CA1131035A - Herbicidal agents containing herbicidal acetanilides and n-dichloroacetyl-2,2-dimethyl-1,3- oxazolidine as antagonistic agent - Google Patents
Herbicidal agents containing herbicidal acetanilides and n-dichloroacetyl-2,2-dimethyl-1,3- oxazolidine as antagonistic agentInfo
- Publication number
- CA1131035A CA1131035A CA332,135A CA332135A CA1131035A CA 1131035 A CA1131035 A CA 1131035A CA 332135 A CA332135 A CA 332135A CA 1131035 A CA1131035 A CA 1131035A
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- Prior art keywords
- carbon atoms
- dimethyl
- acetanilide
- herbicidal
- denotes
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydroponics (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The invention is concerned with a herbicidal agent containing at least one substituted acetanilide of the formula
The invention is concerned with a herbicidal agent containing at least one substituted acetanilide of the formula
Description
3L~3~3~
The present invention relates to herbicidal agents containing substltuted acetanilides as herbicidal active ingre-dients an~ N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine as an-tagonistic agent, and a process for the selective control of un-wanted plant growth with these herbicidal agents~
The present invention is concerned with a herbicidal agent a herbicidal agent containing at least one subsituted aceta-nilide of the formula ~ ~ 2 ~ r\ I, Rl , where R denotes hydrogen, linear or branched alkyl or alkoxy of up to 5 carbon atoms, Rl denotes hydrogen, halogen, or linear or branched alkyl of alkoxy of up to 5 carbon atoms, R2 denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R2 denotes an alkylPne chain of up to 6 carbon atoms which is linked in the o~position and may be substituted by linear or branched alkyl of up to 4 carbon atoms, X denotes chlorine or bromine, and A denotes an azole ring con-taining 1 to 4 nitrogen atoms which is attached via a ring nitro-gen atom and may be mono- or polysubstituted by halogen, phenyl, alkyl~ alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy of up to 4 carbon atoms ln the alkoxy, or alkanoyl o up to 4 carbon atoms, or A denotes a salt of an azole riny containing 2 or 3 nitrogen atoms, as herbicidal active ingredient, and N-dichloroacetyl-2,2-dlmethyl-1,3-oxazoli-dine as antagonistic agent, the ratio of acetanilide to N-dichlo-roacetyl-2,2-dimethyl-1,3-oxazolidine being from 1:2 to 1:0.01 parts by weight.
Substltuted acetanilides of the formula ,-, ~
....
.~
~ ~ 3~.03~
~ ~ o-CH -X I, where R denotes hydrogen, linear or branched alkyl or alkoxy~of up to 5 c~xbon atoms, R denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R2 denotes hy-drogen, halogen, or llnear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R2 denotes an alkylene chain of up to 6 carbon atoms whlch is linked in the o-position and may be substituted by linear or branched alkyl of up~.to 4 carbon atoms, X denotes chlorine or bromlne, and A deno~es an-azole ring containlng 1 to 4 nl~rogen atoms which is attached vla ~ ring nitrogen atom and may be mono~ or polysubstituted by halogen, phenyl, alkyl, aikoxy, alkylthio or per~luoroalkyl, each of up to 4 car~on atoms, cyano~ carboxy, carbalkoxy of up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms, or A
denotes a salt of an azole containing 2 or 3 nitrogen atoms, have an excellent herbicidal action, but cause damage to crops ~uch as Indian corn and Gramineae. . -~
.. . . . . ... ....
B
3~35
The present invention relates to herbicidal agents containing substltuted acetanilides as herbicidal active ingre-dients an~ N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine as an-tagonistic agent, and a process for the selective control of un-wanted plant growth with these herbicidal agents~
The present invention is concerned with a herbicidal agent a herbicidal agent containing at least one subsituted aceta-nilide of the formula ~ ~ 2 ~ r\ I, Rl , where R denotes hydrogen, linear or branched alkyl or alkoxy of up to 5 carbon atoms, Rl denotes hydrogen, halogen, or linear or branched alkyl of alkoxy of up to 5 carbon atoms, R2 denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R2 denotes an alkylPne chain of up to 6 carbon atoms which is linked in the o~position and may be substituted by linear or branched alkyl of up to 4 carbon atoms, X denotes chlorine or bromine, and A denotes an azole ring con-taining 1 to 4 nitrogen atoms which is attached via a ring nitro-gen atom and may be mono- or polysubstituted by halogen, phenyl, alkyl~ alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy of up to 4 carbon atoms ln the alkoxy, or alkanoyl o up to 4 carbon atoms, or A denotes a salt of an azole riny containing 2 or 3 nitrogen atoms, as herbicidal active ingredient, and N-dichloroacetyl-2,2-dlmethyl-1,3-oxazoli-dine as antagonistic agent, the ratio of acetanilide to N-dichlo-roacetyl-2,2-dimethyl-1,3-oxazolidine being from 1:2 to 1:0.01 parts by weight.
Substltuted acetanilides of the formula ,-, ~
....
.~
~ ~ 3~.03~
~ ~ o-CH -X I, where R denotes hydrogen, linear or branched alkyl or alkoxy~of up to 5 c~xbon atoms, R denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R2 denotes hy-drogen, halogen, or llnear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R2 denotes an alkylene chain of up to 6 carbon atoms whlch is linked in the o-position and may be substituted by linear or branched alkyl of up~.to 4 carbon atoms, X denotes chlorine or bromlne, and A deno~es an-azole ring containlng 1 to 4 nl~rogen atoms which is attached vla ~ ring nitrogen atom and may be mono~ or polysubstituted by halogen, phenyl, alkyl, aikoxy, alkylthio or per~luoroalkyl, each of up to 4 car~on atoms, cyano~ carboxy, carbalkoxy of up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms, or A
denotes a salt of an azole containing 2 or 3 nitrogen atoms, have an excellent herbicidal action, but cause damage to crops ~uch as Indian corn and Gramineae. . -~
.. . . . . ... ....
B
3~35
- 2 - O.Z. 0050/033324 It was therefore the object of the invention to provide antagonistic agents which o~fset this poor tolerance of herbici-dal acetanilides by certain crop plants.
Antagonistic agents (antidotes) are chemical compounds as a result o~ the presence of which the tolerance, by certain crop plants, of non-selective or insufficiently selective herbicidal active ingredients is increased without their action on unwanted plants being impaired.
Herbicidal agents containing, in addition to chloroacet-anilides as herbicidal active ingredients, antagonistic dichloroacetamides have been disclosed in U.S. 4~053,297 and German Laid-Open Applications DE-OS 2,218,097 and 2,402,983. Dichloro-acetamides in which the 2 substituents on the nltrogen atom form, with it, a heterocyclic ring which may contain a further hetero atom and is unsubstituted or substituted by alkyl are mentioned inker alia in these publications as possible anti-dotes. N-dichlor-oacetyl-2,2-dimethyl-1,3-oxazolidine is given as an example of this class of compounds.
