CA1259200A - Plant protection agents based on oxime esters - Google Patents
Plant protection agents based on oxime estersInfo
- Publication number
- CA1259200A CA1259200A CA000487113A CA487113A CA1259200A CA 1259200 A CA1259200 A CA 1259200A CA 000487113 A CA000487113 A CA 000487113A CA 487113 A CA487113 A CA 487113A CA 1259200 A CA1259200 A CA 1259200A
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- Prior art keywords
- denotes
- alkyl
- compound
- herbicide
- substituted
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/227—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
-
- 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
- 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings 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
- C07D277/34—Oxygen atoms
-
- 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
- C07D333/06—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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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)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Quinoline Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the disclosure:
The invention relates to agents for protecting crop plants from the phytotoxic side effects of herbi-cides, these agents containing a compound of the formula I
The invention relates to agents for protecting crop plants from the phytotoxic side effects of herbi-cides, these agents containing a compound of the formula I
Description
5~200
-2- 23221-4205 The present application relates to agents for protec~ing crop plants form the phytotoxic side effects of herbicides, these agents containing a compound of the formula I
/Rl Ar-O-A-C-O-N=C \ (I) in which Ar denotes a phenyl, naphthyl or quinolyl radical, each of ~hich can be mono-, di- or tri-substituted by haloyen and/or mono or di-substituted by CF3, (C1-C4)-alkyl, (C1-C4)-alkoxy, CN, NO2, (C1-C8-alkyl)-carbonyl or benzoyl, A denotes a linear or branched hydrocarbon chain with up to four carbon atoms, R1 denotes H, ~Cl-C6)-alkyl, CN or (C1-C4-alkoxy)-carbonyl, or phenyl, which can be substituted by one to three halogen atoms, (cl-c4)-alkyl~ (Cl-C~)-alkoxy, CF3, CN, N02, (C1-C4-alkyl)-carbonyl or benzoyl or by a phenyl or phenoxy radical each of which is optionally mono- or poly-substituted by halogen, ~C1-C4)-alkoxy, (C1-C4)-alkoxy, (C1-C4)-alkyl, nitro, CF3 or CN, and R2 has the meaning of R1, with the exception of hydrogen, or denotes a heterocyclic radical which has 5 or 6 ring members, can contain one to three N, O or S atoms and can be mono-, di- or tri-substituted by halogen or (C1--C4)-alkyl, or R1 and R2 together deno~e an alkylene chain with ~ - 7 carbon atoms, in combination with a phenoxyphenoxy- or heteroaryloYyphel.oxy-carboxylic acid ester herbicide, wherein the ratio of the compound of formula I to the herbicide i5 1:10 to 10:1.
. ~
~25~00 -2a- 23221-4205 In the case of the radical Ar, halogen denotes, in particular, chlorlne.
Preferred compounds of the formula I are those 3L25~2(~
in ~hich Ar denotes phenyl, ~hich is substituted by one or tuo halogen atoms, and A denotes -CH2- or -GH-~H3 Part;cuLarly suitable heterocyclic radicals ~or R2 are thiophene, ~uran, pyrrole~ thiazole, pyrazole, ;m;dazole, oxazole, benzoth;azole, benzoxazole, ;ndole, benzimida~ole, pyrid;ne, pyr;mid;ne, quinol;neand qu;n-oxaline, part;cularly pre~erably th;ophene, furan and pyrsdine.
Examples ~h;ch may be ment;oned o~ the compounds of the formula I are: acetone 0-(4-chlorophenoxyacetyl)-ox;me, acetone 0-(3-chlorophenoxyacetyl3-oxime~ acetone 0-(3,4-d;chlorophenoxyacetyl~-ox;me, acetone 0-S2,4-d;-chlorophenoxyacetyl)-oxime, acetophenone 0-(4-chloro-phenoxyacetyl) ox;me, acetophenone 0-(3,4-d;chlorophen-oxyacetyl)-oxime, benzophenone 0~4-chlorophenoxyacetyl)-oxime, benzophenone 0-(3,4-dichlorophenoxyacetyl)-sxime, 4-chlorobenzophenone O~t4-chlorophenoxyacetyl)-ox;me, 4-2D chlorobenzDphenone 0-(3,4-d;chlorophenoxyacetyl)-o~;me, 2-methyl-~-phenylpropanone 0-(4-chlorophenoxyacetyl)-ox;me, 2-methyl-1-phenylpropanone 0-(3~4-dichlorophenoxy-acetyl)-ox;me, 1-(4-chlorophenyl)-2-methylpropanone 0-(4-chlorophenoxyacetyl)~oxime, 1-t4~chlorophenyl)-2-methyl propanone 0-~3,4-dichlorophenoxyacetyl) ox;me, ben2alde-hyde 0-(4-chlorophenoxyacetyl)-ox;me~ cyclohexanone 0-(4 chlorophenoxyacetyl~-oxime, cyclohexanone 0-(3-chloro-phenoxyacetyl)-ox;me~ cyclohexanone 0-(3,4-d;chloro-phenoxyacetyl)-ox;me, cyclohexanone 0-(2,4-d;chloro-phenoxyacetyl)-ox;me, cycloheptanone 0-(4-chloorophenoxy-acetyl)-ox;me, methyl 2-th;enyl keton@ 0-(4-chlorophen-oxyacetyl~-ox;me, methyl 2-th;enyl ketone 0-~3,4~d;-chlorophenoxyacetyl)-oxime, 3-pyridinealdehyde 0-~4-chlorophenoxyacetyl)~oxime, ethyl 2-(4-chlorophenoxy~
acetyloximino)-prop;onate, ethyl 2-~3,4-dich~orophenDxy-acetyloximino)-propionate, benzophenone 0-[2-~4-chloro-phenoxy)prop;onyl~-ox;me, cyclohexanone 0-C2-(4-chloro-~S92~
~ 4 -phenoxy)prop;onyL~-oxime and methyl 2-thieny~ ketone 0-~2-t4-chlorophenoxy)propionyl~-oxime.
The compounds of the general forruLa I are known in some cases, or they can be prepared by generally known processes, see~ for examp~e, Houben Weyl, Methoden der organischen Chemie (Methods oF Organ;c Chemistry) Vo~ume X/40 pages 180 ~ 187 (1968) and Volume XV/2, pages 137 - 139 (1974~. Some of the compounds of the formula I have already been described as herbicides (U.S~ Patent
/Rl Ar-O-A-C-O-N=C \ (I) in which Ar denotes a phenyl, naphthyl or quinolyl radical, each of ~hich can be mono-, di- or tri-substituted by haloyen and/or mono or di-substituted by CF3, (C1-C4)-alkyl, (C1-C4)-alkoxy, CN, NO2, (C1-C8-alkyl)-carbonyl or benzoyl, A denotes a linear or branched hydrocarbon chain with up to four carbon atoms, R1 denotes H, ~Cl-C6)-alkyl, CN or (C1-C4-alkoxy)-carbonyl, or phenyl, which can be substituted by one to three halogen atoms, (cl-c4)-alkyl~ (Cl-C~)-alkoxy, CF3, CN, N02, (C1-C4-alkyl)-carbonyl or benzoyl or by a phenyl or phenoxy radical each of which is optionally mono- or poly-substituted by halogen, ~C1-C4)-alkoxy, (C1-C4)-alkoxy, (C1-C4)-alkyl, nitro, CF3 or CN, and R2 has the meaning of R1, with the exception of hydrogen, or denotes a heterocyclic radical which has 5 or 6 ring members, can contain one to three N, O or S atoms and can be mono-, di- or tri-substituted by halogen or (C1--C4)-alkyl, or R1 and R2 together deno~e an alkylene chain with ~ - 7 carbon atoms, in combination with a phenoxyphenoxy- or heteroaryloYyphel.oxy-carboxylic acid ester herbicide, wherein the ratio of the compound of formula I to the herbicide i5 1:10 to 10:1.
