 (clecomp.) 3.005 4-Tolyl 2-Chloro 3.006 4-Tolyl 3-Chloro 3.007 4-Tolyl 2-Methyl 3.008 4-Tolyl 3-Methyl 3.009 3,4-Dimethyl-phenyl 2-Fluoro 246-248 (decomp.) 3.010 3,4-Dimethyl-phenyl 3-Fluoro 239-240 3.011 3,4-Dimethyl-phenyl 2-Chloro 3.012 3,4-Dimethyl-phenyl 3-Chloro 223-224 (decomp.) 3.013 3,4-Dimethyl-phenyl 2-Methyl 3.014 3,4-Dimethyl-phenyl 3-Methyl 218-220 (decomp.) 3.015 2-Tolyl 3-Fluoro 236-238 (decomp.) 3.016 1-Naphthyl 3-Fluoro ` 131-133 (decomp.) 3.017 2,4-Dimethyl-phenyl 2-Fluoro 236-238 (decomp.) 3.018 2,4-Dimethyl-phenyl 3-Fluoro 233-234 (decomp.) 3.019 l-Naphthyl 2-Fluoro 240--241 3.020 2,3-Dimethyl-phenyl 3-Fluoro 227-230 (decomp.) 3.021 2,3-Dimethyl-phenyl 2-Fluoro 244-246 (decomp.) ~' ' 2~
Table 3: continued Comp. No. A R m.p. [C]
3.022 2-Tolyl 2-Fluoro 236-237 (decomp.) 3.023 3,5-Dimethyl-phenyl 3-Fluoro 198-200 (decomp.) 3.024 3,5-Dimethyl-phenyl 2-Fluoro 244-246 (decomp.) 3.025 2,5-Dimethyl-phenyl 3-Fluoro 213-215 (decomp.) 3.026 2,5-Dimethyl-phenyl 2-Fluoro 227-229 (decomp.) 3.027 2-Tolyl 3-Methyl 176 (decomp.) 3.028 2-Tolyl 3-Chloro (decomp.) 3.029 l-Naphthyl 3-Chloro 150 3.030 l-Naphthyl 3-Methyl 153-155 (decomp.) :: :
: :
' :.
;~ 9~3 Table 4:
~ SOz-NH-CO-A
a ---Comp. No.¦ A Ra b m.p. [C]
4.001 1-Naphthyl 2-Methyl 6-Methyl 214-216 (decomp.) 4.002 3,4-Dimethyl-phenyl 2-Methyl 6-Methyl 206-208 4.003 2-Tolyl 2-Methyl 6-Methyl 217-219 4.004 l-Naphthyl 2-Fluoro 6-Fluoro 4.005 3,4-Dimethyl-phenyl 2-Fluoro 6-Fluoro 4.006 2-Tolyl 2-Chloro 6-Chloro 4.007 4-Tolyl 2-Fluoro 5-Fluoro 4.008 4-Tolyl 2-Fluoro 5-Fluoro 4.009 4-Tolyl 2-Methyl 5-Methyl ~:
Table 5:
\ _ /
H3C-NH-C0-NH~ -S02-NH-C0-A
Comp No.~ A ~ m.p. I~c¦
Initially a clear solution is formed from which a salt precipitates.
After the addition of 4.6 g of allyl isocyanate the mixture is stirred for 2 hours at room temperature and then for 2 hours at 70C. When the mixture has cooled, it is taken up in a mixture of 1 litre of ice-water and 4.5 g of concentrated sulfuric acid. The resulting precipitate is separated off, washed with ether and dried, yielding 15.1 g of 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-allylurea, m.p. 194-201C (with decomposition).
~xample P4: 1-[4-(N-2,3-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea H3C-NH-C0-NH--~ ~--S02-NH-C0--~ ~-C~3 \CH3 2.8 g of triethylamine are added to a suspension of 6.1 g of 4-(N-2,3-di-methylbenzoylsulfamoyl)-aniline in 50 ml of acetonitrile. 1.3 ml of methyl isocyanate are added dropwise to that mixture. The reaction mixture is stirred for 2 hours at room temperature and then for 6 hours at 50C. After cooling to room temperature, the mi~ture is taken up in 200 ml of ice-water and 15 ml of 2N sulfuric acid. The precipitated pro-duct is separated off and dried, yielding 1-[4-(N-2,3-dimethylbenzoyl-sulfamoyl)-phenyl]-3-methylurea, m.p. 242-244C.
The intermediates and end products listed in the following Tables are obtained in analogous manner.
,:
. ~
9~
Table 1: R~
/N-C0-NH--~ ~--SO2-NH-CO-A
RZ .=.
Comp. No. RlRZN- A m.p. [C]
1.001 Amino Phenyl 1.002 Methylamino Phenyl 237-238 (decomp.) 1.003 Dimethylamino Phenyl 1.004 Methylamino 2-Tolyl 234-236 (decomp.) 1.005 Methylamino 3-Tolyl 216-218 1.006 Methylamino 4-Tolyl 247-249 (decomp.) 1.007 Methylamino 4-Ethyl-phenyl 1.008 Methylamino 4-n-Propyl-phenyl 1.009 Methylamino 4-i-Propyl-phenyl 1.010 Methylamino 4-n-Butyl-phenyl 1.011 Methylamino 4-tert-Buty]-phenyl250-252 (decomp.) 1.012 Methylamino 2-Chlorophenyl 239-241 .(decomp.) 1.013 Methylamino 3-Chlorophenyl 222-224 (decomp.) 1.014 Methylamino 4-Chlorophenyl 246-247 (decomp.) 1.015 Methylamino 2-Fluorophenyl 227-229 (decomp.) 1.016 Methylamino 3-Fluorophenyl 234-235 (decomp.) 1.017 Methylamino 4-Fluorophenyl 1.018 Methylamino 2-Bromophenyl 244-245a (decomp.) 1.019 Methylamino 3-Bromophenyl 1.020 Methylamino 4-Bromophenyl 1.021 Methylamino 2-Iodophenyl 1.022 Methylamino 3-Iodophenyl .
~: . ~- :, ~ ,,. - . .. :
~. , .
2~ 28 - 31 ~
ble 1: continued Comp. No. R1R2N- A m.p. [C]
1.023 Methylamino 4-Iodophenyl 1.024 Methylamino 3-Chloromethyl-phenyl 1.025 Methylamino 2-Trifluoromethyl-phenyl 1.026 Methylamino 3-Trifluormethyl-phenyl 231-233 .(decomp.) 1.027 Methylamino 4-Trifluoromethyl-phenyl 1.028 Methylamino 2-Methoxy-phenyl197-198 (decomp.) 1.029 Methylamino 3-Methoxy-phenyl 1.030 Methylamino 4-Methoxy-phenyl 1.031 Methylamino 2-Ethoxy-phenyl 1.032 Methylamino 3-Ethoxy-phenyl 1.033 Methylamino 4-Ethoxy-phenyl 1.034 Methylamino 2-Methylmercapto-phenyl 1.035 Methylamino 2-Methylsulfonyl-phenyl 1.036 Methylamino 2-Methoxycarbonyl-phenyl 1.037 Methylamino 4-Methoxycarbonyl-phenyl 1.038 Methylamino 2-Nitro-phenyl 1.039 Methylamino 3-Nitro-phenyl 1.040 Methylamino 4-Nitro-phenyl 237-238 (dec omp . ) 1.041 Methylamino 2-Acetyl-phenyl 1.042 Methylamino 4-Acetyl-phenyl 1.043 Methylamino 3-Cyanophenyl 1.044 Methylamino 4-Cyanophenyl 1.045 Methylamino 2,3-Dimethyl-phenyl 242-244 1.046 Methylamino 2,4-Dimethyl-phenyl 239-241 (decomp.) 1.047 Methylamino 2,5-Dimethyl-phenyl 223-224 (decomp.) 1.048 Methylamino 2,6-Dimethyl-phenyl 1.049 Amino 3,4-Dimethyl-phenyl 151-153 (decomp.
2~
Table 1: continued Comp. No. RlR2N- A m.p. ¦C~
1.050 Methylamino 3,4-Dimethyl-phenyl 236-238 (decomp.) 1.051 Dimethylamino 3,4-Dimethyl-phenyl 233-235 (decomp.) 1.052 Ethylamino 3,4-Dimethyl-phenyl > 230 (decomp.) 1.053 Propylamino 3,4-Dimethyl-phenyl 211-213 (decomp.) 1.054 Isopropylamino 3,4-Dimethyl-phenyl 235-236 (decomp.) 1.055 Cyclopropylamino 3,4-Dimethyl-phenyl 229-231 1.056 Butylamino 3,4-Dimethyl-phenyl 200-202 (decomp.
1.057 Isobutylamino 3,4-Dimethyl-phenyl 222-223 (decomp.) 1.058 sec.-~utylamino 3,4-Dimethyl-phenyl 215-218 (decomp.) 1.059 tert.-Butylamino 3,4-Dimethy:L-phenyl 223-225 (decomp.) 1.060 Allylamino 3,4-Dimcthyl-phenyl 194-201 (decomp.) 1.061 Propargylamino 3,4-Dimethyl-phenyl 231-233 (decomp.) 1.062 Cycloheylamino 3,4-Dimethyl-phenyl 1.063 Phenylamino 3,4-Dimethyl-phenyl 230-231 (decomp.) 1.064 2-Methoxy-ethylamino 3,4-Dimethyl-phenyl 166-169 (decomp.) 1.065 Benzylamino 3,4-Dimethyl-phenyl 234-236 (decomp.) 1.066 Pyrrolidinyl 3,4-Dimethyl-phenyl 1.067 Piperidinyl 3,4-Dimethyl-phenyl 1.068 Hexahydroazepinyl 3,4-Dimethy;L-phenyl 1.069 Morpholinyl 3,4-Dimethyl-phenyl 1.070 2-Methyl-piperidinyl 3,4-Dimethyl-phenyl 1.071 3-Methyl-piperidinyl 3,4-Dimethyl-phenyl . _ - . ~
' '` : ;' ' ' "
' ~ ~
32~3 Table 1: continued Comp. No. RlR2N- A m.p. [C
1.0724-Methyl-piperidinyl 3,4-Dimethyl-phenyl 1.073 2,6-Dimethyl-piperidinyl 3,4-Dimethyl-phenyl 1.074 N-Methyl-piperazinyl 3,4-Dimethyl-phenyl 1.075 Thiomorpholinyl 3,4-Dimethyl-phenyl 1.076 Methylamino 3,5-Dimethyl-phenyl 240-242 (decomp.) 1.077 Methylamino 2,3-Dichlorophenyl 1.078 Methylamino 2,4-Dichlorophenyl 1.079 Methylamino 2,5-Dichlorophenyl 1.080 Methylamino 2,6-Dichlorophenyl 1.081 Methylamino 3,4-Dichlorophenyl 240-241 1.382 Methylamino 3,5-Dichlorophenyl 1.083 Methylamino 2,3-Difluorophenyl 1.084 Methylamino 2,4-Difluorophenyl 1.085 Methylamino 2,5-Difluorophenyl 1.086 Methylamino 2,6-Difluorophenyl 1.087 Methylami.no 3,4-Difluorophenyl 1.088 Methylamino 3,5-Difluorophenyl 1.089 Methylamino 3,5-Dimethoxy-phenyl 1.090 Methylamino 2,4-Dimethoxy-phenyl 1.091 Methylamino 2,5-Dimethoxy-phenyl 1.092 Methylamino 2,6-Dimethoxy-phenyl 1.093 Methylamino 3,4-Dimethoxy-phenyl (decomp ) 1.09~ Dimethylamino 3,4-Dimethoxy-phenyl 203-207 . (decomp.) 1.095 Methylamino 3,5-Dimethoxy-phenyl 1.096 Methylamino 3,4-Dinitro-phenyl 1.097 Methylamino 3,5-Dinitro-phenyl 1.098 Methylamino 2-Chloro-3-nitro-phenyl 1.099 Methylamino 2-Chloro-4-nitro-phenyl 1.100 Methylamino 2-Chloro-5-nitro-phenyl ' ' . ':: .