However 9 German Laid-Open Application DE-OS 2,218,097 2C only recommends this antagonistic compound in combination with herbicidally active thiolcarbamates, whereas it is known from German Laid-Open Application DE-OS 2,402,983 and U.S. 4,053g297 that N-dichloroacetyl-2,2-dimethyl-1,3-oxa-zolidine is suitable as an antidote for reducing damage caused to Indian corn by herbicidally active chloroacetanilides.
In addition to the chloroacetyl group 9 these chloroacet-anilides bear on the nitrogen substituted alkyl 9 alkoxyalkyl, alkenyloxyalkyl or cycloalkyloxyalkyl radicals or oxygen-~L~33~1~333,5
Antagonistic agents (antidotes) are chemical compounds as a result o~ the presence of which the tolerance, by certain crop plants, of non-selective or insufficiently selective herbicidal active ingredients is increased without their action on unwanted plants being impaired.
Herbicidal agents containing, in addition to chloroacet-anilides as herbicidal active ingredients, antagonistic dichloroacetamides have been disclosed in U.S. 4~053,297 and German Laid-Open Applications DE-OS 2,218,097 and 2,402,983. Dichloro-acetamides in which the 2 substituents on the nltrogen atom form, with it, a heterocyclic ring which may contain a further hetero atom and is unsubstituted or substituted by alkyl are mentioned inker alia in these publications as possible anti-dotes. N-dichlor-oacetyl-2,2-dimethyl-1,3-oxazolidine is given as an example of this class of compounds.
However 9 German Laid-Open Application DE-OS 2,218,097 2C only recommends this antagonistic compound in combination with herbicidally active thiolcarbamates, whereas it is known from German Laid-Open Application DE-OS 2,402,983 and U.S. 4,053g297 that N-dichloroacetyl-2,2-dimethyl-1,3-oxa-zolidine is suitable as an antidote for reducing damage caused to Indian corn by herbicidally active chloroacetanilides.
In addition to the chloroacetyl group 9 these chloroacet-anilides bear on the nitrogen substituted alkyl 9 alkoxyalkyl, alkenyloxyalkyl or cycloalkyloxyalkyl radicals or oxygen-~L~33~1~333,5
- 3 - O.Z. 0050/033324 and/or sulfur-containing saturated rings attached via a methylene group.
We have now ~ound that N-dichloroacetyl-2,2-dimethyl-1,3--oxazolidone is suitable for increasing the tolerance by crop plants of herbicidal substituted acetanilides of the formula I.
Herbicidal agents containing at least one substituted acet-anilide of the ~ormula I and N-dichloroacetyl-2,2-dimethyl--1,3-oxazolidine may be employed without di~ficutly in Indian corn. The good herbicidal action of the acetanilides is unimpaired, and damage to the crop plants is eliminated.
Acetanilides whose tolerance by crop plants can be increased by N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine are those of the formula I in which R is hydrogen, alkyl of a maximum of 5 carbon atoms, such as methyl 9 ethyl, n-propyl 9 isopropyl, n-butyl, sec-butylg isobutyl, tert-butyl, linear and branched pentyl, and alkoxy o~ a maximum of 5 carbon atoms, such as methoxy, ethoxy, propoxy9 butoxy and pentoxy;
R1 and R2 are hydrogen, halogen, such as fluorine, chlorine, bromine and iodine, alkyl o~ a maximum of 5 carbon 2C atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, linear and branched pentyl, and alkoxy of a maximum of 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxyj and pentoxy;
R2 together with R is an alkylene chain of a maximum of 6 carbon.atoms, linked in the o-position and unsubstituted or substituted by alkyl o~ a maximum of 4 carbon atoms, e.g., ethylene, trimethylene, tetramethylene, 1-methyltrimethylene~
1,1 dimethyltrimethylene, and 1,1-dimethyltetramethylene;
~L~3~35
We have now ~ound that N-dichloroacetyl-2,2-dimethyl-1,3--oxazolidone is suitable for increasing the tolerance by crop plants of herbicidal substituted acetanilides of the formula I.
Herbicidal agents containing at least one substituted acet-anilide of the ~ormula I and N-dichloroacetyl-2,2-dimethyl--1,3-oxazolidine may be employed without di~ficutly in Indian corn. The good herbicidal action of the acetanilides is unimpaired, and damage to the crop plants is eliminated.
Acetanilides whose tolerance by crop plants can be increased by N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine are those of the formula I in which R is hydrogen, alkyl of a maximum of 5 carbon atoms, such as methyl 9 ethyl, n-propyl 9 isopropyl, n-butyl, sec-butylg isobutyl, tert-butyl, linear and branched pentyl, and alkoxy o~ a maximum of 5 carbon atoms, such as methoxy, ethoxy, propoxy9 butoxy and pentoxy;
R1 and R2 are hydrogen, halogen, such as fluorine, chlorine, bromine and iodine, alkyl o~ a maximum of 5 carbon 2C atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, linear and branched pentyl, and alkoxy of a maximum of 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxyj and pentoxy;
R2 together with R is an alkylene chain of a maximum of 6 carbon.atoms, linked in the o-position and unsubstituted or substituted by alkyl o~ a maximum of 4 carbon atoms, e.g., ethylene, trimethylene, tetramethylene, 1-methyltrimethylene~
1,1 dimethyltrimethylene, and 1,1-dimethyltetramethylene;
~L~3~35
- 4 - OOZ. 0050/033324 X is chlorine, bromine or iodine3 pre~erably chlorine;