. ~
~25~00 -2a- 23221-4205 In the case of the radical Ar, halogen denotes, in particular, chlorlne.
Preferred compounds of the formula I are those 3L25~2(~
in ~hich Ar denotes phenyl, ~hich is substituted by one or tuo halogen atoms, and A denotes -CH2- or -GH-~H3 Part;cuLarly suitable heterocyclic radicals ~or R2 are thiophene, ~uran, pyrrole~ thiazole, pyrazole, ;m;dazole, oxazole, benzoth;azole, benzoxazole, ;ndole, benzimida~ole, pyrid;ne, pyr;mid;ne, quinol;neand qu;n-oxaline, part;cularly pre~erably th;ophene, furan and pyrsdine.
Examples ~h;ch may be ment;oned o~ the compounds of the formula I are: acetone 0-(4-chlorophenoxyacetyl)-ox;me, acetone 0-(3-chlorophenoxyacetyl3-oxime~ acetone 0-(3,4-d;chlorophenoxyacetyl~-ox;me, acetone 0-S2,4-d;-chlorophenoxyacetyl)-oxime, acetophenone 0-(4-chloro-phenoxyacetyl) ox;me, acetophenone 0-(3,4-d;chlorophen-oxyacetyl)-oxime, benzophenone 0~4-chlorophenoxyacetyl)-oxime, benzophenone 0-(3,4-dichlorophenoxyacetyl)-sxime, 4-chlorobenzophenone O~t4-chlorophenoxyacetyl)-ox;me, 4-2D chlorobenzDphenone 0-(3,4-d;chlorophenoxyacetyl)-o~;me, 2-methyl-~-phenylpropanone 0-(4-chlorophenoxyacetyl)-ox;me, 2-methyl-1-phenylpropanone 0-(3~4-dichlorophenoxy-acetyl)-ox;me, 1-(4-chlorophenyl)-2-methylpropanone 0-(4-chlorophenoxyacetyl)~oxime, 1-t4~chlorophenyl)-2-methyl propanone 0-~3,4-dichlorophenoxyacetyl) ox;me, ben2alde-hyde 0-(4-chlorophenoxyacetyl)-ox;me~ cyclohexanone 0-(4 chlorophenoxyacetyl~-oxime, cyclohexanone 0-(3-chloro-phenoxyacetyl)-ox;me~ cyclohexanone 0-(3,4-d;chloro-phenoxyacetyl)-ox;me, cyclohexanone 0-(2,4-d;chloro-phenoxyacetyl)-ox;me, cycloheptanone 0-(4-chloorophenoxy-acetyl)-ox;me, methyl 2-th;enyl keton@ 0-(4-chlorophen-oxyacetyl~-ox;me, methyl 2-th;enyl ketone 0-~3,4~d;-chlorophenoxyacetyl)-oxime, 3-pyridinealdehyde 0-~4-chlorophenoxyacetyl)~oxime, ethyl 2-(4-chlorophenoxy~
acetyloximino)-prop;onate, ethyl 2-~3,4-dich~orophenDxy-acetyloximino)-propionate, benzophenone 0-[2-~4-chloro-phenoxy)prop;onyl~-ox;me, cyclohexanone 0-C2-(4-chloro-~S92~
~ 4 -phenoxy)prop;onyL~-oxime and methyl 2-thieny~ ketone 0-~2-t4-chlorophenoxy)propionyl~-oxime.
The compounds of the general forruLa I are known in some cases, or they can be prepared by generally known processes, see~ for examp~e, Houben Weyl, Methoden der organischen Chemie (Methods oF Organ;c Chemistry) Vo~ume X/40 pages 180 ~ 187 (1968) and Volume XV/2, pages 137 - 139 (1974~. Some of the compounds of the formula I have already been described as herbicides (U.S~ Patent
3,914,300; U.S. Patent 3,925,473 and 6erman Patent Z,303,336).
The ~ompounds of the formuLa I can exist in the - syn- or anti-form. The present invent;on relates to both isomers.
15When plant treatment agents, ;n particular herbi-c;des, are used, undesirable damage to the treated crop p~ants may occur. There ;s therefore frequently the need to avo;d the r;sk of possibLe phytotoxicity, especially ~hen herbicides are appl;ed after e~ergence of the crop plants.
Surprisingly, it has been found that compounds of the formula I have the property of reducing or com-pletely eliminating the phytotoxic side effects of plant protection agents, especially of herbicides, when used in crops of useful plantsO The compounds of the formula I are capable of comp~etely eliminating the harmFul side effects of the herbicide without reducing the activity of these herb;cides against har~ful p~ants.
Those compounds ~hich have the property of pro-tecting crop plants from phytotoxic damage by herbicideswithout impair;ng the actual herbicidal action of these agents are called "antidotes" or "safeners".
Certain oxime ethers and esters ~6erman Offen-legungsschriFt 2,808,317~ and aryloxy-aceton;triles and -amide oximes ~European Published Specification 31,938 =
U.S~ Patent 4,414,020~ are already known as safeners~
However, their actions are inadequate.
The field of use of conventional herbic;des can ~2S92~
by very considerably enlarged by addit~on of the safener compound of the formula I.
The present invention thus also relates to a method of protecting crop plants ~rom the phytotoxic side effects o~ plant protection agents, in particular herbicides, ~hich comprises treating the plants, plant seed~ or areas for cultivation with a compound of the iormula ~ be~ore, a~ter or at the same time as with the plant proteotion agent.
The following herbicides may be mentioned as example~, without thereby intending a limitation:
Herbicides of the phenoxyphenoxy- and heteroaryl-oxyphenoxy-carboxylic acid (C1-C4)-alkyl, ~C2-C4)-alkenyl and (C3-C4)-alkinyl ester type, such as methyl 2-(4-(2,4-dichlorophenoxy~-phenoxy)-propionate, methyl. 2-t4-(4-bromo-2-chlorophenoxy)phenoxy)-propionate, methyl 2-(4-(4-trifluoromethylphenoxy)phenoxy)-proplonate, methyl 2-(4-(2-chloro-
The ~ompounds of the formuLa I can exist in the - syn- or anti-form. The present invent;on relates to both isomers.
15When plant treatment agents, ;n particular herbi-c;des, are used, undesirable damage to the treated crop p~ants may occur. There ;s therefore frequently the need to avo;d the r;sk of possibLe phytotoxicity, especially ~hen herbicides are appl;ed after e~ergence of the crop plants.