: ::
Table 1: continued Comp. No. R1R2N- A m.p. [C]
_ _ 1.101 Methylamino 3-Chloro-2-nitro-phenyl 1.102 Methylamino 4-Chloro-2-nitro-phenyl 1.103 Methylamino 3-Chloro-3-nitro-phenyl 1.104 Methylamino 5-Chloro-2-nitro-phenyl l.lO5 Methylamino 2-Methyl-3-nitro-phenyl (decomp ) 1.106 Methylamino 2-Methyl-5-nitro-phenyl 1.107 Methylamino 2-Methyl-6-nitro-phenyl 1.108 Methylamino 3-Methyl-2-nitro-phenyl 1.109 Methylamino 3-Methyl-4-nitro-phenyl 1.110 Methylamino 4-Methyl-3-nitro-phenyl 1.111 Methylamino 5-Methyl-2-nitro-phenyl 1.112 Methylamino 4-Fluoro-3-n:Ltro-phenyl ~
1.113 Methylamino 5-Chloro-2-methoxy-pheny: -¦
1.114 Methylamino 4-Chloro-2-methoxy-pheny:
1.115 Methylamino 4-Chloro-6-fluoro-phenyl 1.116 Methylamino 4-Chloro-2-fluoro-phenyl 1.117 Methylamino 2,4,6-Trimethyl-phenyl 1.118 Methylamino 2,4,5-Trimethoxy-phenyl 1.119 Methylamino 3,4,5-Trimethoxy-phenyl 238-239 1.120 Methylamino 1-Naphthyl 240-242 (decomp.) 1.121 Methylamino 2-Naphthyl 234-235 (decomp.) 1.122 Methylamino 2-Furyl 245-246 (decomp.) 1.123 Dimethylamino 2-Furyl 246-247 (decomp.) 1.124 Methylamino 3-Furyl ~ ' ' , 9Z~
Table 1: continued Comp. No. RlR2N- A m.p. [C]
1.125 Methylamino 2-Thienyl 245-247 (decomp.) 1.126 Methylamino 2-Chloropyridinyl 1.127 Methylamino 2,6-Dichloropyridinyl 138-139 (decomp.) 1.128 Methylamino 2,6-Dibromopyridinyl 1.129 Methylamino Piperonyl 268-270 (decomp.) 1.130 Dimethylamino 3-Tolyl 204-207 (decomp.) 1.131 Cyclopropylamino 3-Trifluoromethyl-phenyl 246-247 1.132 i-Propylamino 3-Tolyl 217-220 (decomp.) 1.133 Dimethylamino 3-Trifluoromethylphenyl 229-230 (decomp.) 1.134 Amino 4-Chloro 226-228 (decomp.) 1.135 Methylamino 2-Carboxyphonyl (decomp.) 1.136 i-Propylamino 2-Tolyl (decomp.) 1.137 Methylamino 3-Bromo-4-Methylphenyl 244-245 (decomp.) 1.138 i-Propylamino l-Naphthyl 235-237 -(decomp.) 1.139 Allylamino 1-Naphthyl 218-219 1.140 Allylamino 2-Tolyl 195-198 1.141 3-Tolylamino 2-Tolyl 197-199 (decomp.) ' :-9~8 Table 1: continued Comp. No. R1R2N- m.p.
1.142 tert.-Butylamino 2-Tolyl (decomp ) 1.143 tert.-Butylamino 2,4-Dimethylphenyl 226-227 (decomp.) 1.144 Propargylamino 1-Naphthyl 149-151 (decomp.) 1.145 sec. Butylamino 2,4-Dimethylphenyl 230-232 (decomp.) 1.146 Propargylamino 2,4-Dimethylphenyl 191-192 (decomp.) 1.147 Methylamino 2-Biphenyl 262-264D
(decomp.) 1.148 sec. Butylamino 2,5-Dimethylphenyl 208-210 (decomp.) 1.149 Dimethylamino 2,4-Dimethylphenyl 206-209 (decomp.) 1.150 Dimethylamino l-Naphthyl >250 (decomp.) 1.151 Dimethylamino 2-Tolyl 236-240 (decomp.) 1.152 Propargylamino 2,5-Dimethyl-phenyl 198-200 1.153 Methylamino 4-Chloromethyl-phenyl 228-229 (decomp.) 1.154 Methylamino 3 (2,3-Tetramethylane)-thienyl >250 1.155 Methylamino 3-(2,3-Tetramethylene)-furyl 1.156 Methylamino 3-(4,5-Dimethyl)-thienyl 238-239 - , .
.
2~ 9~
Table 2:
/N-CO-NH~
R2 \~ SO2-NH-CO-A
j Comp. No. R1R2N- A m.p. [C~
2.001 Amino Phenyl 2.002 Methylamino Phenyl 2.003 Dimethylamino Phenyl 2.004 Methylamino 2-Tolyl 2.005 Methylamino 3-Tolyl 2.006 Methylamino 4-Tolyl 2.007 Methylamino 2-Chlorophenyl 2.008 Methylamino 4-Chlorophenyl 2.009 Methylamino 3-Trifluoromethyl-phenyl 2.010 Methylamino 2,3-Dimethyl-phenyl 2.011 Methylamino 3,4-Dimethyl-phenyl 147-152 2.012 Methylamino 1-Naphthyl 2.013 Methylamino 2-Naphthyl 2.014 Dimethylamino 2-Furyl 216-217 (decomp.) _ .
.: ~
9~3 Table 3:
~R
~ .
H3C-NH-CO-NH--~ S0z-NH-CO--A
Comp. No. A Ra m.p. [C]
3.001 Phenyl 2-Fluoro 3.002 Phenyl 3-Fluoro 3.003 4-Tolyl 2-Fluoro 258-260 (decomp.) 3.004 4-Tolyl 3-Fluoro ca. 270 (clecomp.) 3.005 4-Tolyl 2-Chloro 3.006 4-Tolyl 3-Chloro 3.007 4-Tolyl 2-Methyl 3.008 4-Tolyl 3-Methyl 3.009 3,4-Dimethyl-phenyl 2-Fluoro 246-248 (decomp.) 3.010 3,4-Dimethyl-phenyl 3-Fluoro 239-240 3.011 3,4-Dimethyl-phenyl 2-Chloro 3.012 3,4-Dimethyl-phenyl 3-Chloro 223-224 (decomp.) 3.013 3,4-Dimethyl-phenyl 2-Methyl 3.014 3,4-Dimethyl-phenyl 3-Methyl 218-220 (decomp.) 3.015 2-Tolyl 3-Fluoro 236-238 (decomp.) 3.016 1-Naphthyl 3-Fluoro ` 131-133 (decomp.) 3.017 2,4-Dimethyl-phenyl 2-Fluoro 236-238 (decomp.) 3.018 2,4-Dimethyl-phenyl 3-Fluoro 233-234 (decomp.) 3.019 l-Naphthyl 2-Fluoro 240--241 3.020 2,3-Dimethyl-phenyl 3-Fluoro 227-230 (decomp.) 3.021 2,3-Dimethyl-phenyl 2-Fluoro 244-246 (decomp.) ~' ' 2~
Table 3: continued Comp. No. A R m.p. [C]
3.022 2-Tolyl 2-Fluoro 236-237 (decomp.) 3.023 3,5-Dimethyl-phenyl 3-Fluoro 198-200 (decomp.) 3.024 3,5-Dimethyl-phenyl 2-Fluoro 244-246 (decomp.) 3.025 2,5-Dimethyl-phenyl 3-Fluoro 213-215 (decomp.) 3.026 2,5-Dimethyl-phenyl 2-Fluoro 227-229 (decomp.) 3.027 2-Tolyl 3-Methyl 176 (decomp.) 3.028 2-Tolyl 3-Chloro (decomp.) 3.029 l-Naphthyl 3-Chloro 150 3.030 l-Naphthyl 3-Methyl 153-155 (decomp.) :: :
: :
' :.
;~ 9~3 Table 4:
~ SOz-NH-CO-A
a ---Comp. No.¦ A Ra b m.p. [C]
4.001 1-Naphthyl 2-Methyl 6-Methyl 214-216 (decomp.) 4.002 3,4-Dimethyl-phenyl 2-Methyl 6-Methyl 206-208 4.003 2-Tolyl 2-Methyl 6-Methyl 217-219 4.004 l-Naphthyl 2-Fluoro 6-Fluoro 4.005 3,4-Dimethyl-phenyl 2-Fluoro 6-Fluoro 4.006 2-Tolyl 2-Chloro 6-Chloro 4.007 4-Tolyl 2-Fluoro 5-Fluoro 4.008 4-Tolyl 2-Fluoro 5-Fluoro 4.009 4-Tolyl 2-Methyl 5-Methyl ~:
Table 5:
\ _ /
H3C-NH-C0-NH~ -S02-NH-C0-A
Comp No.~ A ~ m.p. I~c¦
5.001 3,4-Dimethyl-phenyl \ _ / 201-203 \ / (decomp.) .~ 184-186 \ _ / (decomp.) 5.002 2-Tolyl _.~ ~. _ as triethyl-\ ~ amine salt .~ ~. 138-140 5.003 l-Naphthyl ~ ~ as triethyl-~ amine salt ./-~-\, 5.004 2-Tolyl \ /
.~ ~--F
5.005 4-Tolyl ~ . _ .~-\.
5.006 3,4-Dimethyl-phenyl _ .~
\.=./
.\ /--CH3 5.007 2-Tolyl _.~ ~._ .
\.=./
Formulation ExamPles for active ingredients of formula I or mixtures thereof with herbicides Example Fl: Wettable powders a) b) c) compound 1.050 20 % 60 % 0.5 %
sodium lignosulfonate 5 % 5 % 5 %
sodium laurylsulfate 3 % - -sodium diisobutylnaphthalene-sulfonate - 6 % 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed silicic acid 5 % 27 % 27 %
kaolin 67 %
sodium chloride - - 59.5 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
E mple F2: Emulsifiable concentrate a) b) compound 2.011 10 % 1 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 %
cyclohexanone 30 % 10 %
xylene mixture 50 % 79 %
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
Example F3: Dusts a) b) compound 1.050 0.1 % 1 %
talcum 99-9 %
kaolin ~ 99 %
Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
Example F4: Extruder granulate a) b) compound 1.006 10 %1 %
sodium lignosulfonate 2 %2 %
carboxymethylcellulose 1 %1 %
kaolin 87 %96 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
Example F5: Coated granulate compound 1.005 3 %
polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
Example F6: Suspension concentrate a) b) compound 1.050 40 % 5 %
ethylene glycol10 % 10 %
nonylphenol polyethylene glycol ether tl5 moles of ethylene oxide) 6 % 1 %
sodium lignosulfonate10 % 5 %
carboxymethylcellulose1 % 1 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
: :. , , .: ~
.: . . : ' : ::
:
,, ::
:. : , ~ : ~
2C~39~1~
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32 % 77 %
Example F7: Salt solution compound 1.026 5 %
isopropylamine 1 %
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3 %
water 91 %
Example F8: Wettable powders a) b) c) compound 1.050 in admixture with 20 % 60 % 0.5 %
N-[2-(2-methoxyethoxy)-phenyl-sulEonyl]-N'-(4,6-dimethoxy-1,3,5-tria~in-2-yl]-urea sodium lignosulfonate 5 % 5 % 5 %
sodium laurylsulfate 3 %
sodium diisobutylnaphthalene-sulfonate - 6 % 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed silicic acid 5 % 27 % 27 %
~aolin 67 %
sodium chloride - - 59.5 %
The active ingredient mixture is thoroughly mixed with the adjuvants and the resul~ing mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
Example F9: Emulsifiable concentrate a) b) compound 2.011 in admixture with 10 % 1 %
2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy~-propionic acid n-butyl ester octylphenol polyethylene glycol ether (4-S moles of ethylene oxide) 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 %
cyclohexanone 30 % 10 %
xylene mixture 50 % 79 %
Emulsions of any required concentration can be obtained from such concentrates by dilution with water.