A is an azole attached via a rin~ nitrogen atom, e.g~, pyrrole, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole, which be mono- or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, or carbalkoxy with up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms, the substituents being identical or different, such as 2,6-dimethylpyrrole, tetramethylpyrrole, 3(5)-methylpyrazole, 4-methylpyrazole, 3(53-ethylpyrazole, 4-ethylpyrazole, 3(5)-iso-propylpyrazole, 4-isopropylpyrazole, 3,5-dimethylpyrazole, 315-dimethyl-4-acetylpyrazole, 3,5-dimethyl-4-propionylpyrazole, 3,4,5-trimethylpyrazole, 3(5)-phenylpyrazoleg 4-phenylpyrazole, 3,5-diphenylpyrazole, 3(5)-phenyl-5(3)-methylpyrazole, 3(5)--chloropyrazole, 4-chloropyrazole, 4-bromopyrazole, 4-iodo-pyrazole, 3,4,5-trichloropyrazole, 3,4,5-tribromopyrazole, 3,5-dimethyl-11-chloropyrazole, 3,5-dimethyl-4-bromopyrazole, 4-chloro-3(5)~methylpyrazole, 4-bromo-3(5)-methylpyrazole, 4-methyl-3,5-dichloropyrazole, 3(5)-methyl~4,5(3)-dichloro-2C pyrazole, 3(5)-chloro-5(3)-me~hylpyrazole, 4~methoxypyrazole, 3(5)-methyl-5(3~-methoxypyrazole, 3(5)-ethoxy-4,5(3)-dimethyl-pyrazole, 3(5)-methyl-5(3)~trifluoromethylpyrazole, 3,5-bis--trifluoromethylpyrazole, 3(5)-methyl-5(3)-carbethoxypyrazole, 3,5-bis-carbethoxypyrazola, 3,4,5-triscarbethoxypyrazole, ~(5)-methyl-5(3) methylthio-4-carbethoxypyraæola, 4-methyl-3,5--biscarbethoxypyraæole, 4-cyanopyrazole, 4-methoxy-3,5-di-chloropyrazole~ 4,5-dichloroimidazole, 2-ethyl-4,5-dichloro-imidazole, 2-methyl-4,5-dichloroimidazole, 3(5)-methyl-1,2,4-` - 5~-~3~5 O.Z. 0050/03332~
-triazole~ 3,5-dimethyl-1,2,4-triazole, 3(5)-chloro-1,2,4--triazole, 3(5)-bromo-1,2,4-triazole, 3(5)-chloro-5(3)-methyl--192,4-triazole, 3,5-dichloro-1,2,4-triazole, 3,5-dibromo--1,2,4-triazole, 3(5)-chloro-5(3)-cyano-1,2,4-triazole, 3(5) chloro-5(3)-phenyl-1,2,4-triazole, 3(5)-chloro-5(3)--carbomethoxy-1,2,4-triazole, 3(5)-methylthio-1~2,4-triazole, 4(5)-methyl-1,2,3~triazole, 4,5-dimethyl-1,2,3-triazole, 4(5)-phenyl-1,2,3-triazole, 4(5)-chloro-1,2,3-triazole, 1,2,3-triazol-4(5)-yl-carboxylic acid ethyl ester, 1,2,3-tri~
azol-4,5-yl-dicarboxylic acid dimeth~l ester, 5-methyltetra-zole, 5-chlorotetrazole, and tetrazolyl-5-carboxylic acid ethyl ester.
Furthermore, the radical A may, when the optionally sub-stituted azole contains 2 or 3 nitrogen atoms, also be attached in a salt-like manner to one of the usual strong inorganic or organic acids, e.g., hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoboric acid, fluosulfonic acid, and ~ormic acid, a halogenated carboxylic acid, e.g., trichloroacetic acid, an alkanesulfonic acid, e.g., methane-2C ulfonic acid, a halogenated alkanesulfonic acid, e.g., tri-fluoromethanesulf'onic acid and per~luorohexanesul~onic acid, and an arylsul~onic acid, e.g. dodecylbenzenesulfonic acid.
Pre~erred acetanilides are those which bear methyl or ethyl in the 2- and 6-positions on the phenyl ring and hydrogen, methyl or ethyl in the 3-position; sui~able azoles are pyrazole, imidazole, triazole and tetrazole, which are unsubstituted or substituted by lower alkyl, alkoxy, carbalkoxy, cyano or halogen.
~3~C13S
- 6 - O.Z. 0050/03332 In particular, the herbicidal agents accordin~ to the invention contain the following acetanilides:
2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(pyrazol-1-yl-methyl)-acet-anilide, 2-chloro-2',6'-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6-ethyl-N-(4-methoxy-pyrazol-1-yl-methyl) acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(3(5)-methylpyrazol-1-yl)-acetanilide, 2-chloro~2', 6'-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro~2~6~-di~methyl-N-(l~2~4-triazol-l-yl-methyl)-acet anilide~ 2 chloro-2',6'-dimethyl-N-(4-chloropyrazol-1-yl--methyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(pyrazol--1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(3,5-~dimethylpyrazol-1-yl-methyl)-acetanilide, 2~chloro-2',6'-di-ethyl-N-~3~5-dimethylpyrazol-l-yl-methyl)-acetanilide~ 2-chloro--2t~3~6~-trimethyl-N-(3~5-dimethylpyrazol-l-yl-meth7l)-acet-anilide, 2-chloro-2',6'-diethyl-N-(4-methylpyrazol-1-yl-methyl)-~acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4-methylpyrazol--1-ylmethyl)-acetanilide~ 2~chloro-2',3',6~-trimethyl-N~(4-me-2C thylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2',6'-dim~thyl--N-(3~(5)-methylpyrazol-l yl-methyl)~acetanilide, 2-chloro--2',6'-diethyl-N-(3-(5)-methylpyrazol-1-yl-methyl)-ac_tanilide, 2-chloro-2',6'-dimethyl~N-(4-methoxypyrazol-1-yl-methyl)-acet-anilide~ 2-chloro-2'g6'-diethyl-N (pyrazol-1-yl-methyl)-acet~
anilide, 2-chloro-2l,6'-dimethyl-N-(4,5-dichloroirnidazol-1-yl~
-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4,5-di-chloroimidazol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl--6'-ethyl~N-(2-ethyl-l,5-dichloroimidazol-1-yl~methyl)-acet-- 7 - O.Z. 0050/033324 anilide, 2-chloro-2'~6'-diethyl-N-(4,5 dichloroimidazol-1-yl--methyl)-acetanilide, 2-chloro~2'-methyl-6'-ethyl-N-(1,2,4-tri-azol-l-yl-methyl)-acetanilide~ 2-chloro-2',6'-diethyl-N-(1,2,4-~triazol~1-yl-methyl)-acetanilide and 2-chloro-2',3',6'-tri-methyl-N-(1,2,4-triazol-1-yl-methyl)-acetanilide.
A particularly pre~erred agent according to the invention contalns, in addition to N-dichloroacetyl-2,2-dimethyl-1,3--oxazolidine, 2-chloro-21,6'-dimethyl-N-(pyrazol-1-yl-methyl)--acet~nilide as herbicidal active ingredient.
The acetanilides of the ~ormula I are disclosed in German Laid-Open Applications DE-OS 25648,oo8 and DE-OS 2,74~,396.
They may be obtained by reaction of 2-halo-N-halomethylacet-anilides of the formula II with a lH-azole of the formula H-A
in accordance with the ~ollowing equation:
R R
~ /CH2-X I CH2-A
</ \~N~ ~ H-A ~ + HX
R2/~/ CO-CH2-X R2 /~/ CO-CH2-X
Rl R
II
R, R1, R2 and X have the above meanings and A denotes an azole linked via a rin~ nitrogen atom and which may be mono- or poly-substituted by halogeng phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy o~ up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms.