Surprisingly, it has been found that compounds of the formula I have the property of reducing or com-pletely eliminating the phytotoxic side effects of plant protection agents, especially of herbicides, when used in crops of useful plantsO The compounds of the formula I are capable of comp~etely eliminating the harmFul side effects of the herbicide without reducing the activity of these herb;cides against har~ful p~ants.
Those compounds ~hich have the property of pro-tecting crop plants from phytotoxic damage by herbicideswithout impair;ng the actual herbicidal action of these agents are called "antidotes" or "safeners".
Certain oxime ethers and esters ~6erman Offen-legungsschriFt 2,808,317~ and aryloxy-aceton;triles and -amide oximes ~European Published Specification 31,938 =
U.S~ Patent 4,414,020~ are already known as safeners~
However, their actions are inadequate.
The field of use of conventional herbic;des can ~2S92~
by very considerably enlarged by addit~on of the safener compound of the formula I.
The present invention thus also relates to a method of protecting crop plants ~rom the phytotoxic side effects o~ plant protection agents, in particular herbicides, ~hich comprises treating the plants, plant seed~ or areas for cultivation with a compound of the iormula ~ be~ore, a~ter or at the same time as with the plant proteotion agent.
The following herbicides may be mentioned as example~, without thereby intending a limitation:
Herbicides of the phenoxyphenoxy- and heteroaryl-oxyphenoxy-carboxylic acid (C1-C4)-alkyl, ~C2-C4)-alkenyl and (C3-C4)-alkinyl ester type, such as methyl 2-(4-(2,4-dichlorophenoxy~-phenoxy)-propionate, methyl. 2-t4-(4-bromo-2-chlorophenoxy)phenoxy)-propionate, methyl 2-(4-(4-trifluoromethylphenoxy)phenoxy)-proplonate, methyl 2-(4-(2-chloro-
4-trifluoromethylphenoxy)-phenoxy)-propionate, methyl 2-~4-~2,4-dichlorobenzyl)-phenoxy) propionate, ethyl ~-(4-(4-trifluoromethylphenoxy)-phenoxy)-pent-2-enoate, ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)-phenoxy)propionate, proparyyl 2-(4-(3,5-dichloropyrldyl-2-oxy)phenoxy)-proplonate, ethyl 2-~4-(6-chloro-benzoxazol-2-yl-oxy)-phenoxy)-propionate, ethyl 2-~4-(6-chlorobenzothiazol-2-yl-oxy)-phenoxy)-propionate, methyl 2-l4-l3-chloro-5-tri~luoro~ethyl-2-py~idyloxy)-phenoxy)-propionate, butyl 2-~4-(5-tri~luoromethyl-2-pyridyloxy)-phenoxy)-propionate, ethyl 2-(4-(6-chloro-2-quinoxalyloxy)-phenoxy)-propionate and ethyl 2-(4-(6-chloro-2-quinolyloxy)-phenoxy)-propionate.
~s~
The ratio of the amount of antidote (compound of the formula I) to the amount of herbicide can vary within the wide limits of bet~een 1 : 10 and 10 : 1, in particular between 2 : 1 and l , 10. The particular optimum amounts of herbicide and antidote depend on the type of h~erbicide used or on the antidote used, and on the nature of the plant crop to be treated, and can be determined from case to case by appropriate experiments.
The main fields of use for applyin~ the safeners are, above all, cereal crops (wheat, rye, barley and oats), rice, mai~e and sorghum, and also cotton, sugar beet, sugar cane and soybean.
Dependlng on their properties, the safeners can be used for pretreatment of the seed of the crop plants ~seed dressing) or can be introduced into ~he seed furrows before sowing or applied together with the herbicide before or after emergence of the plants. Pre-emergence treatment includes both treatment Qf the area for cultivation before sowing and treatment of the sown areas for cultivation on wh~ch there is as yet no growth.
Simultaneous use of the antidote with the herbi-.~
oi/~
cide in the form o~ tank mixes or finished formulations, ho~ever, is preferred.
The compounds of the ~ormula I or their combina-tion ~ith a herbicide can be used in the customary for-mulations as ~ettable powders, emulsifiable concentrates,granules or microgranules.
~ ettable powders are unclerstood as meanin0 pro-ducts which are uniformly d;spersible in water and ~hich, alongside the active ;ngredient or active ingredients, and in addit;on to a diluent or inert substance if appropriate, also contain ~etting agents, for example polyoxyethylated alkylpheno~s, polyoxyethylated fatty alcohols and alkyl- or alkylphenyl-sulfonates, and dis-persing agents, ~or example sodium lignin-sulfonate, sodium 2,2'-dinaphthylmethane-6,~'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleyl-methyl-taur;de. They are prepared in the customary manner, for example by grinding and mixing the components.
Emuls;fiable concentrates can be prepared, for ~0 exa~ple, by dissolving the active ingredients in an inert organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or higher-boi~ing aromatics or hydrocarbons, ~ith the addition of one or ~ore emu~sif;ers.
In the case of liquid active ingredients, al~ or some of the solvent content can be dispensed ~ith. Examples of emulsifiers which can be used are: calcium salts of alkylarylsulfonic acids, such as Ca dodecylbenzenesu~fon-ate, or non-ionic emulsifiers, such as fatty ac;d poly glycol esters, alkylaryl po~yglyco~ ethers, fatty a~cohol polyglycol ethers, propylene oxide/ethylene oxide conden~
sation products, alkyl polygLycol ethers, sorb;tan fatty dcid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters~
Dusting agents are obtained by grinding the active ingredients with finely div;ded solid substances, for example talc or naturally occurring clays, such as kaolin, bentonite, pyrophy~lite or diatomaceous earth.
Granules can be prepared either by spraying the 3L~J5g20;~3 act;ve ingred;ents onto an adsorbent, granular ;nert material, or by applying active ;ngred;ent concentrates to the surface of carriers, such as sand or kaolin;tss, or a granular ;nert material by means of b;nders, for
~s~
The ratio of the amount of antidote (compound of the formula I) to the amount of herbicide can vary within the wide limits of bet~een 1 : 10 and 10 : 1, in particular between 2 : 1 and l , 10. The particular optimum amounts of herbicide and antidote depend on the type of h~erbicide used or on the antidote used, and on the nature of the plant crop to be treated, and can be determined from case to case by appropriate experiments.
The main fields of use for applyin~ the safeners are, above all, cereal crops (wheat, rye, barley and oats), rice, mai~e and sorghum, and also cotton, sugar beet, sugar cane and soybean.
Dependlng on their properties, the safeners can be used for pretreatment of the seed of the crop plants ~seed dressing) or can be introduced into ~he seed furrows before sowing or applied together with the herbicide before or after emergence of the plants. Pre-emergence treatment includes both treatment Qf the area for cultivation before sowing and treatment of the sown areas for cultivation on wh~ch there is as yet no growth.
Simultaneous use of the antidote with the herbi-.~
oi/~
cide in the form o~ tank mixes or finished formulations, ho~ever, is preferred.