Example F10: Dusts a) b) compound 1.050 in admixture with0.1 % 1 %
N-[2-(2-methoxyethoxy)-phenyl-sulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea talcum 99.9 %
kaolin - 99 %
Ready-for-use dusts are obtained by mixing the active ingredient mixture with the carrier and grinding the resulting mixture in a suitable mill.
Example Fll: Extruder granulate a) b) compound 1.006 in admixture with10 % 1 %
N-[2-(2-methoxyethoxy)-phenyl-sulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea sodium lignosulfonate 2 % 2 %
carboxymethylcellulose 1 % 1 %
kaolin 87 % 96 %
The active ingredient mixture is mixed and ground with the adjuvants, and the resulting mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
2 G~ 8 Example Fl2: Coated granulate compound 1.005 in admixture with 3 %
N-chloroacetyl-N-(2-methoxy-l-methylethyl)-2-ethyl-6-methyl-aniline polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %
The finely ground active ingredient mixture is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
Example F13: Suspension concentrate a) b) compound 1.050 in admixture with40 % 5 %
2-[4-(6-chlorobenzoxazol-2-yloxy)-phenoxy]-propionic acid ethyl ester ethylene glycol lO % 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % l %
sodium lignosulfonate lO % 5 %
carboxymethylcellulose l % 1 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32 % 77 %
Example F14: Salt solution compound 1.026 in admixture with 5 %
2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester isopropylamine l %
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3 %
water 91 %
9~
Biological Examples The ability of the compounds of formula I to protect cultivated plants from the phytotoxic effect of potent herbicides can be seen from the following Examples. In the description of the tests, the compounds of formula I are referred to as antidotes (counter-agents or safeners).
The tests are evaluated firstly by determining the action of the herbicide alone as a percentage, 100 % action corresponding to the death of the plants and O % action denoting no action as in the untreated control plants. Secondly, the action of the herbicide/antidote combina-tion is determined in the same manner also as the herbicidal action ex-pressed as a percentage. The difference between the two resulting per-centages is reproduced as "protective action in %" in the test results.
The action of the herbicide/antidote combination can be evaluated both in the case of direct simultaneous application of the two active ingredients as a tank mix in a single spraying operation and in the case of separate application, including application at different times, for example as in seed dressing with the antidote and post-emergenc:e treatment with herbicide.
Example B1: Test with herbicide and antidote in cultivated sorghum.
Herbicide and antidote are applied together as a tank mix according to the pre-emergence or post-emergence method.
Sorghum seeds of the "Funk G-623" variety are sown in pots of 11 cm dia-meter filled with garden 50il and are raised in a greenhouse under suit-able temperature and light conditions. ~ater and fertiliser are supplied as required. In order to determine the pre-emergence action, a mixture of antidote and herbicide are applied in an amount of water of 550 l/ha immediately after sowing. In order to determine the post-emergence action, the active ingredient mixture is applied post-emergence when the plants are in the 3- to 5-leaf stage. In each case the test is evaluated 21 days after treatment to give the "protective action in percent".
' `' ~- ~ .' ' 213~1D9~8 Test results:
a) pre-emergence test:
test plant: sorghum "Funk G-623"
treatment: pre-emergence with a tank mix of 250 g/ha of compound 1.050 and 125 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
action: 21 days after application: 50 % protective action.
b) _ost-emergence test:
test plan~: sorghum "Funk G-623"
treatment: post-emergence with a tank mix of 250 g/ha of compound 1.050 and 125 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
action: 21 days after application: 45 % protective action.
_xample B2: Test with herbicide and antidote in maize and sorghum. The seeds are dressed with the antidote, the herbicide is applied according to the pre-emergence or post-emergence method.
Maize seeds of the "Blizzard" variety and sorghum seeds of the "Funk G-623" variety that have been dressed with the antidote are sown in pots of 11 cm diameter filled with garden soil and are raised in a green-house under suitable temperature and light conditions. Water and fertiliser are supplied as required. In order to determine the pre-emergence action, the herbicide is applied in an amount of water of 550 l/ha immediately after sowing. In order to determine the post-emergence action, the herbicide is applied post-emergence when the plants are in the 3- to 5-leaf stage. In each case the test is evaluated 12 to 26 days after treatment to give the "protective action in percent".
Test results:
a) Maize tests:
test plant: maize "Blizzard"
treatment: seed dressing with 0.5 g, 1 or 2 g of compound 1.050 per kg of maize seed .:
9~3 Herbicide pre-emergence:
4000 g/ha of N-chloroacetyl-N-(2-methoxy-1-methoxyethyl)-ethyl-6-methyl-aniline, or 240 g/ha of N-[2-(3,3,3-trifluoropropen-1-yl)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
Herbicide post-emergence:
120 g/ha of N-(2-methoxycarbonylthien-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 480 g/ha of N-[2-(3,3,3-trifluoro-propen-l-yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 120 g/ha of N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-difluoro-methoxy-6-methoxypyrimidin-2-yl)-urea, or 120 g/ha of N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-urea, or 120 g/ha of N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)-urea, or 10 g/ha of N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 30 g/ha of 2-[4-(6-chloroquinoxalin-2-yloxy)-phenoxy]-propiorlic acid ethyl ester, or 60 g/ha of 2-~4-(6-chlorobenzoxazol-2-yloxy)-phenoxy]-propionic acid ethyl ester, or 30 g/ha of 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, or 10 g/ha of N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)-urea, or 240, 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenyl-sulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
.
, .
Action: (DAT: days after treatment) Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kgin g/ha herbicide/ in %
seed evaluation _ 2 4000 N-Chloroacetyl-N-(2-methoxy-1- pre/14 DAT 40 ethyl~-2-ethyl-6-methylaniline 1 240 N-[2-(3,3,3-Trifluoropropen-l- pre/20 DAT 25 yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea 1 480 post/20 DAT 30 _ 2 120 N-[2-(2-Methoxyethoxy)- pre/12 DAT 70 phenylsulfonyl]-N'~(4,6-di-methoxy-1,3,5-tria7.in-2-yl)~
1 120 pre/12 DAT 65 0.5 120 pre/12 DAT 65 2 60 pre/12 DAT 65 1 60 pre/12 DAT 65 0.5 60 pre/12 DAT 70 2 30 pre/12 DAT 55 1 30 pre/12 DAT 50 0.5 30 pre/12 DAT 55 2 240 post/20 DAT 65 1 240 post/20 DAT 65 0.5 240 post/20 DAT 50 2 120 post/20 DAT 60 1 120 post/20 DAT 55 0.5 120 post/20 DAT 25 2 60 post/20 DAT 40 1 60 post/20 DAT 40 0.5 60 post/20 DAT 35 2 30 post/20 DAT 25 1 30 post/20 DAT 30 0.5 30 post/20 DAT 15 39~8 Continuation Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kg in g/ha herbicide/ in %
seed evaluation 1 120 N-(2-Methoxycarbonylthien-3-yl- post/16 DAT 20 sulfonyl)-N'-(4-methoxy-
.~ ~--F
5.005 4-Tolyl ~ . _ .~-\.
5.006 3,4-Dimethyl-phenyl _ .~
\.=./
.\ /--CH3 5.007 2-Tolyl _.~ ~._ .
\.=./
Formulation ExamPles for active ingredients of formula I or mixtures thereof with herbicides Example Fl: Wettable powders a) b) c) compound 1.050 20 % 60 % 0.5 %
sodium lignosulfonate 5 % 5 % 5 %
sodium laurylsulfate 3 % - -sodium diisobutylnaphthalene-sulfonate - 6 % 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed silicic acid 5 % 27 % 27 %
kaolin 67 %
sodium chloride - - 59.5 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
E mple F2: Emulsifiable concentrate a) b) compound 2.011 10 % 1 %
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 %
cyclohexanone 30 % 10 %
xylene mixture 50 % 79 %
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
Example F3: Dusts a) b) compound 1.050 0.1 % 1 %
talcum 99-9 %
kaolin ~ 99 %
Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
Example F4: Extruder granulate a) b) compound 1.006 10 %1 %
sodium lignosulfonate 2 %2 %
carboxymethylcellulose 1 %1 %
kaolin 87 %96 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
Example F5: Coated granulate compound 1.005 3 %
polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
Example F6: Suspension concentrate a) b) compound 1.050 40 % 5 %
ethylene glycol10 % 10 %
nonylphenol polyethylene glycol ether tl5 moles of ethylene oxide) 6 % 1 %
sodium lignosulfonate10 % 5 %
carboxymethylcellulose1 % 1 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
: :. , , .: ~
.: . . : ' : ::
:
,, ::
:. : , ~ : ~
2C~39~1~
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32 % 77 %
Example F7: Salt solution compound 1.026 5 %
isopropylamine 1 %
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3 %
water 91 %
Example F8: Wettable powders a) b) c) compound 1.050 in admixture with 20 % 60 % 0.5 %
N-[2-(2-methoxyethoxy)-phenyl-sulEonyl]-N'-(4,6-dimethoxy-1,3,5-tria~in-2-yl]-urea sodium lignosulfonate 5 % 5 % 5 %
sodium laurylsulfate 3 %
sodium diisobutylnaphthalene-sulfonate - 6 % 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 % 2 %
highly dispersed silicic acid 5 % 27 % 27 %
~aolin 67 %
sodium chloride - - 59.5 %
The active ingredient mixture is thoroughly mixed with the adjuvants and the resul~ing mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
Example F9: Emulsifiable concentrate a) b) compound 2.011 in admixture with 10 % 1 %
2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy~-propionic acid n-butyl ester octylphenol polyethylene glycol ether (4-S moles of ethylene oxide) 3 % 3 %
calcium dodecylbenzenesulfonate 3 % 3 %
castor oil polyglycol ether (36 moles of ethylene oxide) 4 % 4 %
cyclohexanone 30 % 10 %
xylene mixture 50 % 79 %
Emulsions of any required concentration can be obtained from such concentrates by dilution with water.
Example F10: Dusts a) b) compound 1.050 in admixture with0.1 % 1 %
N-[2-(2-methoxyethoxy)-phenyl-sulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea talcum 99.9 %
kaolin - 99 %
Ready-for-use dusts are obtained by mixing the active ingredient mixture with the carrier and grinding the resulting mixture in a suitable mill.