The manu~acture o~ N-dichloroacetyl-2,2-dimethyl 1~--oxazolidine i8 disclosed in German Laid-Open Applications DE-OS 2,218,097 and DE-OS 2,402,98~.
1l~3~g~3~
- 8 - O.Z. 0050/033324 N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine itself has scarcely any in~luence, if at all, on the germination and growth of crop and unwanted plants, even at application rates well above those required for an antagonistic sffect.
However, it is capable of considerably reducing the phyto-toxicity of the herbicidal acetanilides of the formula I
to crop plants such as Indian corn, or of eliminating it completely.
In these case of herbicidal acetanilides which are less a~gressive to crop plants, low additions of N-dichloro-ac~tyl-2,2-dimethyl-1,3-oxazolidine are suf~icient. The ratio of acetanilide to N-dichloroacetyl 2,2-dimethyl-1,3-oxa-zolidine may vary within wide limits, and depends on the acetanilide. Suitable ratios of herbicidal active ingre-dient to N-dichloroacetyl-2,2-dimethyl-1~3-oxazolidine are - from 1:2 to 1:0~01 parts by weight.
Acetanilides and antagonistic compounds may be in-corporated into the soil either together or separately and before or after sowing. With acetanilides of the formula I~
2~ the commonest method is to apply them to the surface of the soil immediately after sowing, or in the period between sowing and emergence o~ the young plants. It is also possible to apply them during emergence and shortly therea~ter. In each instance, the antagoniætic agent may be applied simultaneously with the herbicidal active ingredient~ It is also possible to apply the compounds separately - either the antagonist ~irst and then the herbicidal active ingredient, or vice versa -provided that, if the herbicidal active ingredient is applied :1 ~31~3~
- g O.Z. 0050/033324 first, not too much time elapses be~ore the antagonist is applied as otherwise the crop plants may be damaged. The active ingredient and antagonist may be suspended, emulsified or dissolved in a spray liquor or may be in granular ~orm, and may be formulated together or separately. It is also feasible to treat the seed with the antagonist befora sowing. The herbicidal active ingredient is then applied on its own in the usual manner.
The novel herbicidal agents may contain, in addition to acetanilide and N-dichloroacetyl~2,2-dimethyl-1,3-oxazolidine, other herbicidal or growth-regulating active ingredients of di~ferent chemical structure, e.g., 2-chloro-4-ethylamino-6 -isopropylamino-1~3,5-triazine, without the antagonistic effect being impaired.
The agents according to the invention, or, when applied separately~ the herbicidal active ingredients and the antidote are applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous~ oily or other suspensions), dispersîons, emulsions, 2C oil dispersionsg pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The ~orms o~ application depend entirely on the purpose for which the agents are being used; in any case they should ensure very ~ine distribution of the agents according to the invention or their individual components.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil ~ractions o~
medium to high boiling point, such as kerosene or diesel oil, - ~3~ 5 - 10 - O.z. 0050/033324 further coal-tar oils, and oils of vegetable or animal origin~ -aliphaticg cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar sol~ents such as dimethylformamide, dimethyl-sulfoxide, N-methylpyrrolidone, waterg etc. are suitable.
Aqueous formulations may be prepared from emulsion con-centrates~ pastes, oil dispersions or wettable powders by adding water. To prepare emulsions~ pastes and oil dispersions the herbicidal active ingredient and/or antidote, as such or dis~olved in an oil or solventg may be homogenized in water by means of wetting or dispersing a~ents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be prepared ~ om herbicidal active ingredient and/or antidoteg wetting agent, adherent, emulsifying or dispersing agent and possibly sol~ent or oil.
Examples of surfactants are: alkali metal, alkaline earth 2C metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acidg lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts o~ fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-~3~3S
0 Z. 0050/033324lene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and ~ormaldehyde~ polyoxyethylene octylphenol ethers, ethoxyl-ated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol~ alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol3 fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the herbicidal active ingredient and/or anti-dote wit~ a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicîc acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loessS clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, mag-2C nesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate~ and ureas, and vegetable producks such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of herbicidal active ingredient and/or antidote. Application rate3 are from 0.2 to 5 kg of herbicidal active ingredient per hectare. This amount of herbicidal active ingredient is applied, together or separately, with ~IL3~33~
such an amount of antidote to give a ratio of herbicidal active ingredient to antagonist of from 1:2 to 1:0.01 parts by weight.
Examples of formulations are given below.
I. 40 parts by weight of a mixture of 4 parts by weight of 2-chloro-2l,6'-dimethyl-N-(pyrazol-l-yl-methyl)-acetamide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl-1,3--oxazolidine is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable~
aqueous dispersion is obtained. Dilution in 1003000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of the mixture of active ingredient + antidote.
II. 3 parts by weight of a mixturs of 1 part by weight of 2-chloro-2',6'-dimethyl-N-(pyrazol-l-yl-methyl)-acetanilide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl-1,3--oxaæolidine is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the mixture of active ingredient + antidote.
2C III. 30 parts by weight of a mixture of 1 part by weight of 2~chloro 2'-methyl-6'-ethyl-N-~1,2,4-triazol-1-yl-methyl)~acet-anilide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl--1,3~oxazolidine is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of para~in oil which has been sprayed onto the surface of this silica gel. A ~ormulation is obtained having good adherence.
~l3~3~
- 13 - O.Z. 0050/033324 IV. 20 parts by weight of a mixture of 8 parts by weight of 2-chloro-2'-methyl~5~-ethyl~N-(pyrazol-1-yl-methyl)-acet-anilide and 1 part by weight of N-dichloroacetyl~2,2-dimethyl--1,3-oxazolidine is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dis-persion is obtained.
V. 20 parts by weight of a mixture of 10 parts by weight of 2-chloro-2',6 7 -dimethyl-N-(4l5-dichloroimidazol-1-yl--methyl~-acetanilide and 1 part by weight of N-dichloro~
acetyl-2,2-dimethyl-1,3 oxazolidine is dissol~ed in a mix-ture consisting of 40 parts by weight o~ cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctyl-phenol, and ~0 parts by weight of the adduct oP 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing 2C it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the mixture of active ingredient ~ antidote.
Gr~enhouse experiments show that the use of the herbicidal agents according to the invention increases the tolerance of the herbicidal acetanilides by the crop plants without the herbicidal action being affected.
Plastic boxes 51 cm long, 32 cm wide and 6 cm deep were filled with loamy sand (pH:6 to 7) containing about 1.5% humus.
L33~
- 14 - O.Z. 0050/033324 Indian corn (Zea mays) was sown sha]low, in rows, in this substrate. Echinochloa crus-galli was scattered at random as unwanted plant~ The non-sterilized soil also additionally contained viable weed seeds which contributed to the weed population. A field with crop plants growing in it and in-fested with weeds was thus simulated.