The compounds of the ~ormula I or their combina-tion ~ith a herbicide can be used in the customary for-mulations as ~ettable powders, emulsifiable concentrates,granules or microgranules.
~ ettable powders are unclerstood as meanin0 pro-ducts which are uniformly d;spersible in water and ~hich, alongside the active ;ngredient or active ingredients, and in addit;on to a diluent or inert substance if appropriate, also contain ~etting agents, for example polyoxyethylated alkylpheno~s, polyoxyethylated fatty alcohols and alkyl- or alkylphenyl-sulfonates, and dis-persing agents, ~or example sodium lignin-sulfonate, sodium 2,2'-dinaphthylmethane-6,~'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleyl-methyl-taur;de. They are prepared in the customary manner, for example by grinding and mixing the components.
Emuls;fiable concentrates can be prepared, for ~0 exa~ple, by dissolving the active ingredients in an inert organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or higher-boi~ing aromatics or hydrocarbons, ~ith the addition of one or ~ore emu~sif;ers.
In the case of liquid active ingredients, al~ or some of the solvent content can be dispensed ~ith. Examples of emulsifiers which can be used are: calcium salts of alkylarylsulfonic acids, such as Ca dodecylbenzenesu~fon-ate, or non-ionic emulsifiers, such as fatty ac;d poly glycol esters, alkylaryl po~yglyco~ ethers, fatty a~cohol polyglycol ethers, propylene oxide/ethylene oxide conden~
sation products, alkyl polygLycol ethers, sorb;tan fatty dcid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters~
Dusting agents are obtained by grinding the active ingredients with finely div;ded solid substances, for example talc or naturally occurring clays, such as kaolin, bentonite, pyrophy~lite or diatomaceous earth.
Granules can be prepared either by spraying the 3L~J5g20;~3 act;ve ingred;ents onto an adsorbent, granular ;nert material, or by applying active ;ngred;ent concentrates to the surface of carriers, such as sand or kaolin;tss, or a granular ;nert material by means of b;nders, for
5 example polyvinyl alcohol, sod;um polyacrylate or mineral o;ls. It is also possible for suitable active ingred;ents to be granulated in the mann~r customary for the pre-parat;on of fertiliz~r granules - ;f des;red mixed with ~ert;l;zers.
The total act;ve insredient concentrat;on in ~ettable po~ders is about 1 to ~0% by weight; the remain-der to make up to 100X by weight consists of the usual formulat;on constituents. In the case of emulsifiable concentrates, the act;ve ;ngred;ent concentrat;on can be about 10 to 80X by ~e;ght. Dust-l;ke formulations usually contain 5 to 20% by ~eight of active ;ngredient, and solutions wh;ch can be spray~d contain about 1 to 20X
by we;ght. The act;ve ;ngred;ent content ;n granules partly depends on ~hether the act;ve compound ;s in the liqu;d or solid form and on what granulation auxiliaries~
fillers and the like are used.
The active ingredient formulations ment;oned also conta;n, if appropriate, the part;cular customary tack;-fiers, wetting agents, d;spersing agents, emulsif;ers, penetration agents, solvents, f;llers or carriers.
For use, the concentrates in the commerc;ally avai~ab~e form are diluted, ;f appropr;ate, ;n the cus-tomary ~anner, for examp~e by means of water ;n the case of wettable powders, e~uls;f;able concentrates, d;sper-s;ons and in some cases also m;crogranules. Dust-~;ke and granular formulations and solut;ons ~h;ch can be sprayed are usually not additionally diluted with other inert substances before use.
The requ;red appl;cation amounts of the compounds of the formula I can vary ~ithin wide limits, depending on the indication, and thsy can also vary as a function of external conditions, such as soil conditions and climate cond;tions~ and with the nature of the herbicide ~ 25~
~ 9 _ used. In general, ho~ever, they are between 0.01 and 10 kg of act;ve ingredient/ha.
The examples which follo~ serve further to ;llus-trate the invention.
Preparation of the compounds of the formula I and their physical data 1. 1-(4-Chlorophenyl)-2-methylpropanone 0-(4-chloro-phenoxyacetyl?-oxime A solut;on of 10.3 y ~0 05 mole) of 4~chloro-phenoxyacetyl chloride in 20 ml of toluene was addeddrop~ise to a solution of 9.9 9 (0.05 mole) of 1-~4-chlorophenyl)-2-methyl-propanone oxime and 5.0 9 ~0.05 mole) of triethylamine in 100 ml of anhydrous toluene at 50C, ~ith stirring. The mixture was stirred at 40 -50C for 8 hours and cooled, the solvent ~as removed ona rotary evaporator, the residue ~as taken up in 200 ml of methylene chloride and the organic phase was washed t~ice ~ith 100 ml of water each time. After the organic phase had been dr;ed w;th Na2S04, the methylene chloride had been evaporated off and solvent ~hich still adhered had been removed under a high vacuum~ 14.7 9 (80.5X of theory) of 1-(4-chlorophenyl)-2-methylpropanone D-(4-chlorophenoxyacetyl)-oxime of n2p = 1.583 were obta;ned 2. Cyclohexanone 0-C2-~4-chLoro~henoxy)-propio~y~
A solution of 11.0 9 (0.05 ~ole) of 2-(4-chloro phenoxy)-propionyl chlor;de in 20 ml of toluene ~as added drop~ise to a solution of 5~7 9 (0.05 mole) of cyclo-hexanone ox;me and 5.0 9 (0.05 mole~ of tr;ethylam;ne in 100 ml of anhydrous toluene at 50C, ~ith stirring.
- 30 The mixture was stirred at 40 - 50C for 8 hours and cooled, the solvent ~as removed on a rotary evaporator, the res;due was taken up ;n 200 ml of methylene chlor;de and the organ;c phase was ~ashed tw;ce with 100 ml of water each time. After the organ;c phase had been dried w;th Na2S04, the methy~ene chlor;de had been evaporated off and the solid which remained had been recrystallised from n-hexane/diisopropyl ether (1 : 1), 9~6 y (64.4X of theory) of cyclohexanone 0-~2-(4-chlorophenoxy)-propion-125~20'3 yl~oxime of melting point 66 - 6~C were obta;ned.
The compounds l;sted ;n Table I ~ere obtained ;n a n a na l ogous ma nner .
c5g~
~ab~e 1: Phenoxyalkanoic acid oxime esters X3~3-o-A-C:-o-N=C
y 11~R2 Com- Meltin~
~ound X Y A R1 R~ p~ant roc~, __ ~ ~ ~
3 4~Cl H C~ - C~, . CHS 1, 5394 4 4-Cl 2~Cl -CH2- -t:H, CHs 77-79 4-Gl 3-Cl CH2 - -CHs CH3 65-67
The total act;ve insredient concentrat;on in ~ettable po~ders is about 1 to ~0% by weight; the remain-der to make up to 100X by weight consists of the usual formulat;on constituents. In the case of emulsifiable concentrates, the act;ve ;ngred;ent concentrat;on can be about 10 to 80X by ~e;ght. Dust-l;ke formulations usually contain 5 to 20% by ~eight of active ;ngredient, and solutions wh;ch can be spray~d contain about 1 to 20X
by we;ght. The act;ve ;ngred;ent content ;n granules partly depends on ~hether the act;ve compound ;s in the liqu;d or solid form and on what granulation auxiliaries~
fillers and the like are used.