Example Fll: Extruder granulate a) b) compound 1.006 in admixture with10 % 1 %
N-[2-(2-methoxyethoxy)-phenyl-sulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea sodium lignosulfonate 2 % 2 %
carboxymethylcellulose 1 % 1 %
kaolin 87 % 96 %
The active ingredient mixture is mixed and ground with the adjuvants, and the resulting mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
2 G~ 8 Example Fl2: Coated granulate compound 1.005 in admixture with 3 %
N-chloroacetyl-N-(2-methoxy-l-methylethyl)-2-ethyl-6-methyl-aniline polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %
The finely ground active ingredient mixture is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
Example F13: Suspension concentrate a) b) compound 1.050 in admixture with40 % 5 %
2-[4-(6-chlorobenzoxazol-2-yloxy)-phenoxy]-propionic acid ethyl ester ethylene glycol lO % 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % l %
sodium lignosulfonate lO % 5 %
carboxymethylcellulose l % 1 %
37 % aqueous formaldehyde solution 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32 % 77 %
Example F14: Salt solution compound 1.026 in admixture with 5 %
2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester isopropylamine l %
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3 %
water 91 %
9~
Biological Examples The ability of the compounds of formula I to protect cultivated plants from the phytotoxic effect of potent herbicides can be seen from the following Examples. In the description of the tests, the compounds of formula I are referred to as antidotes (counter-agents or safeners).
The tests are evaluated firstly by determining the action of the herbicide alone as a percentage, 100 % action corresponding to the death of the plants and O % action denoting no action as in the untreated control plants. Secondly, the action of the herbicide/antidote combina-tion is determined in the same manner also as the herbicidal action ex-pressed as a percentage. The difference between the two resulting per-centages is reproduced as "protective action in %" in the test results.
The action of the herbicide/antidote combination can be evaluated both in the case of direct simultaneous application of the two active ingredients as a tank mix in a single spraying operation and in the case of separate application, including application at different times, for example as in seed dressing with the antidote and post-emergenc:e treatment with herbicide.
Example B1: Test with herbicide and antidote in cultivated sorghum.
Herbicide and antidote are applied together as a tank mix according to the pre-emergence or post-emergence method.
Sorghum seeds of the "Funk G-623" variety are sown in pots of 11 cm dia-meter filled with garden 50il and are raised in a greenhouse under suit-able temperature and light conditions. ~ater and fertiliser are supplied as required. In order to determine the pre-emergence action, a mixture of antidote and herbicide are applied in an amount of water of 550 l/ha immediately after sowing. In order to determine the post-emergence action, the active ingredient mixture is applied post-emergence when the plants are in the 3- to 5-leaf stage. In each case the test is evaluated 21 days after treatment to give the "protective action in percent".
' `' ~- ~ .' ' 213~1D9~8 Test results:
a) pre-emergence test:
test plant: sorghum "Funk G-623"
treatment: pre-emergence with a tank mix of 250 g/ha of compound 1.050 and 125 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
action: 21 days after application: 50 % protective action.
b) _ost-emergence test:
test plan~: sorghum "Funk G-623"
treatment: post-emergence with a tank mix of 250 g/ha of compound 1.050 and 125 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
action: 21 days after application: 45 % protective action.
_xample B2: Test with herbicide and antidote in maize and sorghum. The seeds are dressed with the antidote, the herbicide is applied according to the pre-emergence or post-emergence method.
Maize seeds of the "Blizzard" variety and sorghum seeds of the "Funk G-623" variety that have been dressed with the antidote are sown in pots of 11 cm diameter filled with garden soil and are raised in a green-house under suitable temperature and light conditions. Water and fertiliser are supplied as required. In order to determine the pre-emergence action, the herbicide is applied in an amount of water of 550 l/ha immediately after sowing. In order to determine the post-emergence action, the herbicide is applied post-emergence when the plants are in the 3- to 5-leaf stage. In each case the test is evaluated 12 to 26 days after treatment to give the "protective action in percent".
Test results:
a) Maize tests:
test plant: maize "Blizzard"
treatment: seed dressing with 0.5 g, 1 or 2 g of compound 1.050 per kg of maize seed .:
9~3 Herbicide pre-emergence:
4000 g/ha of N-chloroacetyl-N-(2-methoxy-1-methoxyethyl)-ethyl-6-methyl-aniline, or 240 g/ha of N-[2-(3,3,3-trifluoropropen-1-yl)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
Herbicide post-emergence:
120 g/ha of N-(2-methoxycarbonylthien-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 480 g/ha of N-[2-(3,3,3-trifluoro-propen-l-yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 120 g/ha of N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-difluoro-methoxy-6-methoxypyrimidin-2-yl)-urea, or 120 g/ha of N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-urea, or 120 g/ha of N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)-urea, or 10 g/ha of N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 30 g/ha of 2-[4-(6-chloroquinoxalin-2-yloxy)-phenoxy]-propiorlic acid ethyl ester, or 60 g/ha of 2-~4-(6-chlorobenzoxazol-2-yloxy)-phenoxy]-propionic acid ethyl ester, or 30 g/ha of 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, or 10 g/ha of N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)-urea, or 240, 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenyl-sulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
.
, .
Action: (DAT: days after treatment) Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kgin g/ha herbicide/ in %
seed evaluation _ 2 4000 N-Chloroacetyl-N-(2-methoxy-1- pre/14 DAT 40 ethyl~-2-ethyl-6-methylaniline 1 240 N-[2-(3,3,3-Trifluoropropen-l- pre/20 DAT 25 yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea 1 480 post/20 DAT 30 _ 2 120 N-[2-(2-Methoxyethoxy)- pre/12 DAT 70 phenylsulfonyl]-N'~(4,6-di-methoxy-1,3,5-tria7.in-2-yl)~
1 120 pre/12 DAT 65 0.5 120 pre/12 DAT 65 2 60 pre/12 DAT 65 1 60 pre/12 DAT 65 0.5 60 pre/12 DAT 70 2 30 pre/12 DAT 55 1 30 pre/12 DAT 50 0.5 30 pre/12 DAT 55 2 240 post/20 DAT 65 1 240 post/20 DAT 65 0.5 240 post/20 DAT 50 2 120 post/20 DAT 60 1 120 post/20 DAT 55 0.5 120 post/20 DAT 25 2 60 post/20 DAT 40 1 60 post/20 DAT 40 0.5 60 post/20 DAT 35 2 30 post/20 DAT 25 1 30 post/20 DAT 30 0.5 30 post/20 DAT 15 39~8 Continuation Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kg in g/ha herbicide/ in %
seed evaluation 1 120 N-(2-Methoxycarbonylthien-3-yl- post/16 DAT 20 sulfonyl)-N'-(4-methoxy-
6-methyl-1,3,5-triazin-2-yl)-urea 1 120 N-(2-Methoxycarbonylphenyl post/16 DAT 15 sulfonyl)-N'-(4-difluoro-methoxy-6-methoxy-pyrimidin-2- . .
yl)-urea ., 1 120 N-(2-Methoxycarbonylphenyl post/16 DAT 20 sulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)~
urea _ _ 1 120 N-(2-Methoxycarbonylphenyl post/16 DAT 20 sulfonyl)-N'-(4,6-bis-difluoro-methoxy-pyrimidin-2-yl)-urea 1 10 N-[2-(2-Chloroethoxy)-phenyl post/16 DAT 35 sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea 1 30 2-~4-(6-Chloroquinoxalin-2- postll6 DAT 30 yloxy)-phenoxy]-propionic acid ethyl ester 1 30 2-[4-(3,5-Dichloropyridin-2- post/16 DAT 45 yloxy)-phenoxy]-propionic acid propargyl ester _ 1 10 N-(2-hethoxycarbonylphenyl- post/16 DAT 30 sulfonyl)-N'-(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)-urea 1 60 2-[4-(6-Chlorobenzoxa2O1-2- postl16 DAT 30 yloxy)-phenoxy]-propionic acid ethyl ester 2~
b) Sorghum tests:
test plant: Sorghum "Funk G-623"
treatment: Seed dressing with 0.5 g, 1 or 2 g of compound 1.050 per kg of sorghum seed Herbicide pre-emergence:
1000 g/ha of N-chloroacetyl-N-(2-methoxy-1-methoxyethyl)-ethyl-6-methyl-aniline, or 250 g/ha of N-[2-(3,3,3-trifluoropropen-1-yl)-phenyl-sulfonyl]-N'-t4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
Herbicide post-emergence:
480 g/ha of N-[2-~3,3,3-trifluoropropen-1-yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 15 g/ha of 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-propionic acid ethyl ester, or 60 g/ha of 2-[4-(6-chlorobenzoxazol-2-yloxy)-phenoxy]-propionic acid ethyl ester, or 15 g/ha of 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, or 30 g/ha of 2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, or 240, 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethnxy-1,3,5-triazin-2-yl)-urea.
. ~ , 9~3 Action: (DAT: days after treatment) Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kg in g/ha herbicide/ in %
seed evaluation 1 1000 N-Chloroacetyl-N-(2-methoxy-1- pre/26 DAT 35 ethyl)-2-ethyl-6-methylaniline 1 250 N-[2-(3,3,3-Trifluoropropen-l- pre/20 DAT 45 yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea 1 480 . post/20 DAT 40 _ 2 120 N-[2-(2-Methoxyethoxy)- pre/12 DAT 55 phenylsulfonyl]-N'-(4,6-di-methoxy-1,3,5-triazin-2-yl)-1 120 pre/12 DAT 55 0.5 120 pre/12 DAT 60 2 60 pre/12 DAT 55 pre/12 DAT 50 0.5 60 pre/12 DAT 60 2 30 pre/12 DAT 70 1 30 . pretl2 DAT 65 0.5 30 pre/12 DAT 70 2 240 postl20 DAT 50 1 240 post/20 DAT 60 0.5 240 post/20 DAT 60 2 120 . post/20 DAT 50 1 120 post/20 DAT 65 0.5 120 post/20 DAT 60 2 60 post/20 DAT 45 1 60 post/20 DAT 65 0.5 60 post/20 DAT 60 2 30 post/20 DAT 30 1 30 postl20 DAT 45 0.5 30 post/20 DAT 50 ,, , '' `,:, '. ':
. . : .
2~ 28 Continuation Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kg in g/ha herbicide/ in %
seed evaluation 1 60 2-[4-(6-Chlorobenzoxazol- post/16 DAT 33 2-yloxy)-phenoxy]-propionic acid ethyl ester 1 15 2-[4-(6-Chloroquinoxalin-2- post/16 DAT 40 yloxy)-phenoxy]-propionic acid ethyl ester _ 1 15 2-[4-(3,5-Dichloropyridin-2- post/16 DAT 50 yloxy)-phenoxy]-propionic acid propargyl ester 1 30 2-[4-(5-Trifluoromethylpyridin- post/16 DAT 20 2-yloxy)-phenoxy]-propionic butyl ester ._ Test results:
Example B3: Test with herbicide and antidote in rice. The seeds are soaked in antidote dispersion, the herbicide is applied according to the pre-emergence method.
Rice seeds of the "S-201" variety are soaked for 48 hours in an aqueousdispersion of the antidote, then stored dry for 24 hours and Einally sown on the surface in pots (9 x 9 cm) filled with boggy garden soil.