The active ingredients and the antagonist were applied separately and in the mixtures given below. They were emul-si~ied or suspended in water as vehicle and the liquor was sprayed through finely distrihuting nozzles onto the soil surface, either immediately after sowing or prior to emergence of the test plants After sowing and treatment the boxes were sprinkler-irrigated and covered with transparent plastic hoods until the plants emerged. These measures ensured that the plants germinated and took root uniformly. The boxes were set up in the greenhouse at from 18 to 30C. These greenhouse experiments were monitored until 3 to 5 Indian corn leaves had developed.
The scale for assessing the action of the agents was 0 2C to 100, 0 denoting normal emergence and development of the plants, with reference to the untreated control, and 100 denoting non-germination or withering of the plants. It should be borne in mind here that, for instance in Indian corn, odd crippled or retarded plants may occur even under completely normal conditions and without any chemical treat-ment.
~L~3~3S
- 15 - O.Z. 0050/033324 The following table shows the extent to which N~dichloro-acetyl 2,2 dimethyl-1,3-oxazolidine increases the tolerance by Indian corn of acetanilides of the ~ormula I, e.g., 2-chloro-2',6'-dimethyl-N-(pyrazol 1-yl-methyl)-acetanilide.
- 16 -0 ~ Z . 0050/033324 . ~' ~ ~ ~ o, o~ o~ ~ 8 S ~ ,, .
o .,~ ~ a) ~ s 3 la)O
~o ~ ~ rq _^ O S:: ~ ~~ O ~ O
~I O O ~ ~/1 .
S ~ ~ ~
O . N O Ls~ O
C E ~a S ~ ~ N ~ N N
~ X
o a) a~ Z
~ h O = C~ ~ S
h --~ C~ . ~) 3 O S ~ ~ ,~ ~
S E~ ,o O , , C~ ~ ~
~:~1 .'''. 'J-~ ' + b~D
E e ~ ,, ~ Z~ C~N E
H I ~ :C O C O
.Q S~ O C~ cC S~
~ ~ x e :~: ¢ o- o ..~,.. ..' , . .
A is an azole attached via a rin~ nitrogen atom, e.g~, pyrrole, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole, which be mono- or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, or carbalkoxy with up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms, the substituents being identical or different, such as 2,6-dimethylpyrrole, tetramethylpyrrole, 3(5)-methylpyrazole, 4-methylpyrazole, 3(53-ethylpyrazole, 4-ethylpyrazole, 3(5)-iso-propylpyrazole, 4-isopropylpyrazole, 3,5-dimethylpyrazole, 315-dimethyl-4-acetylpyrazole, 3,5-dimethyl-4-propionylpyrazole, 3,4,5-trimethylpyrazole, 3(5)-phenylpyrazoleg 4-phenylpyrazole, 3,5-diphenylpyrazole, 3(5)-phenyl-5(3)-methylpyrazole, 3(5)--chloropyrazole, 4-chloropyrazole, 4-bromopyrazole, 4-iodo-pyrazole, 3,4,5-trichloropyrazole, 3,4,5-tribromopyrazole, 3,5-dimethyl-11-chloropyrazole, 3,5-dimethyl-4-bromopyrazole, 4-chloro-3(5)~methylpyrazole, 4-bromo-3(5)-methylpyrazole, 4-methyl-3,5-dichloropyrazole, 3(5)-methyl~4,5(3)-dichloro-2C pyrazole, 3(5)-chloro-5(3)-me~hylpyrazole, 4~methoxypyrazole, 3(5)-methyl-5(3~-methoxypyrazole, 3(5)-ethoxy-4,5(3)-dimethyl-pyrazole, 3(5)-methyl-5(3)~trifluoromethylpyrazole, 3,5-bis--trifluoromethylpyrazole, 3(5)-methyl-5(3)-carbethoxypyrazole, 3,5-bis-carbethoxypyrazola, 3,4,5-triscarbethoxypyrazole, ~(5)-methyl-5(3) methylthio-4-carbethoxypyraæola, 4-methyl-3,5--biscarbethoxypyraæole, 4-cyanopyrazole, 4-methoxy-3,5-di-chloropyrazole~ 4,5-dichloroimidazole, 2-ethyl-4,5-dichloro-imidazole, 2-methyl-4,5-dichloroimidazole, 3(5)-methyl-1,2,4-` - 5~-~3~5 O.Z. 0050/03332~
-triazole~ 3,5-dimethyl-1,2,4-triazole, 3(5)-chloro-1,2,4--triazole, 3(5)-bromo-1,2,4-triazole, 3(5)-chloro-5(3)-methyl--192,4-triazole, 3,5-dichloro-1,2,4-triazole, 3,5-dibromo--1,2,4-triazole, 3(5)-chloro-5(3)-cyano-1,2,4-triazole, 3(5) chloro-5(3)-phenyl-1,2,4-triazole, 3(5)-chloro-5(3)--carbomethoxy-1,2,4-triazole, 3(5)-methylthio-1~2,4-triazole, 4(5)-methyl-1,2,3~triazole, 4,5-dimethyl-1,2,3-triazole, 4(5)-phenyl-1,2,3-triazole, 4(5)-chloro-1,2,3-triazole, 1,2,3-triazol-4(5)-yl-carboxylic acid ethyl ester, 1,2,3-tri~
azol-4,5-yl-dicarboxylic acid dimeth~l ester, 5-methyltetra-zole, 5-chlorotetrazole, and tetrazolyl-5-carboxylic acid ethyl ester.
Furthermore, the radical A may, when the optionally sub-stituted azole contains 2 or 3 nitrogen atoms, also be attached in a salt-like manner to one of the usual strong inorganic or organic acids, e.g., hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoboric acid, fluosulfonic acid, and ~ormic acid, a halogenated carboxylic acid, e.g., trichloroacetic acid, an alkanesulfonic acid, e.g., methane-2C ulfonic acid, a halogenated alkanesulfonic acid, e.g., tri-fluoromethanesulf'onic acid and per~luorohexanesul~onic acid, and an arylsul~onic acid, e.g. dodecylbenzenesulfonic acid.
Pre~erred acetanilides are those which bear methyl or ethyl in the 2- and 6-positions on the phenyl ring and hydrogen, methyl or ethyl in the 3-position; sui~able azoles are pyrazole, imidazole, triazole and tetrazole, which are unsubstituted or substituted by lower alkyl, alkoxy, carbalkoxy, cyano or halogen.