The active ingredient formulations ment;oned also conta;n, if appropriate, the part;cular customary tack;-fiers, wetting agents, d;spersing agents, emulsif;ers, penetration agents, solvents, f;llers or carriers.
For use, the concentrates in the commerc;ally avai~ab~e form are diluted, ;f appropr;ate, ;n the cus-tomary ~anner, for examp~e by means of water ;n the case of wettable powders, e~uls;f;able concentrates, d;sper-s;ons and in some cases also m;crogranules. Dust-~;ke and granular formulations and solut;ons ~h;ch can be sprayed are usually not additionally diluted with other inert substances before use.
The requ;red appl;cation amounts of the compounds of the formula I can vary ~ithin wide limits, depending on the indication, and thsy can also vary as a function of external conditions, such as soil conditions and climate cond;tions~ and with the nature of the herbicide ~ 25~
~ 9 _ used. In general, ho~ever, they are between 0.01 and 10 kg of act;ve ingredient/ha.
The examples which follo~ serve further to ;llus-trate the invention.
Preparation of the compounds of the formula I and their physical data 1. 1-(4-Chlorophenyl)-2-methylpropanone 0-(4-chloro-phenoxyacetyl?-oxime A solut;on of 10.3 y ~0 05 mole) of 4~chloro-phenoxyacetyl chloride in 20 ml of toluene was addeddrop~ise to a solution of 9.9 9 (0.05 mole) of 1-~4-chlorophenyl)-2-methyl-propanone oxime and 5.0 9 ~0.05 mole) of triethylamine in 100 ml of anhydrous toluene at 50C, ~ith stirring. The mixture was stirred at 40 -50C for 8 hours and cooled, the solvent ~as removed ona rotary evaporator, the residue ~as taken up in 200 ml of methylene chloride and the organic phase was washed t~ice ~ith 100 ml of water each time. After the organic phase had been dr;ed w;th Na2S04, the methylene chloride had been evaporated off and solvent ~hich still adhered had been removed under a high vacuum~ 14.7 9 (80.5X of theory) of 1-(4-chlorophenyl)-2-methylpropanone D-(4-chlorophenoxyacetyl)-oxime of n2p = 1.583 were obta;ned 2. Cyclohexanone 0-C2-~4-chLoro~henoxy)-propio~y~
A solution of 11.0 9 (0.05 ~ole) of 2-(4-chloro phenoxy)-propionyl chlor;de in 20 ml of toluene ~as added drop~ise to a solution of 5~7 9 (0.05 mole) of cyclo-hexanone ox;me and 5.0 9 (0.05 mole~ of tr;ethylam;ne in 100 ml of anhydrous toluene at 50C, ~ith stirring.
- 30 The mixture was stirred at 40 - 50C for 8 hours and cooled, the solvent ~as removed on a rotary evaporator, the res;due was taken up ;n 200 ml of methylene chlor;de and the organ;c phase was ~ashed tw;ce with 100 ml of water each time. After the organ;c phase had been dried w;th Na2S04, the methy~ene chlor;de had been evaporated off and the solid which remained had been recrystallised from n-hexane/diisopropyl ether (1 : 1), 9~6 y (64.4X of theory) of cyclohexanone 0-~2-(4-chlorophenoxy)-propion-125~20'3 yl~oxime of melting point 66 - 6~C were obta;ned.
The compounds l;sted ;n Table I ~ere obtained ;n a n a na l ogous ma nner .
c5g~
~ab~e 1: Phenoxyalkanoic acid oxime esters X3~3-o-A-C:-o-N=C
y 11~R2 Com- Meltin~
~ound X Y A R1 R~ p~ant roc~, __ ~ ~ ~
3 4~Cl H C~ - C~, . CHS 1, 5394 4 4-Cl 2~Cl -CH2- -t:H, CHs 77-79 4-Gl 3-Cl CH2 - -CHs CH3 65-67
6 4-Cl 2-CH, -CHi~- CH, -t:H, 60-61
7 4-Cl H -CH2 - c~ ~ 82- 84
8 4-Cl 2-Cl -CH2 - ~CH, ~) 80- 81
9 4-Cl 3~1:1 -CH2 - -C:H~ ~ 89-91 4-Cl 2-CH, -CH2 - -CH, ~ 87 11 4-Cl H -CH2 - -H ~ 96-97 12 4-Cl 2~oCl -CH2- -H ~ 102 103 1~ 3-t:l H -CH2 - -H ~ 82 14 4-Cl H . , H- -H ~ 91 4-Cl H ~ oCI3l t:H( CH ) 1. 52E~4 16 4-C:1 2-C:1 -CH,! - -C:H3 -CH~ C}13 ~ 1, 5420 17 4 - Cl 3-Cl -CH9 - -CH~~CH( CH, ),~ 1. 5400 18 4; Cl ~1 _CH- CH, -Ci3(CH~ 1~5262 ~!:H, Continuation of Tab~e 1 Compounl X Y A Rl R~2 n2 N ~ . . ~ _ . e ~ _ 19 4-Cl 2-CH, -CH~2 - -CH~ CH(CH3 )~ 1, 5254 2t) 4-Cl H -CH~2- -EH(t:H~, )Q ~> 1~5670 21 3-Cl H -CH,2- ~CH(CH3 )~ ~ 1.5650 22 4-Cl 3-Cl -eH2 - CH( CH, ) ~ 1. 5745 23 4-Cl 2-CH3 -CH2 - -CH( CH3~ ) ~)--Cl 1. 5685 24 4-Cl 3-Cl -CH2 - CH~ C~ ) ~Cl 1. 5765 3-C:1 H -CH2 - -CHt CH, ) ~--Cl 1. 5702 26 4- Cl H -CH2 ~) ~) 102-103 27 3-Cl H ; CH2- ~) ~) 93 28 4-Cl ;2~ l -CH2- ~ ~) 70-71 29 4-CH3 El -CH2 - ~ -~) 9B
4-~1 3-Cl -CH2- ~ ~ 101-103 31 4-Cl H ~ ~ ~ 83-84 ~3 32 4-Cl ~ -C}15~- ~ ~-~:1 g4-9~
33 4-t~l 3-Cl -CH,!- ~ ~ 1 78-79 34 4-t:l H -~H- ~ ~1 96-9E~
CH, ~s~
Cont; nuat i on of Tab L e Meltinq C ~m- X _ A R1 R~
4-C1 H -CH- -CH~ ~ 86- 88 36 4-C1 ~ -CH2 '~-CH,~ ~ IBO
37 3-C:1 H CH2 ~~-CH~ ~ 76 38 4-C1 3-C1 -CH2 ~~-CH~ ~ 104-105 39 4-C1 H -CH2 - ~H~ )S ~ 1 J 5535 3-C1 H -CH2- (CH~ )~S~ 69-71 41 4-Cl 2-Cl -CH2 - - ( CH2 ~s - 1. 5642 42 4-Cl 3-Cl -CH2 - - ( CH2 )5 - 72-74 43 4-CH~ H -CH2- -(CH2 )3- 51 44 4-Cl H -CH2 - - ( CH;~ 1~ 5515 4-Cl 2-Cl -CH2- -(CH2 )6- 1.5590 46 4-Cl ~-Cl -CH2 -(CH2 )6- 1.5605 47 4-C~ H -CH - _ ~ t H~ )6 - 57 58 H~
48 3-t:l H -CH2 - - ( CH2 ~6 - 47 49 4 CH!, H -I:H2 - - ( CH )~ - 1. 5381 12S~
Cont; nuat i on of Tab l e I r C~m- X ~y A Rl R2 Meltir~
pound n~ant _ ~ . _ _ D
4-Cl H -CH2- -(~H2 )7- 1.5484 51 4-Cl 3-Cl -CH2 - - ( CH2 ~7 - 73_74 52 4-Cl 2-t:H~ -CH2- D~C~I2 )7- 1~5475 53 3-Cl H -CH2- -(CH2 )7- 40-41 54 4-Cl H -CH- -CH, -COz C2 H~ 1. 4805 CH, 4-Cl H -CHz _ -C~ -C2 C2 H~ 1. 4744 56 4-Cl 3- ::1 CH2 - -CH~ -C2 C2 Hg 54 57 4~Cl H -CH- -CH(CH3 )2 ~ 78-80 5B 4-Cl H ; CH2 H ~N ; l __ .- . ~ . . --... _ :IL25~
A. Formulation exampl s 1. An ant;dote concentrate wh;ch ;s readily emuls;-fiable in ~ater is obtained from 25X by weight of com-pound 3 (of the formula I~, 50X by ~e;ght of xylene, 10%
by ~eight of cyclohexanone, 8X by we;ght of calcium do-decylbenzenesulfonate, 4X by ~eight of ethoxylated castor oil (40 moles of ethylene oxide~ and 3X by weight of ethoxyLated nonyLphenol (10 moles of ethylene ox;de).