Immediately after sowing the surface of the soil is sprayed with the herbicide in an amount of water of 550 l/ha. The plants are raised in a greenhouse under suitable temperature and light conditions. Water and fertiliser are supplied as required. The test is evaluated 26 days after treatment to give the "protective action in percent".
.. . .
'~ '.: - :,, .
32~
Test resul~s_ test plant: rice "S-201"
treatment: 48 hours soaking of the seeds in a 300 ppm solution of com-pound 1.050 followed by pre-emergence application of 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea action: 26 days after application: 55 % protective action.
yl)-urea ., 1 120 N-(2-Methoxycarbonylphenyl post/16 DAT 20 sulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)~
urea _ _ 1 120 N-(2-Methoxycarbonylphenyl post/16 DAT 20 sulfonyl)-N'-(4,6-bis-difluoro-methoxy-pyrimidin-2-yl)-urea 1 10 N-[2-(2-Chloroethoxy)-phenyl post/16 DAT 35 sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea 1 30 2-~4-(6-Chloroquinoxalin-2- postll6 DAT 30 yloxy)-phenoxy]-propionic acid ethyl ester 1 30 2-[4-(3,5-Dichloropyridin-2- post/16 DAT 45 yloxy)-phenoxy]-propionic acid propargyl ester _ 1 10 N-(2-hethoxycarbonylphenyl- post/16 DAT 30 sulfonyl)-N'-(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)-urea 1 60 2-[4-(6-Chlorobenzoxa2O1-2- postl16 DAT 30 yloxy)-phenoxy]-propionic acid ethyl ester 2~
b) Sorghum tests:
test plant: Sorghum "Funk G-623"
treatment: Seed dressing with 0.5 g, 1 or 2 g of compound 1.050 per kg of sorghum seed Herbicide pre-emergence:
1000 g/ha of N-chloroacetyl-N-(2-methoxy-1-methoxyethyl)-ethyl-6-methyl-aniline, or 250 g/ha of N-[2-(3,3,3-trifluoropropen-1-yl)-phenyl-sulfonyl]-N'-t4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
Herbicide post-emergence:
480 g/ha of N-[2-~3,3,3-trifluoropropen-1-yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, or 15 g/ha of 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-propionic acid ethyl ester, or 60 g/ha of 2-[4-(6-chlorobenzoxazol-2-yloxy)-phenoxy]-propionic acid ethyl ester, or 15 g/ha of 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, or 30 g/ha of 2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, or 240, 120, 60 or 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethnxy-1,3,5-triazin-2-yl)-urea.
. ~ , 9~3 Action: (DAT: days after treatment) Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kg in g/ha herbicide/ in %
seed evaluation 1 1000 N-Chloroacetyl-N-(2-methoxy-1- pre/26 DAT 35 ethyl)-2-ethyl-6-methylaniline 1 250 N-[2-(3,3,3-Trifluoropropen-l- pre/20 DAT 45 yl)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea 1 480 . post/20 DAT 40 _ 2 120 N-[2-(2-Methoxyethoxy)- pre/12 DAT 55 phenylsulfonyl]-N'-(4,6-di-methoxy-1,3,5-triazin-2-yl)-1 120 pre/12 DAT 55 0.5 120 pre/12 DAT 60 2 60 pre/12 DAT 55 pre/12 DAT 50 0.5 60 pre/12 DAT 60 2 30 pre/12 DAT 70 1 30 . pretl2 DAT 65 0.5 30 pre/12 DAT 70 2 240 postl20 DAT 50 1 240 post/20 DAT 60 0.5 240 post/20 DAT 60 2 120 . post/20 DAT 50 1 120 post/20 DAT 65 0.5 120 post/20 DAT 60 2 60 post/20 DAT 45 1 60 post/20 DAT 65 0.5 60 post/20 DAT 60 2 30 post/20 DAT 30 1 30 postl20 DAT 45 0.5 30 post/20 DAT 50 ,, , '' `,:, '. ':
. . : .
2~ 28 Continuation Safener Herbicide Mode of protec-dressing -applica- application tive quantity tion rate of action in g/kg in g/ha herbicide/ in %
seed evaluation 1 60 2-[4-(6-Chlorobenzoxazol- post/16 DAT 33 2-yloxy)-phenoxy]-propionic acid ethyl ester 1 15 2-[4-(6-Chloroquinoxalin-2- post/16 DAT 40 yloxy)-phenoxy]-propionic acid ethyl ester _ 1 15 2-[4-(3,5-Dichloropyridin-2- post/16 DAT 50 yloxy)-phenoxy]-propionic acid propargyl ester 1 30 2-[4-(5-Trifluoromethylpyridin- post/16 DAT 20 2-yloxy)-phenoxy]-propionic butyl ester ._ Test results:
Example B3: Test with herbicide and antidote in rice. The seeds are soaked in antidote dispersion, the herbicide is applied according to the pre-emergence method.
Rice seeds of the "S-201" variety are soaked for 48 hours in an aqueousdispersion of the antidote, then stored dry for 24 hours and Einally sown on the surface in pots (9 x 9 cm) filled with boggy garden soil.
Immediately after sowing the surface of the soil is sprayed with the herbicide in an amount of water of 550 l/ha. The plants are raised in a greenhouse under suitable temperature and light conditions. Water and fertiliser are supplied as required. The test is evaluated 26 days after treatment to give the "protective action in percent".
.. . .
'~ '.: - :,, .
32~
Test resul~s_ test plant: rice "S-201"
treatment: 48 hours soaking of the seeds in a 300 ppm solution of com-pound 1.050 followed by pre-emergence application of 30 g/ha of N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea action: 26 days after application: 55 % protective action.
Claims (71)
1. N-acylsulfamoylphenylureas of formula I
(I) wherein A is a radical selected from the group , , , or , each of R1 and R2, independently of the other, is hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, or C1-C4alkyl substituted by C1-C4alkoxy or by or R1 and R2 together form a C4-C6alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, sulfur, SO, SO2, NH or by -N(C1-C4alkyl)-, R3 is hydrogen or C1-C4alkyl, each of R and R , independently of the other is hydrogen, halogen, cyano, nitro, trifluoromethyl, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRm or -OSO2-C1-C4alkyl, or Ra and Rb together form a C3-C4alkylene bridge, which can be substituted by halogen or by C1-C4alkyl, or a C3-C4alkenylene bridge, which can be substituted by halogen or by C3-C4alkyl, or a C4alkadienylene bridge which can be substituted by halogen or by C1-C4alkyl, and each of Rg and Rh, indepen-dently of the other, is hydrogen, halogen, Cl-C4alkyl, trifluoromethyl, methoxy, methylthio or -COORi, wherein Rc is hydrogen, halogen, C1-C4-alkyl or methoxy, Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4-alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj or -CONRkRm, Re is hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4alkylene bridge, Rf is hydrogenl halogen or C1-C4alkyl, each of Rx and Ry, independently of the other, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, -COOR4 , trifluoromethyl, nitro or cyano, each of Rj, Rk and Rm , indepen-dently of the others, is hydrogen or C1-C4alkyl, Rk and Rm together form a C4-C6alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, NH or by -N(C1-C4alkyl)-, and Rn is C1-C4alkyl, phenyl, or phenyl sub-stituted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl.
(I) wherein A is a radical selected from the group , , , or , each of R1 and R2, independently of the other, is hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, or C1-C4alkyl substituted by C1-C4alkoxy or by or R1 and R2 together form a C4-C6alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, sulfur, SO, SO2, NH or by -N(C1-C4alkyl)-, R3 is hydrogen or C1-C4alkyl, each of R and R , independently of the other is hydrogen, halogen, cyano, nitro, trifluoromethyl, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRm or -OSO2-C1-C4alkyl, or Ra and Rb together form a C3-C4alkylene bridge, which can be substituted by halogen or by C1-C4alkyl, or a C3-C4alkenylene bridge, which can be substituted by halogen or by C3-C4alkyl, or a C4alkadienylene bridge which can be substituted by halogen or by C1-C4alkyl, and each of Rg and Rh, indepen-dently of the other, is hydrogen, halogen, Cl-C4alkyl, trifluoromethyl, methoxy, methylthio or -COORi, wherein Rc is hydrogen, halogen, C1-C4-alkyl or methoxy, Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4-alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj or -CONRkRm, Re is hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4alkylene bridge, Rf is hydrogenl halogen or C1-C4alkyl, each of Rx and Ry, independently of the other, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, -COOR4 , trifluoromethyl, nitro or cyano, each of Rj, Rk and Rm , indepen-dently of the others, is hydrogen or C1-C4alkyl, Rk and Rm together form a C4-C6alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, NH or by -N(C1-C4alkyl)-, and Rn is C1-C4alkyl, phenyl, or phenyl sub-stituted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl.
2. Compounds of formula I according to claim 1 wherein A is a radical selected from the group , , , or , each of R1 and R2, independently of the other, is hydrogen, C1-C3alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, or C1-C4alkyl substituted by C1-C4alkoxy or by or R1 and R2 together form a C4-C6alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, sulfur, SO, SO2, NH or by -N(Cl-C4alkyl)-, R3 is hydrogen or C1-C4alkyl, each of Ra and Rb, independently of the other, is hydrogen, halogen, cyano, nitro, trifluoromethyl, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRm or -OSO2-C1-C4alkyl, and each of Rg and Rh, independently of the other, is hydrogen, halogen, C1-C4alkyl, trifluoromethyl, methoxy, methylthio or -COORj, wherein Rc is hydrogen, halogen, C1-C4alkyl or methoxy, Rd is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkyl-sulfonyl, -COORj or -CONRkRm, R is hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4-alkylene bridge, Rf is hydrogen, halogen or C1-C4alkyl, each of Rx and RY, independently of the other, is hydrogen, halogen, C1-C4alkyl, C1-C4-alkoxy, C1-C4alkylthio, -COOR4, trifluoromethyl, nitro or cyano, each of Rj, Rk and Rm, independently of the others, is hydrogen or C1-C4alkyl, Rk and Rm together form a C4-C6alkylene bridge, or a C4-C6alkylene bridge interrupted by oxygen, NH or by -N(C1-C4alkyl)-, and Rn is C1-C4alkyl, phenyll or phenyl substituted by halogen, C1-C4alkyl, methoxy, nitro or by trifluoromethyl.
3. Compounds according to claim 1 wherein Rb is hydrogen.
4. Compounds according to claim 1 wherein the sulfamoyl group occupies the 4-position of the phenyl ring.
5. Compounds according to claim 1 wherein R2 and R3 are hydrogen.
6. Compounds according to claim 1 wherein R is hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
7. Compounds according to claim 1 wherein R2, R3 and Rb are hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
8. Compounds according to claim 1 wherein A is the group
9. Compounds according to claim 8 wherein R2, R3 and Rb are hydrogen and the sulfamoyl group occupies the 4-position of the phenyl ring.
10. Compounds according to claim 1 falling within the scope of sub-formula Ia (Ia)
11. Compounds according to claim 10 wherein Rc is hydrogen.
12. Compounds according to claim 11 wherein R1, Rg and Rh are C1-C4alkyl.
13. 1-[4-(N-4-methylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
14. 1-[4-(N-3-methylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
15. 1-[4-(N-4-tert.-butylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
16. 1-[4-(N-3-trifluoromethylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
17. 1-[4-(N-4-nitrobenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
18. 1-[4-(N-2,3-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
19. 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
20. 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3,3-dimethylurea according to claim 1.
21. 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-ethylurea according to claim 1.
22. 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-allylurea according to claim 1.