~3~C13S
- 6 - O.Z. 0050/03332 In particular, the herbicidal agents accordin~ to the invention contain the following acetanilides:
2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(pyrazol-1-yl-methyl)-acet-anilide, 2-chloro-2',6'-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6-ethyl-N-(4-methoxy-pyrazol-1-yl-methyl) acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(3(5)-methylpyrazol-1-yl)-acetanilide, 2-chloro~2', 6'-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro~2~6~-di~methyl-N-(l~2~4-triazol-l-yl-methyl)-acet anilide~ 2 chloro-2',6'-dimethyl-N-(4-chloropyrazol-1-yl--methyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(pyrazol--1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(3,5-~dimethylpyrazol-1-yl-methyl)-acetanilide, 2~chloro-2',6'-di-ethyl-N-~3~5-dimethylpyrazol-l-yl-methyl)-acetanilide~ 2-chloro--2t~3~6~-trimethyl-N-(3~5-dimethylpyrazol-l-yl-meth7l)-acet-anilide, 2-chloro-2',6'-diethyl-N-(4-methylpyrazol-1-yl-methyl)-~acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4-methylpyrazol--1-ylmethyl)-acetanilide~ 2~chloro-2',3',6~-trimethyl-N~(4-me-2C thylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2',6'-dim~thyl--N-(3~(5)-methylpyrazol-l yl-methyl)~acetanilide, 2-chloro--2',6'-diethyl-N-(3-(5)-methylpyrazol-1-yl-methyl)-ac_tanilide, 2-chloro-2',6'-dimethyl~N-(4-methoxypyrazol-1-yl-methyl)-acet-anilide~ 2-chloro-2'g6'-diethyl-N (pyrazol-1-yl-methyl)-acet~
anilide, 2-chloro-2l,6'-dimethyl-N-(4,5-dichloroirnidazol-1-yl~
-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4,5-di-chloroimidazol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl--6'-ethyl~N-(2-ethyl-l,5-dichloroimidazol-1-yl~methyl)-acet-- 7 - O.Z. 0050/033324 anilide, 2-chloro-2'~6'-diethyl-N-(4,5 dichloroimidazol-1-yl--methyl)-acetanilide, 2-chloro~2'-methyl-6'-ethyl-N-(1,2,4-tri-azol-l-yl-methyl)-acetanilide~ 2-chloro-2',6'-diethyl-N-(1,2,4-~triazol~1-yl-methyl)-acetanilide and 2-chloro-2',3',6'-tri-methyl-N-(1,2,4-triazol-1-yl-methyl)-acetanilide.
A particularly pre~erred agent according to the invention contalns, in addition to N-dichloroacetyl-2,2-dimethyl-1,3--oxazolidine, 2-chloro-21,6'-dimethyl-N-(pyrazol-1-yl-methyl)--acet~nilide as herbicidal active ingredient.
The acetanilides of the ~ormula I are disclosed in German Laid-Open Applications DE-OS 25648,oo8 and DE-OS 2,74~,396.
They may be obtained by reaction of 2-halo-N-halomethylacet-anilides of the formula II with a lH-azole of the formula H-A
in accordance with the ~ollowing equation:
R R
~ /CH2-X I CH2-A
</ \~N~ ~ H-A ~ + HX
R2/~/ CO-CH2-X R2 /~/ CO-CH2-X
Rl R
II
R, R1, R2 and X have the above meanings and A denotes an azole linked via a rin~ nitrogen atom and which may be mono- or poly-substituted by halogeng phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy o~ up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms.
The manu~acture o~ N-dichloroacetyl-2,2-dimethyl 1~--oxazolidine i8 disclosed in German Laid-Open Applications DE-OS 2,218,097 and DE-OS 2,402,98~.
1l~3~g~3~
- 8 - O.Z. 0050/033324 N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine itself has scarcely any in~luence, if at all, on the germination and growth of crop and unwanted plants, even at application rates well above those required for an antagonistic sffect.
However, it is capable of considerably reducing the phyto-toxicity of the herbicidal acetanilides of the formula I
to crop plants such as Indian corn, or of eliminating it completely.
In these case of herbicidal acetanilides which are less a~gressive to crop plants, low additions of N-dichloro-ac~tyl-2,2-dimethyl-1,3-oxazolidine are suf~icient. The ratio of acetanilide to N-dichloroacetyl 2,2-dimethyl-1,3-oxa-zolidine may vary within wide limits, and depends on the acetanilide. Suitable ratios of herbicidal active ingre-dient to N-dichloroacetyl-2,2-dimethyl-1~3-oxazolidine are - from 1:2 to 1:0~01 parts by weight.
Acetanilides and antagonistic compounds may be in-corporated into the soil either together or separately and before or after sowing. With acetanilides of the formula I~
2~ the commonest method is to apply them to the surface of the soil immediately after sowing, or in the period between sowing and emergence o~ the young plants. It is also possible to apply them during emergence and shortly therea~ter. In each instance, the antagoniætic agent may be applied simultaneously with the herbicidal active ingredient~ It is also possible to apply the compounds separately - either the antagonist ~irst and then the herbicidal active ingredient, or vice versa -provided that, if the herbicidal active ingredient is applied :1 ~31~3~
- g O.Z. 0050/033324 first, not too much time elapses be~ore the antagonist is applied as otherwise the crop plants may be damaged. The active ingredient and antagonist may be suspended, emulsified or dissolved in a spray liquor or may be in granular ~orm, and may be formulated together or separately. It is also feasible to treat the seed with the antagonist befora sowing. The herbicidal active ingredient is then applied on its own in the usual manner.
The novel herbicidal agents may contain, in addition to acetanilide and N-dichloroacetyl~2,2-dimethyl-1,3-oxazolidine, other herbicidal or growth-regulating active ingredients of di~ferent chemical structure, e.g., 2-chloro-4-ethylamino-6 -isopropylamino-1~3,5-triazine, without the antagonistic effect being impaired.
The agents according to the invention, or, when applied separately~ the herbicidal active ingredients and the antidote are applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous~ oily or other suspensions), dispersîons, emulsions, 2C oil dispersionsg pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The ~orms o~ application depend entirely on the purpose for which the agents are being used; in any case they should ensure very ~ine distribution of the agents according to the invention or their individual components.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil ~ractions o~
medium to high boiling point, such as kerosene or diesel oil, - ~3~ 5 - 10 - O.z. 0050/033324 further coal-tar oils, and oils of vegetable or animal origin~ -aliphaticg cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar sol~ents such as dimethylformamide, dimethyl-sulfoxide, N-methylpyrrolidone, waterg etc. are suitable.
Aqueous formulations may be prepared from emulsion con-centrates~ pastes, oil dispersions or wettable powders by adding water. To prepare emulsions~ pastes and oil dispersions the herbicidal active ingredient and/or antidote, as such or dis~olved in an oil or solventg may be homogenized in water by means of wetting or dispersing a~ents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be prepared ~ om herbicidal active ingredient and/or antidoteg wetting agent, adherent, emulsifying or dispersing agent and possibly sol~ent or oil.
Examples of surfactants are: alkali metal, alkaline earth 2C metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acidg lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts o~ fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-~3~3S
0 Z. 0050/033324lene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and ~ormaldehyde~ polyoxyethylene octylphenol ethers, ethoxyl-ated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol~ alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol3 fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the herbicidal active ingredient and/or anti-dote wit~ a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicîc acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loessS clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, mag-2C nesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate~ and ureas, and vegetable producks such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of herbicidal active ingredient and/or antidote. Application rate3 are from 0.2 to 5 kg of herbicidal active ingredient per hectare. This amount of herbicidal active ingredient is applied, together or separately, with ~IL3~33~
such an amount of antidote to give a ratio of herbicidal active ingredient to antagonist of from 1:2 to 1:0.01 parts by weight.
Examples of formulations are given below.
I. 40 parts by weight of a mixture of 4 parts by weight of 2-chloro-2l,6'-dimethyl-N-(pyrazol-l-yl-methyl)-acetamide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl-1,3--oxazolidine is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable~
aqueous dispersion is obtained. Dilution in 1003000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of the mixture of active ingredient + antidote.
II. 3 parts by weight of a mixturs of 1 part by weight of 2-chloro-2',6'-dimethyl-N-(pyrazol-l-yl-methyl)-acetanilide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl-1,3--oxaæolidine is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the mixture of active ingredient + antidote.
2C III. 30 parts by weight of a mixture of 1 part by weight of 2~chloro 2'-methyl-6'-ethyl-N-~1,2,4-triazol-1-yl-methyl)~acet-anilide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl--1,3~oxazolidine is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of para~in oil which has been sprayed onto the surface of this silica gel. A ~ormulation is obtained having good adherence.
~l3~3~
- 13 - O.Z. 0050/033324 IV. 20 parts by weight of a mixture of 8 parts by weight of 2-chloro-2'-methyl~5~-ethyl~N-(pyrazol-1-yl-methyl)-acet-anilide and 1 part by weight of N-dichloroacetyl~2,2-dimethyl--1,3-oxazolidine is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dis-persion is obtained.
V. 20 parts by weight of a mixture of 10 parts by weight of 2-chloro-2',6 7 -dimethyl-N-(4l5-dichloroimidazol-1-yl--methyl~-acetanilide and 1 part by weight of N-dichloro~
acetyl-2,2-dimethyl-1,3 oxazolidine is dissol~ed in a mix-ture consisting of 40 parts by weight o~ cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctyl-phenol, and ~0 parts by weight of the adduct oP 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing 2C it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the mixture of active ingredient ~ antidote.
Gr~enhouse experiments show that the use of the herbicidal agents according to the invention increases the tolerance of the herbicidal acetanilides by the crop plants without the herbicidal action being affected.
Plastic boxes 51 cm long, 32 cm wide and 6 cm deep were filled with loamy sand (pH:6 to 7) containing about 1.5% humus.
L33~
- 14 - O.Z. 0050/033324 Indian corn (Zea mays) was sown sha]low, in rows, in this substrate. Echinochloa crus-galli was scattered at random as unwanted plant~ The non-sterilized soil also additionally contained viable weed seeds which contributed to the weed population. A field with crop plants growing in it and in-fested with weeds was thus simulated.
The active ingredients and the antagonist were applied separately and in the mixtures given below. They were emul-si~ied or suspended in water as vehicle and the liquor was sprayed through finely distrihuting nozzles onto the soil surface, either immediately after sowing or prior to emergence of the test plants After sowing and treatment the boxes were sprinkler-irrigated and covered with transparent plastic hoods until the plants emerged. These measures ensured that the plants germinated and took root uniformly. The boxes were set up in the greenhouse at from 18 to 30C. These greenhouse experiments were monitored until 3 to 5 Indian corn leaves had developed.
The scale for assessing the action of the agents was 0 2C to 100, 0 denoting normal emergence and development of the plants, with reference to the untreated control, and 100 denoting non-germination or withering of the plants. It should be borne in mind here that, for instance in Indian corn, odd crippled or retarded plants may occur even under completely normal conditions and without any chemical treat-ment.
~L~3~3S
- 15 - O.Z. 0050/033324 The following table shows the extent to which N~dichloro-acetyl 2,2 dimethyl-1,3-oxazolidine increases the tolerance by Indian corn of acetanilides of the ~ormula I, e.g., 2-chloro-2',6'-dimethyl-N-(pyrazol 1-yl-methyl)-acetanilide.
- 16 -0 ~ Z . 0050/033324 . ~' ~ ~ ~ o, o~ o~ ~ 8 S ~ ,, .
o .,~ ~ a) ~ s 3 la)O
~o ~ ~ rq _^ O S:: ~ ~~ O ~ O
~I O O ~ ~/1 .
S ~ ~ ~
O . N O Ls~ O
C E ~a S ~ ~ N ~ N N
~ X
o a) a~ Z
~ h O = C~ ~ S
h --~ C~ . ~) 3 O S ~ ~ ,~ ~
S E~ ,o O , , C~ ~ ~
~:~1 .'''. 'J-~ ' + b~D
E e ~ ,, ~ Z~ C~N E
H I ~ :C O C O
.Q S~ O C~ cC S~
~ ~ x e :~: ¢ o- o ..~,.. ..' , . .
Claims (5)
1. A herbicidal agent containing at least one substituted acetanilide of the formula I, where R denotes hydrogen, linear or branched alkyl or alkoxy of up to 5 carbon atoms, R1 denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R2 denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R2 denotes an alkylene chain of up to 6 carbon atoms which is linked in the o-position and may be substituted by linear or branched alkyl of up to 4 carbon atoms, X denotes chlorine or bromine, and A denotes an azole ring con-taining 1 to 4 nitrogen atoms which is attached via a ring nitro-gen atom and may be mono- or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy of up to 4 carbon atoms in the alkoxy, or alkanoyl or up to 4 carbon atoms, or A denotes a salt of an azole ring containing 2 or 3 nitrogen atoms, as herbicidal active ingredient, and N-dichloroacetyl-2,2-dimethyl-1,3-oxazoli-dine as antagonistic agent, the ratio of acetanilide to N-dichlo-roacetyl-2,2-dimethyl-1,3-oxazolidine being from 1:2 to 1:0.01 parts by weight.
2. A herbicidal agent as claimed in claim 1, wherein the herbicidal active ingredient is 2-chloro-2'6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide.