The act;ve ingredient is dissolved ;n the stated amounts of solvent, with stirring and gentle warming, and the emulsifiers are then added. The mixture is subse-quently stirred at slightly elevated temperatures until the solut;on is clear and free from streaks.
2. A concentrate of a phenoxycarboxylic acid ester and an antidote (10 : 1) which is readily emulsifiable in ~ater ;s obta;ned from 12.00X by weight of ethyl 2-~4-(6-chlorobenzoxazol-2-yl-oxy)-phenoxyJ-propionate, 1.20X by ~eight of compound 3 (of the formula I), b9.00X
by weight of xylene, 7.80X by ~eight of calcium dodecyl-benzenesulfonate, 6.00% by ~eight of ethoxylated nonyl-phenol (10 moles of ethylene oxide) and 4.00% by we;ght of ethoxylated castor o;l (40 moles of ethylene oxide).
The formulation is prepared as described under ExampLe 1).
3. A concentrate of a phenoxycarboxylic acid ester and an ant;dote (1 : 103 ~h;ch is readily emuls;fiable in ~ater is obta;ned from 4.0X by ~eight of ethy~ 2-~4-(6-chlorobenzoxazol-2-y~ oxy)-phenoxy]-propionate, 40.0%
by ~e;ght of compound 3 of the formula I, 30.0% by ueight of xylene, 20.0% by ~eight of cyclohexanone, 4.0% by ~eight of calcium dodecylbenzenesulfonate and 2.0% by weight of ethoxylated castor oil ~40 moles of ethylene ox;de).
The formulation is prepared as described under Example 1).
. 8iolosical examples Example 1 ~heat was grown to the 3 - 4 leaf stage in a 125~
greenhouse in pots of 9 cm ~ and then treated with the herbicide and the antidote compounds. The herbicide was applied here together with the antidote in the form of aqueous suspensions or emulsions as a tank mix, the amount of water applied, when converted, being 800 l/ha.
3 weeks after the treatment, the plants were evaluated for any damage caused by the herbicides applied, the degree of lasting ;nh;bit;on of growth be;ng particularly taken into consideration.
4-~1 3-Cl -CH2- ~ ~ 101-103 31 4-Cl H ~ ~ ~ 83-84 ~3 32 4-Cl ~ -C}15~- ~ ~-~:1 g4-9~
33 4-t~l 3-Cl -CH,!- ~ ~ 1 78-79 34 4-t:l H -~H- ~ ~1 96-9E~
CH, ~s~
Cont; nuat i on of Tab L e Meltinq C ~m- X _ A R1 R~
4-C1 H -CH- -CH~ ~ 86- 88 36 4-C1 ~ -CH2 '~-CH,~ ~ IBO
37 3-C:1 H CH2 ~~-CH~ ~ 76 38 4-C1 3-C1 -CH2 ~~-CH~ ~ 104-105 39 4-C1 H -CH2 - ~H~ )S ~ 1 J 5535 3-C1 H -CH2- (CH~ )~S~ 69-71 41 4-Cl 2-Cl -CH2 - - ( CH2 ~s - 1. 5642 42 4-Cl 3-Cl -CH2 - - ( CH2 )5 - 72-74 43 4-CH~ H -CH2- -(CH2 )3- 51 44 4-Cl H -CH2 - - ( CH;~ 1~ 5515 4-Cl 2-Cl -CH2- -(CH2 )6- 1.5590 46 4-Cl ~-Cl -CH2 -(CH2 )6- 1.5605 47 4-C~ H -CH - _ ~ t H~ )6 - 57 58 H~
48 3-t:l H -CH2 - - ( CH2 ~6 - 47 49 4 CH!, H -I:H2 - - ( CH )~ - 1. 5381 12S~
Cont; nuat i on of Tab l e I r C~m- X ~y A Rl R2 Meltir~
pound n~ant _ ~ . _ _ D
4-Cl H -CH2- -(~H2 )7- 1.5484 51 4-Cl 3-Cl -CH2 - - ( CH2 ~7 - 73_74 52 4-Cl 2-t:H~ -CH2- D~C~I2 )7- 1~5475 53 3-Cl H -CH2- -(CH2 )7- 40-41 54 4-Cl H -CH- -CH, -COz C2 H~ 1. 4805 CH, 4-Cl H -CHz _ -C~ -C2 C2 H~ 1. 4744 56 4-Cl 3- ::1 CH2 - -CH~ -C2 C2 Hg 54 57 4~Cl H -CH- -CH(CH3 )2 ~ 78-80 5B 4-Cl H ; CH2 H ~N ; l __ .- . ~ . . --... _ :IL25~
A. Formulation exampl s 1. An ant;dote concentrate wh;ch ;s readily emuls;-fiable in ~ater is obtained from 25X by weight of com-pound 3 (of the formula I~, 50X by ~e;ght of xylene, 10%
by ~eight of cyclohexanone, 8X by we;ght of calcium do-decylbenzenesulfonate, 4X by ~eight of ethoxylated castor oil (40 moles of ethylene oxide~ and 3X by weight of ethoxyLated nonyLphenol (10 moles of ethylene ox;de).