23. 1-[4-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-phenylurea according to claim 1.
24. 1-[4-tN-3,5-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
25. 1-[4-(N-3,4-dichlorobenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
26. 1-[4-(N-3,4-dimethoxybenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
27. 1-[4-(N-3,4-dimethoxybenzoylsulfamoyl)-phenyl]-3,3-dimethylurea according to claim 1.
28. 1-[4-(N-2,4,5-trimethoxybenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
29. 1-[4-(N-1-naphthylcarbonylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
30. 1-[4-(N-2-furylcarbonylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
31. 1-[4-(N-2-furylcarbonylsulfamoyl)-phenyl] 3,3-dimsthylurea according to claim 1.
32. 1-[4-(N--2-thienylcarbonylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
33. 1-[4-(N-piperonyloylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
34. 1-[4-(N-3-methylbenzoylsulfamoyl)-phenyl]-3,3-dimethylurea according to claim 1.
35. 1-[4-(N-3-trifluoromethylbenzoylsulfamoyl)-phenyl]-3-cyclopropylurea according to claim 1.
36. 1-[3-(N-3,4-dimethylbenzoylsulfamoyl)-phenyl]-3-methylurea according to claim 1.
37. 1-[3-(N-2-furylcarbonylsulfamoyl)-phenyl]-3,3-dimethylurea according to claim 1.
38. A composition for protecting cultivated plants from the phytotoxic action of sulfonylurea herbicides, chloroacetanilide herbicides, acyl-cyclohexanedione herbicides or aryloxyphenoxypropionic acid herbicides, which composition contains a compound of formula I according to claim 1.
39. A composition for protecting cultivated plants from the phytotoxic action of sulfonylurea herbicides, chloroacetanilide herbicides or aryl-oxyphenoxypropionic acid herbicides, which composition contains a com-pound of formula I according to claim 1.
40. A composition according to claim 39 wherein the cultivated plants are rice, maize, sorghum, cereals or soybeans.
41. A composition according to claim 40 wherein the cultivated plants are rice, maize or sorghum.
42. A composition according to claim 39 wherein the cultivated plants are sorghum and the herbicides are sulfonylureas.
43. A composition according to claim 39, wherein it is used for protect-ing cultivated plants from the phytotoxic action of suLfonylurea herbicides of formula II
(II) wherein E is a group , , , or , n is O or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, C1-C4haloalkoxy, C1-C4haloalkylthio, C2-C4haloalkenyl, chlorine or C1-C4-alkoxycarbonyl, R5 is trifluoromethyl or di(C1-Chalkyl)carbamoyl, Rs is C1-C4alkoxycarbonyl, R7 is C1-C4alkoxycarbonyl, and R8 is C1-C4alkyl.
(II) wherein E is a group , , , or , n is O or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, C1-C4haloalkoxy, C1-C4haloalkylthio, C2-C4haloalkenyl, chlorine or C1-C4-alkoxycarbonyl, R5 is trifluoromethyl or di(C1-Chalkyl)carbamoyl, Rs is C1-C4alkoxycarbonyl, R7 is C1-C4alkoxycarbonyl, and R8 is C1-C4alkyl.
44. A composition according to claim 43 wherein the sulfonylureas of formula II are selected from the group:
N-(3-trifluoromethylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(3-dimethylcarbamoylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(1-methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylthien-3-yl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxy-carbonylbenzylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-ethoxycarbonylphenyl-sulfonyl)-N'-(4-chloro-6-methoxypyrimidin-2-yl)-urea, N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl 1,3,5-triazin-2-yl)-urea, N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea and N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
N-(3-trifluoromethylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(3-dimethylcarbamoylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(1-methyl-4-ethoxycarbonylpyrazol-2-ylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylthien-3-yl-sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxy-carbonylbenzylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-ethoxycarbonylphenyl-sulfonyl)-N'-(4-chloro-6-methoxypyrimidin-2-yl)-urea, N-(2-methoxy-carbonylphenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N'-methylurea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea, N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl 1,3,5-triazin-2-yl)-urea, N-[2-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea and N-[2-(2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea.
45. A composition according to claim 39, wherein it is used for protect-ing cultivated plants from the phytotoxic action of chloroacetanilide herbicides of formula III
(III) wherein L is a C1-C4alkylene bridge, each of R9, R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-C5alkoxyalkyl or C2-C5alkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyrrolyl, unsubsti-tuted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxa-diazol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, unsub-stituted or substituted 1,2,4-triazol-3-yl, unsubstituted or substituted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or sub-stituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetrahydro-furyl.
(III) wherein L is a C1-C4alkylene bridge, each of R9, R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-C5alkoxyalkyl or C2-C5alkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyrrolyl, unsubsti-tuted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxa-diazol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, unsub-stituted or substituted 1,2,4-triazol-3-yl, unsubstituted or substituted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or sub-stituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetrahydro-furyl.
46. A composition according to claim 45 wherein the chloroacetanilides of formula III are selected from the group:
N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline, N-chlorvacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxysthyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(methoxy-ethyl)-2,6-diethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methyl-aniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline, N-chloro-acetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline, N-(2-ethoxy-ethyl)-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-(2-n-propoxy-ethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methyl-aniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline, N-chloroacetyl-N-(2,2-di-ethoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methyl-ethylt-2,3-dimethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-methyl-aniline, N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline, N-chloro-acetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline, N-(2-ethoxy-2-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(1-ethyl-1-methoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-methoxy-6-methylaniline, N-n-butoxymethyl-N-chloro-acetyl-2-tert.-butylaniline, N-(2-ethoxyethyl-2-methylethyl)-2,6-di-methylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-chloro-6-methyl-aniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2,3,6-trimethylaniline, N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline, N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-di-methylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methyl-aniline, N-chloroacetyl-N-(2-furylmethyl)-2,6-dimethylaniline, N-chloro-acetyl-N-(2-furylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-tetrahydrofurylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(N,N-di-methylcarbamoylmethyl)-2,6-dimethylaniline, N-(n-butoxymethyl)-N-chloro-acetyl-2,6-diethylaniline, N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-di-ethylaniline, N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-di-methylaniline, N-chloroacetyl-N-isopropyl-2,3-dimethylaniline, N-chloro-acetyl-N-isopropyl-2-chloroaniline, N-chloroacetyl-N-(lH-pyrazol-1-yl-methyl)-2,6-dimethylaniline, N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert.-butylaniline, N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline and N-chloroacetyl-N-(1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl)-2,6-diethylaniline.
N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline, N-chlorvacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxysthyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(methoxy-ethyl)-2,6-diethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methyl-aniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline, N-chloro-acetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline, N-(2-ethoxy-ethyl)-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-(2-n-propoxy-ethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline, N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methyl-aniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline, N-chloroacetyl-N-(2,2-di-ethoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-1-methyl-ethylt-2,3-dimethylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-methyl-aniline, N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline, N-chloro-acetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline, N-(2-ethoxy-2-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(1-ethyl-1-methoxyethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-methoxy-6-methylaniline, N-n-butoxymethyl-N-chloro-acetyl-2-tert.-butylaniline, N-(2-ethoxyethyl-2-methylethyl)-2,6-di-methylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-chloro-6-methyl-aniline, N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline, N-(2-ethoxyethyl)-N-chloroacetyl-2,3,6-trimethylaniline, N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline, N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-di-methylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methyl-aniline, N-chloroacetyl-N-(2-furylmethyl)-2,6-dimethylaniline, N-chloro-acetyl-N-(2-furylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-tetrahydrofurylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(N,N-di-methylcarbamoylmethyl)-2,6-dimethylaniline, N-(n-butoxymethyl)-N-chloro-acetyl-2,6-diethylaniline, N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-di-ethylaniline, N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-di-methylaniline, N-chloroacetyl-N-isopropyl-2,3-dimethylaniline, N-chloro-acetyl-N-isopropyl-2-chloroaniline, N-chloroacetyl-N-(lH-pyrazol-1-yl-methyl)-2,6-dimethylaniline, N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(lH-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2,6-diethylaniline, N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert.-butylaniline, N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline and N-chloroacetyl-N-(1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl)-2,6-diethylaniline.
47. A composition according to claim 39, wherein it is used to protect cultivated plants from the phytotoxic action of aryloxyphenoxypropionic acid herbicides of formula IV
(IV) wherein Q is a radical , , , or and T is -NR15R16, -N(CN)Rl7, -OR13, SR18 or -o-N=CR19R20, wherein R13 is halogen or trifluoromethyl, R14 is hydrogen or halogen, each of R15 and R16, independently of the other, is hydrogen, C1-C8alkoxy, C1-C3alkyl, phenyl or benzyl, R15 and R16 together with the nitrogen atom carrying them form a 5- or 6-membered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, R18 is hydrogen or the equiv alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C1-C4alkylammonium or C1-C4hydroxyalkylammonium radical; a C1-Cgalkyl radical that is unsubstituted or mono- or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, C1-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR21, -COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl, CONH-C1-C4alkyl, -N(C1-C4alkoxy)-C1l-C4alkyl or by di-C1-C4alkylamino; a C3-C9alkenyl radical that is unsubstituted or substituted by halogen or by C1-C4-alkoxy; a C3-C9alkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-C9cycloalkyl; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1-C4alkoxy, acetyl, -COOR2l, COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4alkyl, or together they form a 3- to 6-membered alkyleno chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3-C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
(IV) wherein Q is a radical , , , or and T is -NR15R16, -N(CN)Rl7, -OR13, SR18 or -o-N=CR19R20, wherein R13 is halogen or trifluoromethyl, R14 is hydrogen or halogen, each of R15 and R16, independently of the other, is hydrogen, C1-C8alkoxy, C1-C3alkyl, phenyl or benzyl, R15 and R16 together with the nitrogen atom carrying them form a 5- or 6-membered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, R18 is hydrogen or the equiv alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C1-C4alkylammonium or C1-C4hydroxyalkylammonium radical; a C1-Cgalkyl radical that is unsubstituted or mono- or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, C1-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR21, -COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl, CONH-C1-C4alkyl, -N(C1-C4alkoxy)-C1l-C4alkyl or by di-C1-C4alkylamino; a C3-C9alkenyl radical that is unsubstituted or substituted by halogen or by C1-C4-alkoxy; a C3-C9alkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-C9cycloalkyl; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1-C4alkoxy, acetyl, -COOR2l, COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4alkyl, or together they form a 3- to 6-membered alkyleno chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3-C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
48. A composition according to claim 47 wherein the aryloxyphenoxy-propionic acid derivatives of formula IV are selected from the group:
2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-thiopropionic acid propargyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid methyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy~-propionic acid butyl ester, 2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, 2-[4-(5-trifluoromethyl-pyridin-2-yloxy)-phenoxy]-propionic acid mPthyl ester, 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-propionic acid ethyl ester and 2-[4-(6-chlorobenzoxazolin-2-yloxy)-phenoxy]-propionic acid ethyl ester.
2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-propionic acid propargyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-thiopropionic acid propargyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid methyl ester, 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy~-propionic acid butyl ester, 2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy]-propionic acid butyl ester, 2-[4-(5-trifluoromethyl-pyridin-2-yloxy)-phenoxy]-propionic acid mPthyl ester, 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-propionic acid ethyl ester and 2-[4-(6-chlorobenzoxazolin-2-yloxy)-phenoxy]-propionic acid ethyl ester.