3. A process for the selective control of unwanted plant growth in Indian corn and other cereal crops, wherein a herbicidal agent as claimed in claim 1 is applied to the plants and/or their habitat before, during or after sowing of the crop plants, or before or during emergence of the crop plants, at such a rate that the amount of the herbicidal acetanilide of the formu-la I as set forth in claim 1 is from 0.2 to 5 kg per hectare.
4. A process for protecting Indian corn and other cereal crops from injury due to a herbicidal acetanilide of for-mula I as set forth in claim 1, wherein 0.2 to 5 kg per hectare of said acetanilide and an antidotally effective amount of N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine are applied to the plants or their habitat.
5. A process for protecting Indian corn and other cereal crops from injury due to a herbicidal acetanilide of the formula I as set forth in claim 1, wherein the crop seed is trea-ted with an antidotally effective amount of N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine, and then 0.2 to 5 kg per hectare of said acetanilide is applied before, during or after sowing of the crops plants, or before or during emergence of the crop plants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782832940 DE2832940A1 (en) | 1978-07-27 | 1978-07-27 | HERBICIDAL AGENTS |
| DEP2832940.0 | 1978-07-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131035A true CA1131035A (en) | 1982-09-07 |
Family
ID=6045510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA332,135A Expired CA1131035A (en) | 1978-07-27 | 1979-07-19 | Herbicidal agents containing herbicidal acetanilides and n-dichloroacetyl-2,2-dimethyl-1,3- oxazolidine as antagonistic agent |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0009091B1 (en) |
| JP (1) | JPS5520762A (en) |
| AT (1) | ATE403T1 (en) |
| AU (1) | AU525934B2 (en) |
| BR (1) | BR7904718A (en) |
| CA (1) | CA1131035A (en) |
| CS (1) | CS208674B2 (en) |
| DD (1) | DD145050A5 (en) |
| DE (2) | DE2832940A1 (en) |
| DK (1) | DK315079A (en) |
| ES (1) | ES482838A1 (en) |
| GR (1) | GR66590B (en) |
| HU (1) | HU181850B (en) |
| IL (1) | IL57856A (en) |
| MA (1) | MA18538A1 (en) |
| NZ (1) | NZ191130A (en) |
| PL (1) | PL114581B2 (en) |
| PT (1) | PT69977A (en) |
| RO (1) | RO76714A (en) |
| ZA (1) | ZA793831B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1231710A (en) * | 1979-07-19 | 1988-01-19 | Haken Pieter Ten | Heterocyclic compounds having fungicidal, herbicidal and plant-growth regulating properties |
| JPS6362204U (en) * | 1986-10-06 | 1988-04-25 | ||
| JP3967431B2 (en) * | 1997-09-03 | 2007-08-29 | 株式会社トクヤマ | Ethenylamide herbicide composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1174865A (en) * | 1971-04-16 | 1984-09-25 | Ferenc M. Pallos | Thiolcarbamate herbicides containing nitrogen containing antidote |
| US4021224A (en) * | 1971-12-09 | 1977-05-03 | Stauffer Chemical Company | Herbicide compositions |
| CH574207A5 (en) * | 1973-01-25 | 1976-04-15 | Ciba Geigy Ag | |
| US4053297A (en) * | 1975-04-21 | 1977-10-11 | Velsicol Chemical Corporation | Selective herbicidal compositions |
| DE2648008C3 (en) * | 1976-10-23 | 1980-09-04 | Basf Ag, 6700 Ludwigshafen | Acetanilide |
| IL53938A0 (en) * | 1977-02-02 | 1978-04-30 | Bayer Ag | Novel n-substituted halogenoacetanilides, their preparation and their use as herbicides |
| DE2744396A1 (en) * | 1977-10-03 | 1979-04-12 | Basf Ag | ACETANILIDE |
-
1978
- 1978-07-27 DE DE19782832940 patent/DE2832940A1/en active Pending
-
1979
- 1979-06-27 GR GR59452A patent/GR66590B/el unknown
- 1979-07-18 EP EP79102527A patent/EP0009091B1/en not_active Expired
- 1979-07-18 AT AT79102527T patent/ATE403T1/en not_active IP Right Cessation
- 1979-07-18 DE DE7979102527T patent/DE2961361D1/en not_active Expired
- 1979-07-19 CA CA332,135A patent/CA1131035A/en not_active Expired
- 1979-07-20 IL IL57856A patent/IL57856A/en unknown
- 1979-07-23 JP JP9272879A patent/JPS5520762A/en active Pending
- 1979-07-24 MA MA18735A patent/MA18538A1/en unknown
- 1979-07-24 BR BR7904718A patent/BR7904718A/en unknown
- 1979-07-25 AU AU49207/79A patent/AU525934B2/en not_active Ceased
- 1979-07-25 RO RO7998268A patent/RO76714A/en unknown
- 1979-07-25 PL PL1979217377A patent/PL114581B2/en unknown
- 1979-07-25 PT PT69977A patent/PT69977A/en unknown
- 1979-07-25 DD DD79214607A patent/DD145050A5/en unknown
- 1979-07-26 NZ NZ191130A patent/NZ191130A/en unknown
- 1979-07-26 DK DK315079A patent/DK315079A/en not_active Application Discontinuation
- 1979-07-26 CS CS795202A patent/CS208674B2/en unknown
- 1979-07-26 ZA ZA00793831A patent/ZA793831B/en unknown
- 1979-07-26 ES ES482838A patent/ES482838A1/en not_active Expired
- 1979-07-26 HU HU79BA3823A patent/HU181850B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HU181850B (en) | 1983-11-28 |
| ATE403T1 (en) | 1981-12-15 |
| BR7904718A (en) | 1980-05-13 |
| PT69977A (en) | 1979-08-01 |
| GR66590B (en) | 1981-03-30 |
| AU525934B2 (en) | 1982-12-09 |
| DD145050A5 (en) | 1980-11-19 |
| IL57856A0 (en) | 1979-11-30 |
| MA18538A1 (en) | 1980-04-01 |
| PL217377A2 (en) | 1980-06-02 |
| AU4920779A (en) | 1980-01-31 |
| EP0009091A1 (en) | 1980-04-02 |
| ZA793831B (en) | 1980-08-27 |
| IL57856A (en) | 1982-12-31 |
| DE2961361D1 (en) | 1982-01-21 |
| PL114581B2 (en) | 1981-02-28 |
| DE2832940A1 (en) | 1980-02-14 |
| EP0009091B1 (en) | 1981-11-18 |
| RO76714A (en) | 1981-05-30 |
| ES482838A1 (en) | 1980-04-16 |
| DK315079A (en) | 1980-01-28 |
| NZ191130A (en) | 1981-07-13 |
| JPS5520762A (en) | 1980-02-14 |
| CS208674B2 (en) | 1981-09-15 |
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| MKEX | Expiry |