The act;ve ingredient is dissolved ;n the stated amounts of solvent, with stirring and gentle warming, and the emulsifiers are then added. The mixture is subse-quently stirred at slightly elevated temperatures until the solut;on is clear and free from streaks.
2. A concentrate of a phenoxycarboxylic acid ester and an antidote (10 : 1) which is readily emulsifiable in ~ater ;s obta;ned from 12.00X by weight of ethyl 2-~4-(6-chlorobenzoxazol-2-yl-oxy)-phenoxyJ-propionate, 1.20X by ~eight of compound 3 (of the formula I), b9.00X
by weight of xylene, 7.80X by ~eight of calcium dodecyl-benzenesulfonate, 6.00% by ~eight of ethoxylated nonyl-phenol (10 moles of ethylene oxide) and 4.00% by we;ght of ethoxylated castor o;l (40 moles of ethylene oxide).
The formulation is prepared as described under ExampLe 1).
3. A concentrate of a phenoxycarboxylic acid ester and an ant;dote (1 : 103 ~h;ch is readily emuls;fiable in ~ater is obta;ned from 4.0X by ~eight of ethy~ 2-~4-(6-chlorobenzoxazol-2-y~ oxy)-phenoxy]-propionate, 40.0%
by ~e;ght of compound 3 of the formula I, 30.0% by ueight of xylene, 20.0% by ~eight of cyclohexanone, 4.0% by ~eight of calcium dodecylbenzenesulfonate and 2.0% by weight of ethoxylated castor oil ~40 moles of ethylene ox;de).
The formulation is prepared as described under Example 1).
. 8iolosical examples Example 1 ~heat was grown to the 3 - 4 leaf stage in a 125~
greenhouse in pots of 9 cm ~ and then treated with the herbicide and the antidote compounds. The herbicide was applied here together with the antidote in the form of aqueous suspensions or emulsions as a tank mix, the amount of water applied, when converted, being 800 l/ha.
3 weeks after the treatment, the plants were evaluated for any damage caused by the herbicides applied, the degree of lasting ;nh;bit;on of growth be;ng particularly taken into consideration.
10 The results from Table 1 illustrate that the compounds according to the invention can very effectively reduce severe herbicidal damage.
Mixtures of herbicides and compounds according to the invention are thus suitable for selectively com-bating weeds in cereals.
Table 1 Combination of Dose Herbicidal action herbicide/antidote kg of a.i./ha in % TA
20 H1 + Compound No. 7 2 + 2.5 38 H1 + Compound No. 3 2 ~ 2.5 40 H1 + Compound No. 4 2 + 2.5 60 H1 + Compound No. 5 2 + 2.5 45 H1 + Compound No. 11 2 + 2.5 65 25 H1 + Compound No. 16 2 + 2.5 50 H1 + Compound No. 15 2 ~ 2.5 25 H1 + Compound No. 39 2 + 2.5 20 H1 + Compound No. 42 2 + 2.5 60 H1 + Compound No. 41 2 + 2.5 30 30 H1 + Compound No. 26 2 + 2.5 35 H1 + Compound No. 17 2 + 2.5 20 H1 + Compound No. 4~ 2 + 2.5 60 H1 + Compound No. 20 2 + 2.5 40 H1 + Compound No. 22 2 + 2.5 50 35 H1 + Compound No. 1 2 + 2.5 50 H1 + Compound No. 24 2 + 2.5 50 H1 + Compound No. 25 2 + 2.5 60 H1 + Compound No. 23 2 + 2.5 6û
2~
Comb;nation of Dose Herb;c;dal action herbicide/antidote kg of a.i./ha in % TA
H1 + Compound No. 14 2 + 2.5 60 H1 + Compound No. 2 2 + 2.5 60 H1 + Compound No. 53 2 + 2.5 50 H1 + Compound No~ 38 2 + 2.5 50 H1 t Compound No. 47 2 ~ 2~5 50 H1 + Compound No. 30 2 + 2.5 65 H1 + Compound No. 51 2 + 2.5 45 10 H1 + Compound No. 36 2 + 2.5 40 H1 + Compound No. 50 2 + 2.5 30 H1 + Compound No. 33 2 + 2.5 55 H1 + Compound No. 13 2 + 2.5 65 Hl + Compound No. 56 2 + 2.5 30 __ __ Abbreviations:
H1 = ~ethyl 2-C4-(6-chlorobenzoxazol-2-yl-o~y)-phenoxy~-propionate) TA = Triticum aestivum a.i. = act;ve ;ngredient
Mixtures of herbicides and compounds according to the invention are thus suitable for selectively com-bating weeds in cereals.
Table 1 Combination of Dose Herbicidal action herbicide/antidote kg of a.i./ha in % TA
20 H1 + Compound No. 7 2 + 2.5 38 H1 + Compound No. 3 2 ~ 2.5 40 H1 + Compound No. 4 2 + 2.5 60 H1 + Compound No. 5 2 + 2.5 45 H1 + Compound No. 11 2 + 2.5 65 25 H1 + Compound No. 16 2 + 2.5 50 H1 + Compound No. 15 2 ~ 2.5 25 H1 + Compound No. 39 2 + 2.5 20 H1 + Compound No. 42 2 + 2.5 60 H1 + Compound No. 41 2 + 2.5 30 30 H1 + Compound No. 26 2 + 2.5 35 H1 + Compound No. 17 2 + 2.5 20 H1 + Compound No. 4~ 2 + 2.5 60 H1 + Compound No. 20 2 + 2.5 40 H1 + Compound No. 22 2 + 2.5 50 35 H1 + Compound No. 1 2 + 2.5 50 H1 + Compound No. 24 2 + 2.5 50 H1 + Compound No. 25 2 + 2.5 60 H1 + Compound No. 23 2 + 2.5 6û
2~
Comb;nation of Dose Herb;c;dal action herbicide/antidote kg of a.i./ha in % TA
H1 + Compound No. 14 2 + 2.5 60 H1 + Compound No. 2 2 + 2.5 60 H1 + Compound No. 53 2 + 2.5 50 H1 + Compound No~ 38 2 + 2.5 50 H1 t Compound No. 47 2 ~ 2~5 50 H1 + Compound No. 30 2 + 2.5 65 H1 + Compound No. 51 2 + 2.5 45 10 H1 + Compound No. 36 2 + 2.5 40 H1 + Compound No. 50 2 + 2.5 30 H1 + Compound No. 33 2 + 2.5 55 H1 + Compound No. 13 2 + 2.5 65 Hl + Compound No. 56 2 + 2.5 30 __ __ Abbreviations:
H1 = ~ethyl 2-C4-(6-chlorobenzoxazol-2-yl-o~y)-phenoxy~-propionate) TA = Triticum aestivum a.i. = act;ve ;ngredient
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An agent for protecting crop plants from the phytotoxic side effects of herbicides, this agent containing a compound of the formula I
(I) in which Ar denotes a phenyl, naphthyl or quinolyl radical, each of which can be mono-, di- or tri-substituted by halogen and/or mono-or di-substituted by CF3, (C1-C4)-alkyl, (C1-C4)-alkoxy, CN, NO2, (C1-C8-alkyl)-carbonyl or benzoyl, A denotes a linear or branched hydrocarbon chain with up to four carbon atoms, R1 denotes H, (C1-C6)-alkyl, CN or (C1-C4-alkoxy)-carbonyl, or phenyl, which can be substituted by one to three halogen atoms, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3, CN, NO2, (C1-C4-alkyl)-carbonyl or benzoyl or by a phenyl or phenoxy radical each of which is optionally mono- or poly-substituted by halogen, (C1-C4)-alkoxy, (C1-C4)-alkyl, nitro, CF3 or CN, and R2 has the meaning of R1, with the exception of hydrogen, or denotes a heterocyclic radical which has 5 or 6 ring members, can contain one to three N, O or S atoms and can be mono-, di- or tri-substituted by halogen or (C1-C4)-alkyl, or R1 and R2 together denote an alkylene chain with 4 - 7 carbon atoms, in combination with a phenoxyphenoxy- or heteroaryloxyphenoxy-carboxylic acid ester herbicide, wherein the ratio of said compound of formula I to said herbicide is 1:10 to 10:1.
(I) in which Ar denotes a phenyl, naphthyl or quinolyl radical, each of which can be mono-, di- or tri-substituted by halogen and/or mono-or di-substituted by CF3, (C1-C4)-alkyl, (C1-C4)-alkoxy, CN, NO2, (C1-C8-alkyl)-carbonyl or benzoyl, A denotes a linear or branched hydrocarbon chain with up to four carbon atoms, R1 denotes H, (C1-C6)-alkyl, CN or (C1-C4-alkoxy)-carbonyl, or phenyl, which can be substituted by one to three halogen atoms, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3, CN, NO2, (C1-C4-alkyl)-carbonyl or benzoyl or by a phenyl or phenoxy radical each of which is optionally mono- or poly-substituted by halogen, (C1-C4)-alkoxy, (C1-C4)-alkyl, nitro, CF3 or CN, and R2 has the meaning of R1, with the exception of hydrogen, or denotes a heterocyclic radical which has 5 or 6 ring members, can contain one to three N, O or S atoms and can be mono-, di- or tri-substituted by halogen or (C1-C4)-alkyl, or R1 and R2 together denote an alkylene chain with 4 - 7 carbon atoms, in combination with a phenoxyphenoxy- or heteroaryloxyphenoxy-carboxylic acid ester herbicide, wherein the ratio of said compound of formula I to said herbicide is 1:10 to 10:1.
2. An agent as claimed in claim 1, in which, in formula I, Ar denotes phenyl, which is substituted by one or two halogen atoms, and A denotes -CH2- or
3. An agent as claimed in claim 1 or 2, in which the ratio of antidote to herbicide is 2:1 to 1:10.
4. A method of reducing the phytotoxicity of a herbicide towards crop plants, which comprises treating the plants, plant seeds or areas for cultivation with an effective amount of a compound of the formula I as defined in claim 1 before, after or at the same time as with the herbicide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3426719.0 | 1984-07-20 | ||
| DE19843426719 DE3426719A1 (en) | 1984-07-20 | 1984-07-20 | PLANT PROTECTIVE AGENTS BASED ON OXIMESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1259200A true CA1259200A (en) | 1989-09-12 |
Family
ID=6241098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000487113A Expired CA1259200A (en) | 1984-07-20 | 1985-07-19 | Plant protection agents based on oxime esters |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0170906B1 (en) |
| JP (1) | JPS6137703A (en) |
| AT (1) | ATE50685T1 (en) |
| AU (1) | AU581009B2 (en) |
| CA (1) | CA1259200A (en) |
| DD (1) | DD235551A5 (en) |
| DE (2) | DE3426719A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698539A (en) * | 1992-05-30 | 1997-12-16 | Hoechst Aktiengesellschaft | Mixtures of herbicides and antidotes, (hetero)-aryloxy compounds, their preparation, compositions containing them, and their use |
| US5739079A (en) * | 1992-08-01 | 1998-04-14 | Hoechst Aktiengesellschaft | Substituted (hetero) aryl compounds, process for their preparation, agents containing them and their use as safeners |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2030129A1 (en) * | 1989-11-29 | 1991-05-30 | Thomas Saupe | 1,8-napthalenedicarboximides as antidotes |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914300A (en) * | 1971-12-23 | 1975-10-21 | Shell Oil Co | Phenyl ketoxime derivatives |
| DE2303336A1 (en) * | 1973-01-20 | 1974-07-25 | Schering Ag | HERBICIDAL MIXTURES |
| US3925473A (en) * | 1973-12-12 | 1975-12-09 | Schering Ag | Herbicidal oxime esters of phenoxyalkanoic esters and their use as selective herbicides |
| CH632130A5 (en) * | 1977-03-02 | 1982-09-30 | Ciba Geigy Ag | Compositions on the basis of oxime ethers, oxime esters or oxime carbamates which are suitable in agriculture for crop protection |
| DE3000076A1 (en) * | 1980-01-03 | 1981-09-03 | Hoechst Ag, 6000 Frankfurt | GROWTH-PROMOTING AND PLANT-PROTECTING AGENTS |
| US4566901A (en) * | 1982-05-06 | 1986-01-28 | Ciba-Geigy Corporation | Novel oxime ethers, the preparation thereof, compositions containing them and the use thereof |
-
1984
- 1984-07-20 DE DE19843426719 patent/DE3426719A1/en not_active Withdrawn
-
1985
- 1985-07-09 DE DE8585108478T patent/DE3576271D1/en not_active Expired - Fee Related
- 1985-07-09 AT AT85108478T patent/ATE50685T1/en active
- 1985-07-09 EP EP85108478A patent/EP0170906B1/en not_active Expired - Lifetime
- 1985-07-18 DD DD85278733A patent/DD235551A5/en unknown
- 1985-07-18 JP JP15712585A patent/JPS6137703A/en active Pending
- 1985-07-19 CA CA000487113A patent/CA1259200A/en not_active Expired
- 1985-07-19 AU AU45198/85A patent/AU581009B2/en not_active Ceased
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698539A (en) * | 1992-05-30 | 1997-12-16 | Hoechst Aktiengesellschaft | Mixtures of herbicides and antidotes, (hetero)-aryloxy compounds, their preparation, compositions containing them, and their use |
| US5739079A (en) * | 1992-08-01 | 1998-04-14 | Hoechst Aktiengesellschaft | Substituted (hetero) aryl compounds, process for their preparation, agents containing them and their use as safeners |
| US6482947B1 (en) | 1992-08-01 | 2002-11-19 | Hoechst Aktiengesellschaft | Substituted (hetero) aryl compounds, process for their preparation, agents containing them and their use as safeners |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE50685T1 (en) | 1990-03-15 |
| DD235551A5 (en) | 1986-05-14 |
| DE3576271D1 (en) | 1990-04-12 |
| AU581009B2 (en) | 1989-02-09 |
| EP0170906A1 (en) | 1986-02-12 |
| JPS6137703A (en) | 1986-02-22 |
| EP0170906B1 (en) | 1990-03-07 |
| AU4519885A (en) | 1986-01-23 |
| DE3426719A1 (en) | 1986-01-23 |
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| MKEX | Expiry |