49. A composition according to claim 38, wherein it is used for protect-ing cultivated plants from the phytotoxic action of acylcyclohexanedione herbicides of formula IX
(IX) wherein A1 is a 2- to 7-membered alkylene bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n1 is 0, 1 or 2, R2z is C1-C4alkyl or benzyl, R23 is C1-C6alkyl unsubstituted or sub-stituted by halogen, C1-C4alkoxy or by C1-C4alkylthio; C3-C6cycloalkyl;
phenyl, benzyl or phenylethyl wherein the phenyl ring can be substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C1-C4haloalkoxy, cyano or by nitro, X1 is oxygen or a radical -NOR24, and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl.
(IX) wherein A1 is a 2- to 7-membered alkylene bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n1 is 0, 1 or 2, R2z is C1-C4alkyl or benzyl, R23 is C1-C6alkyl unsubstituted or sub-stituted by halogen, C1-C4alkoxy or by C1-C4alkylthio; C3-C6cycloalkyl;
phenyl, benzyl or phenylethyl wherein the phenyl ring can be substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C1-C4haloalkoxy, cyano or by nitro, X1 is oxygen or a radical -NOR24, and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl.
S0. A composition according to claim 49 wherein the acylcyclohexanedione herbicides are selected from the group:
5-(1-methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-cyclopropylcarbonylcyclohexane-1,3-di-one, 5-(1-methylthiocyclobutan-1-yl)-2-(2,3-dichlorobenzoyl)-cyclohexane-1,3-dione, 5-(1-methylsulfonylcyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dione, 5-(1-ethylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dione and 5-(1-methylthiocyclopropan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclohexan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-(1-allyloxyimino-n-butyryl)-cyclohexane-1,3-dione and 5-(1-methylthiocyclo-pentan-l-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-l-yl)-2-[1-(trans-3-chloroallyloxyimino)-n-butyryl]-cyclohexane-1,3-dione, 5-(l-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(cis-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione and 5-(1-ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione.
5-(1-methylthiocyclobutan-1-yl)-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-cyclopropylcarbonylcyclohexane-1,3-di-one, 5-(1-methylthiocyclobutan-1-yl)-2-(2,3-dichlorobenzoyl)-cyclohexane-1,3-dione, 5-(1-methylsulfonylcyclobutan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dione, 5-(1-ethylthiocyclopropan-1-yl)-2-propionylcyclohexane-1,3-dione and 5-(1-methylthiocyclopropan-1-yl)-2-n-butyrylcyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclohexan-1-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclobutan-1-yl)-2-(1-allyloxyimino-n-butyryl)-cyclohexane-1,3-dione and 5-(1-methylthiocyclo-pentan-l-yl)-2-(1-ethoxyimino-n-butyryl)-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-l-yl)-2-[1-(trans-3-chloroallyloxyimino)-n-butyryl]-cyclohexane-1,3-dione, 5-(l-methylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione, 5-(1-methylthiocyclopropan-1-yl)-2-[1-(cis-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione and 5-(1-ethylthiocyclopropan-1-yl)-2-[1-(trans-3-chloroallyloxyimino)-propionyl]-cyclohexane-1,3-dione.
51. The use of sulfamoylphenylureas of formula I according to claim 1 for protecting cultivated plants against the harmful effect of sulfonylurea herbicides, chloroacetanilide herbicides, acylcyclohexanedione herbicides or aryloxyphenoxypropionic acid herbicides.
52. The use of sulfamoylphenylureas of formula I according to claim 1 for protecting cultivated plants against the harmful effect of sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxypropionic acid herbicides.
53. The use according to claim 52 wherein the sulfonylurea herbicides are compounds of formula II
(II) wherein E is a group , , , or , n is 0 or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, C1-C4haloalkoxy, C1-C4haloalkylthio, C2-C4haloalkenyl, chlorine or C1-C4-alkoxycarbonyl, R5 is trifluoromethyl or di(C1-C4alkyl)carbamoyl, R~ is C1-C4alkoxycarbonyl, R7 is C1-C4,alkoxycarbonyl, and R8 is C1-C4alkyl.
(II) wherein E is a group , , , or , n is 0 or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, C1-C4haloalkoxy, C1-C4haloalkylthio, C2-C4haloalkenyl, chlorine or C1-C4-alkoxycarbonyl, R5 is trifluoromethyl or di(C1-C4alkyl)carbamoyl, R~ is C1-C4alkoxycarbonyl, R7 is C1-C4,alkoxycarbonyl, and R8 is C1-C4alkyl.
54. The use according to claim 52 wherein the chloroacetanilide herbicides are compounds of formula III
(III) wherein L is a C1-C4alkylene bridge, each of R9, R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-Csalkoxyalkyl or C2-Csalkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyrrolyl, unsubsti-tuted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxa-diazol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, unsub-stituted or substituted 1,2,4-triaæol-3-yl, unsubstituted or substituted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or sub-stituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetrahydro-furyl.
(III) wherein L is a C1-C4alkylene bridge, each of R9, R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-Csalkoxyalkyl or C2-Csalkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstituted or substituted pyrrolyl, unsubsti-tuted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxa-diazol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, unsub-stituted or substituted 1,2,4-triaæol-3-yl, unsubstituted or substituted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or sub-stituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetrahydro-furyl.
55. The use according to claim 52 wherein the aryloxyphenoxypropionic acid herbicides are compounds of formula IV
(IV) wherein Q is a radical , , , or and T is -NR1sR16, -N(CN)R17, -OR18, SR18 or -O-N=CR19R20, wherein R13 is halogen or trifluoromethyl, R14 is hydrogen or halogen, each of R15 and R15, independently of the other, is hydrogen, C1-C8alkoxy, C1-C8alkyl, phenyl or benzyl, R15 and R15 together with the nitrogen atom carrying them form a 5- or 6-mambered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, R18 is hydrogen or the equiv-alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C1-C4alkylammonium or C1-C4hydroxyalkylammonium radical; a C1-C9alkyl radical that is unsubstituted or mono-or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, C1-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR2l, -COSR21, -CONHz, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl, CONH-C1-C4alkyl, -N(C1-C4alkoxy)-C1-C4alkyl or by di-C1-C4alkylamino; a C3-C9alkenyl radical that is unsubstituted or substituted by.halogen or by C1-C4-alkoxy; a C3-C9alkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-C9cycloalkyl; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1 C4alkoxy, acetyl, -COOR21, COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4alkyl, or together they form a 3- to 6-membered alkylene chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3 C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
(IV) wherein Q is a radical , , , or and T is -NR1sR16, -N(CN)R17, -OR18, SR18 or -O-N=CR19R20, wherein R13 is halogen or trifluoromethyl, R14 is hydrogen or halogen, each of R15 and R15, independently of the other, is hydrogen, C1-C8alkoxy, C1-C8alkyl, phenyl or benzyl, R15 and R15 together with the nitrogen atom carrying them form a 5- or 6-mambered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, R18 is hydrogen or the equiv-alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C1-C4alkylammonium or C1-C4hydroxyalkylammonium radical; a C1-C9alkyl radical that is unsubstituted or mono-or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, C1-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR2l, -COSR21, -CONHz, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl, CONH-C1-C4alkyl, -N(C1-C4alkoxy)-C1-C4alkyl or by di-C1-C4alkylamino; a C3-C9alkenyl radical that is unsubstituted or substituted by.halogen or by C1-C4-alkoxy; a C3-C9alkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-C9cycloalkyl; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1 C4alkoxy, acetyl, -COOR21, COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4alkyl, or together they form a 3- to 6-membered alkylene chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3 C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
56. The use according to claim 51 wherein the acylcyclohexanedione herbicides are compounds of formula IX
(IX) wherein A1 is a 2- to 7-membered alkylene bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n' is 0, 1 or 2, R22 is C1-C4alkyl or benzyl, R23 is C1-C6alkyl unsubstituted or sub-stituted by halogen, C1-C4alkoxy or by C1-C4alkylthio; C3-C6cycloalkyl;
phenyl, benzyl or phenylethyl wherein the phenyl ring can be substituted by halogen, C1-C 4 alkyl, C1-C 4 alkoxy, C1-C 4 alkylthio, C1-C4haloalkyl, C1-C4haloalkoxy, cyano or by nitro, X1 is oxygen or a radical -NOR24, and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl .
(IX) wherein A1 is a 2- to 7-membered alkylene bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n' is 0, 1 or 2, R22 is C1-C4alkyl or benzyl, R23 is C1-C6alkyl unsubstituted or sub-stituted by halogen, C1-C4alkoxy or by C1-C4alkylthio; C3-C6cycloalkyl;
phenyl, benzyl or phenylethyl wherein the phenyl ring can be substituted by halogen, C1-C 4 alkyl, C1-C 4 alkoxy, C1-C 4 alkylthio, C1-C4haloalkyl, C1-C4haloalkoxy, cyano or by nitro, X1 is oxygen or a radical -NOR24, and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl .
57. A herbicidal composition for selectively controlling weeds in crops of useful plants, which contains as active ingredients both a sulfonyl-urea herbicide, an acylcyclohexanedione herbicide, a chloroacetanilide herbicide or an aryloxyphenoxypropionic acid herbicide and a counter-agent of formula I according to claim 1.
58. A herbicidal composition for selectively controlling weeds in crops of useful plants, which contains as active ingredients both a sulfonyl-urea herbicide, a chloroacetanilide herbicide or an aryloxyphenoxy-propionic acid herbicide and a counter-agent of formula I according to claim 1.
59. A composition according to claim 57 wherein the acylcyciohexanedione herbicide is a compound of formula IX
(IX) wherein A1 is a 2- to 7-membered alkylsne bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n1 is 0, 1 or 2, R22 is C1-C4alkyl or benzyl, R23 is C1-C6alkyl unsubstituted or sub-stituted by halogen, C1-C4alkoxy or by C1-C4alkylthio; C3-cscycloalkyl;
phenyl, benzyl or phenylethyl wherein the phenyl ring can be substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C1-C4haloalkoxy, cyano or by nitro, X1 is oxygen or a radical -NOR24, and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl .
(IX) wherein A1 is a 2- to 7-membered alkylsne bridge, a 3- to 7-membered alkenylene bridge which can be mono- or poly-unsaturated, n1 is 0, 1 or 2, R22 is C1-C4alkyl or benzyl, R23 is C1-C6alkyl unsubstituted or sub-stituted by halogen, C1-C4alkoxy or by C1-C4alkylthio; C3-cscycloalkyl;
phenyl, benzyl or phenylethyl wherein the phenyl ring can be substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C1-C4haloalkoxy, cyano or by nitro, X1 is oxygen or a radical -NOR24, and R24 is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl or C3-C6alkynyl .
60. A composition according to claim 58 wherein the sulfonylurea herbicide is a compound of formula II
(II) wherein E is a group , , , or , n is 0 or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, C1-C4haloalkoxy, C1 C4haloalkylthio, C2-C4haloalkenyl, chlorine or C1-C4alkoxycarbonyl, Rs is trifluoromethyl or di(C1-C4alkyl)carbamoyl, R6 is C1-C4alkoxycarbonyl, R7 is C1-C4alkoxycarbonyl, and R8 is C1-C4-alkyl.
(II) wherein E is a group , , , or , n is 0 or 1, G is hydrogen or methyl, X is methoxy, ethoxy, difluoro-methoxy, methyl or chlorine, Y is CH or N, Z is methoxy, methyl, di-fluoromethoxy, cyclopropyl or methylamino, R4 is C2-Csalkoxyalkoxy, C1-C4haloalkoxy, C1 C4haloalkylthio, C2-C4haloalkenyl, chlorine or C1-C4alkoxycarbonyl, Rs is trifluoromethyl or di(C1-C4alkyl)carbamoyl, R6 is C1-C4alkoxycarbonyl, R7 is C1-C4alkoxycarbonyl, and R8 is C1-C4-alkyl.
61. A composition according to claim 58 wherein the chloroacetanilide herbicide is a compound of formula III
(III) wherein L is a C1-C4alkylene bridge, each of R9, R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-C5alkoxyalkyl or C2-C5alkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstiuted or substituted pyrrolyl, unsub-stituted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxadiazol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, un-substituted or substituted 1,2,4-triazol-3-yl, unsubstituted or substi-tuted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or substituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetra-hydrofuryl.
(III) wherein L is a C1-C4alkylene bridge, each of R9, R10 and R11, indepen-dently of the others, is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C2-C5alkoxyalkyl or C2-C5alkylthioalkyl, and R12 is C1-C4alkoxy, -COOH, C1-C4alkoxycarbonyl, -CONH2, C1-C4alkylcarbamoyl, di-C1-C4alkylcarbamoyl, cyano, C1-C4alkylcarbonyl, unsubstituted or substituted benzoyl, unsubstituted or substituted furyl, unsubstituted or substituted thienyl, unsubstiuted or substituted pyrrolyl, unsub-stituted or substituted pyrazolyl, unsubstituted or substituted 1,3,4-oxadiazol-2-yl, unsubstituted or substituted 1,3,4-thiadiazol-2-yl, un-substituted or substituted 1,2,4-triazol-3-yl, unsubstituted or substi-tuted dioxolanyl, unsubstituted or substituted dioxanyl, unsubstituted or substituted 1,3,4-triazol-2-yl or unsubstituted or substituted tetra-hydrofuryl.
62. A composition according to claim 53 wherein the aryloxyphenoxy-propionic acid herbicide is a compound of formula IV
(IV) wherein Q is a radical , , , or and T is -NR15R16, -N(CN)R18, -OR18, SR18 or -O-N=CR19R20, wherein R18 is halogen or trifluoromethyl, R14 is hydrogen or halogen, each of Rls and R16, independently of the other, is hydrogen, C1-Cgalkoxy, C1-C8alkyl, phenyl or benzyl, R15 and R16 together with the nitrogen atom carrying them form a 5- or 6-membered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, R18 is hydrogen or the equiv-alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C1-C4alkylammonium or C1-C4hydroxyalkylammonium radical; a C1-C9alkyl radical that is unsubstituted or mono-or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, C1-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR21, -COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di C1-C4alkyl, CONH-C1-C4alkyl, -N(C1-C4alkoxy)-C1-C4alkyl or by di-C1-C4alkylamino; a C3-C9alkenyl radical that is unsubstituted or substituted by halogen or by C1-C4-alkoxy; a C3-C9alkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-C9cycloalkyl; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1-C4alkoxy, acetyl, -COOR2l, COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4,alkyl, or together they form a 3- to 6-membered alkylene chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3-C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
(IV) wherein Q is a radical , , , or and T is -NR15R16, -N(CN)R18, -OR18, SR18 or -O-N=CR19R20, wherein R18 is halogen or trifluoromethyl, R14 is hydrogen or halogen, each of Rls and R16, independently of the other, is hydrogen, C1-Cgalkoxy, C1-C8alkyl, phenyl or benzyl, R15 and R16 together with the nitrogen atom carrying them form a 5- or 6-membered saturated nitrogen heterocycle that may be interrupted by an oxygen or a sulfur atom, R17 is C1-C4alkyl, C3-C4-alkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, R18 is hydrogen or the equiv-alent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C1-C4alkylammonium or C1-C4hydroxyalkylammonium radical; a C1-C9alkyl radical that is unsubstituted or mono-or poly-substituted by amino, halogen, hydroxy, cyano, nitro, phenyl, C1-C4alkoxy, polyethoxy having from 2 to 6 ethylene oxide units, -COOR21, -COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di C1-C4alkyl, CONH-C1-C4alkyl, -N(C1-C4alkoxy)-C1-C4alkyl or by di-C1-C4alkylamino; a C3-C9alkenyl radical that is unsubstituted or substituted by halogen or by C1-C4-alkoxy; a C3-C9alkynyl radical that is unsubstituted or substituted by halogen or by C1-C4alkoxy; C3-C9cycloalkyl; or phenyl that is unsubsti-tuted or substituted by cyano, C1-C4alkyl, C1-C4alkoxy, acetyl, -COOR2l, COSR21, -CONH2, -CON(C1-C4alkoxy)-C1-C4alkyl, -CO-N-di-C1-C4alkyl or by -CONH-C1-C4alkyl, each of R19 and R20, independently of the other, is C1-C4,alkyl, or together they form a 3- to 6-membered alkylene chain, and R21 is hydrogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkoxyalkyl, C3-C6-alkenyl, C3-C6haloalkyl, C3-C6alkynyl or C3-C6haloalkynyl.
63. A method of selectively controlling weeds in crops of useful plants wherein the cultivated plants or the cultivation area thereof is treated both with a sulfonylurea herbicide, an acylcyclohexanedione herbicide, a chloroacetanilide herbicide or an aryloxyphenoxypropionic acid herbicide and with an effective amount of an N-acylsulfamoylphenylurea of formula I
according to claim 1 as counter-agent.
according to claim 1 as counter-agent.
64. A method of protecting cultivated plants from damage that occurs when sulfonylurea harbicides, acylcyclohexanedione herbicides, chloroacet-anilide herbicides or aryloxyphenoxypropionic acid herbicides are applied, which method comprises treating either the cultivation area of the plants before or during application of the herbicide or treating the seeds or the cuttings of the plants or the plants themselves with an effective amount of an N-acylsulfamoylphenylurea of formula I according to claim 1.
65. A method of selectively controlling weeds in crops of useful plants wherain the cultivated plants or the cultivation area thereof is treated both with a sulfonylurea herbicide, a chloroacetanilide herbicide or an aryloxyphenoxypropionic acid herbicide and with an effective amount of an N-acylsulfamoylphenylurea of formula I according to claim 1 as counter-agent.
66. A method of protecting cultivated plants from damage that occurs when sulfonylurea herbicides, chloroacetanilide herbicides or aryloxyphenoxy-propionic acid herbicides are applied, which method comprises treating either the cultivation area of the plants before or during application of the herbicide or treating the seeds or the cuttings of the plants or the plants themselves with an effective amount of an N-acylsulfamoylphenyl-urea of formula I according to claim 1.
67. Seeds of useful plants, which have been treated with an antagonisti-cally effective amount of an N-acylsulfamoylphenylurea of formula I
according to claim 1.
according to claim 1.
68. Seeds according to claim 67 wherein the seeds are seeds of cereals, soybeans, rice, maize or sorghum.
69. Seeds according to claim 67 wherein the seeds are seeds of sorghum, maize or rice.
70. A process for the preparation of the sulfamoylphenylureas of formula I wherein R1 is as defined under formula I in claim 1 with the excep-tion of hydrogen and R2 is hydrogen, in which process a sulfamoyl-aniline of formula V
(V) wherein A, R3, Ra and Rb are as defined under formula I, is reacted with an isocyanate of formula VI
R1-N=C=O (VI) wherein R1 is as defined under formula I with the exception of hydrogen.
(V) wherein A, R3, Ra and Rb are as defined under formula I, is reacted with an isocyanate of formula VI
R1-N=C=O (VI) wherein R1 is as defined under formula I with the exception of hydrogen.
71. A process for the preparation of compounds of formula I according to claim 1, in which process a sulfamoylphenylurea of formula VII
(VII) wherein R1, R2, R3, R and R are as defined under formula I, is acylated with a carboxylic acid halide of formula VIII
Hal-CO-A (VIII) wherein A is as defined under formula I and Hal is chlorine or brc~mine.
FO 7.5/IH/kg*
(VII) wherein R1, R2, R3, R and R are as defined under formula I, is acylated with a carboxylic acid halide of formula VIII
Hal-CO-A (VIII) wherein A is as defined under formula I and Hal is chlorine or brc~mine.
FO 7.5/IH/kg*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH391488 | 1988-10-20 | ||
| CH3914/88-2 | 1988-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2000928A1 true CA2000928A1 (en) | 1990-04-20 |
Family
ID=4266215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002000928A Abandoned CA2000928A1 (en) | 1988-10-20 | 1989-10-18 | Sulfamoylphenyl ureas |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0365484B1 (en) |
| JP (1) | JP2753872B2 (en) |
| AT (1) | ATE84302T1 (en) |
| BR (1) | BR8905321A (en) |
| CA (1) | CA2000928A1 (en) |
| DE (1) | DE58903221D1 (en) |
| ES (1) | ES2054088T3 (en) |
| GR (1) | GR3007133T3 (en) |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH482396A (en) * | 1966-03-19 | 1969-12-15 | Bayer Ag | Herbicidal agent |
| DE2334607A1 (en) * | 1973-07-07 | 1975-01-30 | Bayer Ag | SULFONYLOXYPHENYLURA, METHOD OF MANUFACTURING AND USING AS HERBICIDES |
-
1989
- 1989-10-11 DE DE8989810778T patent/DE58903221D1/en not_active Expired - Fee Related
- 1989-10-11 AT AT89810778T patent/ATE84302T1/en not_active IP Right Cessation
- 1989-10-11 EP EP89810778A patent/EP0365484B1/en not_active Expired - Lifetime
- 1989-10-11 ES ES89810778T patent/ES2054088T3/en not_active Expired - Lifetime
- 1989-10-18 CA CA002000928A patent/CA2000928A1/en not_active Abandoned
- 1989-10-20 BR BR898905321A patent/BR8905321A/en not_active Application Discontinuation
- 1989-10-20 JP JP1273625A patent/JP2753872B2/en not_active Expired - Lifetime
-
1993
- 1993-02-25 GR GR920402949T patent/GR3007133T3/el unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU719424B2 (en) * | 1996-05-29 | 2000-05-11 | Bayer Cropscience Ag | Novel N-acylsulfonamides, novel mixtures of herbicides and antidotes, and their use |
| US20100304967A1 (en) * | 2007-11-01 | 2010-12-02 | Syngenta Crop Protection, Inc. | Method of protecting rice crops |
| US20100137139A1 (en) * | 2008-11-29 | 2010-06-03 | Bayer Cropscience Ag | Herbicide/safener combination |
| US11129387B2 (en) | 2016-07-08 | 2021-09-28 | Kumiai Chemical Industry Co., Ltd. | Herbicide composition |
| CN113943234A (en) * | 2021-10-27 | 2022-01-18 | 常州大学 | Preparation method of sulfonylphenylurea herbicide safener |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2753872B2 (en) | 1998-05-20 |
| EP0365484A1 (en) | 1990-04-25 |
| ES2054088T3 (en) | 1994-08-01 |
| JPH02174754A (en) | 1990-07-06 |
| GR3007133T3 (en) | 1993-07-30 |
| ATE84302T1 (en) | 1993-01-15 |
| BR8905321A (en) | 1990-10-16 |
| DE58903221D1 (en) | 1993-02-18 |
| EP0365484B1 (en) | 1993-01-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |