CA1144770A - Herbicidal agents containing haloacetanilides and tetrahydro-1,3-oxazines - Google Patents
Herbicidal agents containing haloacetanilides and tetrahydro-1,3-oxazinesInfo
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Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention relates to a herbicidal agent comprising haloacetanilides in combinaison with an antagonistic agent selected among tetrahydro-1,3-oxazines of the formula
The present invention relates to a herbicidal agent comprising haloacetanilides in combinaison with an antagonistic agent selected among tetrahydro-1,3-oxazines of the formula
Description
77~
This is a division of the Canadian p~ten-t application n 331.488 filed on July 10th, 1979.
The present invention relates to herbicidal agents containing, as herbicidal active ingredients, substituted acetanilides and, as antagonistic agents, tetrahydro-1,3-oxazines. The invention also relates to a process for selectively combating unwanted plant growth with these herbicidal agents.
Substituted acetanilides of the formula R2 ~ \ Co-C~ -X I, 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 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 azole which is attached via a ring nitrogen atom and may be mono ox polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or per-fluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy of up to 4 carbon atoms in t~le alkoxy, or alkanoyl of up to 4 carbon atoms, or ~ denotes salts of azoles containing 2 or 3 nitrogen atoms, have an excellent her~icidal action, but cause damage to crops such as Indian corn and Gramineae.
Therefore, it becomes necessary to add antagonistic agents to offset this poor tolerance of herbicidal acetanilides by certain crop plants. ~.
'7~
Herbicidal agents containing, in addition to chloroacetanilides as herbicidal active ingredients, antagonistic compounds have been disclosed in the United States patent n 3,719,466 and German Laid~Open Applications DE_OS nos 2,218,097 and 2,402,983.
United States patent n 3,719,~66 teaches that damage to sorghum and wheat caused by the herbiciae
This is a division of the Canadian p~ten-t application n 331.488 filed on July 10th, 1979.
The present invention relates to herbicidal agents containing, as herbicidal active ingredients, substituted acetanilides and, as antagonistic agents, tetrahydro-1,3-oxazines. The invention also relates to a process for selectively combating unwanted plant growth with these herbicidal agents.
Substituted acetanilides of the formula R2 ~ \ Co-C~ -X I, 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 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 azole which is attached via a ring nitrogen atom and may be mono ox polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or per-fluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, carbalkoxy of up to 4 carbon atoms in t~le alkoxy, or alkanoyl of up to 4 carbon atoms, or ~ denotes salts of azoles containing 2 or 3 nitrogen atoms, have an excellent her~icidal action, but cause damage to crops such as Indian corn and Gramineae.
Therefore, it becomes necessary to add antagonistic agents to offset this poor tolerance of herbicidal acetanilides by certain crop plants. ~.
'7~
Herbicidal agents containing, in addition to chloroacetanilides as herbicidal active ingredients, antagonistic compounds have been disclosed in the United States patent n 3,719,466 and German Laid~Open Applications DE_OS nos 2,218,097 and 2,402,983.
United States patent n 3,719,~66 teaches that damage to sorghum and wheat caused by the herbiciae
2~chloro-2',6'-diethyl-N-(methoxymethyl)~acetanilide can be avoided by treating the seed with an antagonistic agent such as N,N-diallylacetamide.
German Laid-Open Application DE-OS
n 2,218,097 mentions combinations of the same ac-tive ingredient and other herbicidal acetanilides with antagonistic amides, e.g., N,N diallyldichloroacetamide. However, these amides are preferably used as antidotes for herbicidal thiolcarbamates.
German ~aid-Open Application DE-OS n 2,~02,983 relates to herbicidal agents containing dichloroacetamides known from German Laid-Open Application DE-OS n 2,218,097, or dichloroacetamides s-tructurally simi.lar to them, and chloro~
acetanilides oE a dif~erent constitution, especially N-(2'-methoxyethyl)-2,6-dimethylchloroacetanilide. These agents are suitable merely for selective weed control in Indian corn. Also said to be suitable as antagonistic compounds are, inter alia, dichloroacetamides in which both substituents on the nitrogen atom ~orm, with it, a 6-membered heterocycle containing a further hetero atom and which is unsubstituted or mono- or polysubstituted by lower alkyl.
However the only representative of this group which is mentioned is N-dichloroacetylmorpholine.
The invention relates to herbicidal agents containing at least one substituted acetanilide of the formula I
~4g~
~ N I, ,' ~ _// CO-C112-X
where R denotes hydrogen, linear or branched alkyl or alkoxy of up to 5 carbon atoms, R denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R denotes an alkylene chain of up to 6 carbon atoms which is linked in -the o-position and may be substi-tuted by linear or branched alkyl of up to 4 arbon atoms, X denotes I chlorine or bromine, and A denotes azole which i5 attached - via a ring nitrogen atom and may be mono-or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or per-fluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, 20 carbalkoxy of up to carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms, or A denotes salts of azoles containing 2 or 3 ni-trogen atoms; and at least one tetrahydro-1,3-oxazine of the formula II . .
R \ ~ 11 4 / l ~-CO-R
R ~ ~7 77~
where R clenotes linear or branched haloalkyl of up to 3 carbon atoms, R , R , R , R and R are identical or different and each denotes hydrogen or linear or branched alkyl oE up to 3 carbon atoms, R6 denotes hydrogen or linear or branched alkyl of up -to 8 carbon atoms, R7 denotes hydrogen~ linear or branched alkyl of up to ~ carbon atoms, alkoxyalkyl of up to 6 carbon atoms or dialkoxyalkyl of up to 8 carbon atoms, and R6 and R7 may together form a methylene chain of 4 o~ 5 carbon atoms;may be used both in Indian corn and in cereal crops. These tetrahydro-1,3-oxazines are excellently suited for increasing the tolerance of crop plants to herbicidal substituted acetanilides oE the formula I. The good herbicidal action of the acetanilides is retained and damage to the crop plants is prevented.
Acetanilides w~ose tolerance by crop plants can be increased by the -tetrahydro-1,3-oxazines are those of the formula I in which R is hydrogen, alkyl of a maximum oE 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i.sobu-tyl, tert-butyl, linear and branched pentyl, and alkoxy o:E a maximum oE 5 carbon atoms, I such as methoxy, ethoxy, propoxy, butoxy and pentoxy;
Rl and R are hydrogen, halogen, such as fluorine, chlorine, bromine and iodine, alkyl of a maximum of 5 carbon atoms, such as methyl, ethyl, p-propyl, isopropyl, p-butyl, sec-butyl, isobutyl, tert-butyl, linear and branched pentyl, a~d alkoxy of a maximum of 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, and pentoxy;
.
7(:) R2 together with R is an alkylene chain of a maximum Or 6 carbon atom~, linked in the o-po~ition and unsub3tituted or sub3tituted by alkyl Or a maximum of 4 carbon atom~, e.g., ethyleneg trimethylene, tetramethylene, 1-methyltri~ethylene, 1,1-dimethyltrimethylene, and 1,1-dimethyltetramethylene, X is chlorine, bromine or iodine, preferably chlorine;
A i~ an azole attached via a ring 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 Or up to 4 carbon atoms, the sub~tituents being identical or dif~erent, ~uch a~
2,6~dimethylpyrrole, tetramethylpyrrole, 3(5)-methylpyrazole, 4-methylpyrazole, ~(5)-ethylpyrazole, 4-ethylpyrazole, 3(5)-i~o-propylpyrazole, 4-isopropylpyrazole, 3,5-dimethylpyrazole,
German Laid-Open Application DE-OS
n 2,218,097 mentions combinations of the same ac-tive ingredient and other herbicidal acetanilides with antagonistic amides, e.g., N,N diallyldichloroacetamide. However, these amides are preferably used as antidotes for herbicidal thiolcarbamates.
German ~aid-Open Application DE-OS n 2,~02,983 relates to herbicidal agents containing dichloroacetamides known from German Laid-Open Application DE-OS n 2,218,097, or dichloroacetamides s-tructurally simi.lar to them, and chloro~
acetanilides oE a dif~erent constitution, especially N-(2'-methoxyethyl)-2,6-dimethylchloroacetanilide. These agents are suitable merely for selective weed control in Indian corn. Also said to be suitable as antagonistic compounds are, inter alia, dichloroacetamides in which both substituents on the nitrogen atom ~orm, with it, a 6-membered heterocycle containing a further hetero atom and which is unsubstituted or mono- or polysubstituted by lower alkyl.
However the only representative of this group which is mentioned is N-dichloroacetylmorpholine.
The invention relates to herbicidal agents containing at least one substituted acetanilide of the formula I
~4g~
~ N I, ,' ~ _// CO-C112-X
where R denotes hydrogen, linear or branched alkyl or alkoxy of up to 5 carbon atoms, R denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R denotes hydrogen, halogen, or linear or branched alkyl or alkoxy of up to 5 carbon atoms, R together with R denotes an alkylene chain of up to 6 carbon atoms which is linked in -the o-position and may be substi-tuted by linear or branched alkyl of up to 4 arbon atoms, X denotes I chlorine or bromine, and A denotes azole which i5 attached - via a ring nitrogen atom and may be mono-or polysubstituted by halogen, phenyl, alkyl, alkoxy, alkylthio or per-fluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy, 20 carbalkoxy of up to carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms, or A denotes salts of azoles containing 2 or 3 ni-trogen atoms; and at least one tetrahydro-1,3-oxazine of the formula II . .
R \ ~ 11 4 / l ~-CO-R
R ~ ~7 77~
where R clenotes linear or branched haloalkyl of up to 3 carbon atoms, R , R , R , R and R are identical or different and each denotes hydrogen or linear or branched alkyl oE up to 3 carbon atoms, R6 denotes hydrogen or linear or branched alkyl of up -to 8 carbon atoms, R7 denotes hydrogen~ linear or branched alkyl of up to ~ carbon atoms, alkoxyalkyl of up to 6 carbon atoms or dialkoxyalkyl of up to 8 carbon atoms, and R6 and R7 may together form a methylene chain of 4 o~ 5 carbon atoms;may be used both in Indian corn and in cereal crops. These tetrahydro-1,3-oxazines are excellently suited for increasing the tolerance of crop plants to herbicidal substituted acetanilides oE the formula I. The good herbicidal action of the acetanilides is retained and damage to the crop plants is prevented.
Acetanilides w~ose tolerance by crop plants can be increased by the -tetrahydro-1,3-oxazines are those of the formula I in which R is hydrogen, alkyl of a maximum oE 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i.sobu-tyl, tert-butyl, linear and branched pentyl, and alkoxy o:E a maximum oE 5 carbon atoms, I such as methoxy, ethoxy, propoxy, butoxy and pentoxy;
Rl and R are hydrogen, halogen, such as fluorine, chlorine, bromine and iodine, alkyl of a maximum of 5 carbon atoms, such as methyl, ethyl, p-propyl, isopropyl, p-butyl, sec-butyl, isobutyl, tert-butyl, linear and branched pentyl, a~d alkoxy of a maximum of 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, and pentoxy;
.
7(:) R2 together with R is an alkylene chain of a maximum Or 6 carbon atom~, linked in the o-po~ition and unsub3tituted or sub3tituted by alkyl Or a maximum of 4 carbon atom~, e.g., ethyleneg trimethylene, tetramethylene, 1-methyltri~ethylene, 1,1-dimethyltrimethylene, and 1,1-dimethyltetramethylene, X is chlorine, bromine or iodine, preferably chlorine;
A i~ an azole attached via a ring 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 Or up to 4 carbon atoms, the sub~tituents being identical or dif~erent, ~uch a~
2,6~dimethylpyrrole, tetramethylpyrrole, 3(5)-methylpyrazole, 4-methylpyrazole, ~(5)-ethylpyrazole, 4-ethylpyrazole, 3(5)-i~o-propylpyrazole, 4-isopropylpyrazole, 3,5-dimethylpyrazole,
3,5-dimethyl-4-acetylpyrazole, 3,5-dimethyl-4-propionylpyrazole, 3,4,5-trimethylpyr~zole, 3(5)-phenylpyrazole, 4-phenylpyrazole, 3,5-diphenylpyrazole, 3(5)-phenyl-5(3)-methylpyrazole, 3(5)-2C -chloropyrazole, 4-chloropyrazole, 4-bromopyrazole, 4-iodo-pyrazole, 3,4,5-tribromopyrazole~ 3,5-dimethyl-4-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)-dichloropyrazole~ 3(5)-chloro-5(3)-methyl-pyrazole~ 4-methoxypyrazole, 3(5)-methyl-5(3)-methoxypyrazole, 3(5)-ethoxy-4,5(3)-dimethylpyrazole, ~(5)-methyl-5(3)~trifluoro-methylpyraæole, 3,5-bi~-tri~luoromethylpyrazole, 3(5~methyl-D5 ( 3)-carbethoxypyrazole, 3~5 bis-carbethoxypyrazole, 3,4,5-tri~-carbethoxypyrazole, 3(5)-methyl-5~3)-methylthio-4-carbethoxypyrazole, `." -` 1~4~
.. .
4-methyl-3,5-biscarbethoxypyrazole, 4-cyanopyrazole, 4-methoxy--3,5-dichloropyrazole, 4,5-dichloroimidazoleg 2-ethyl-4,5-di-chloroimidazole, 2-methyl-4,5-dichloroimidazole, 3(5)-methyl--1,2,4-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--1,2,4-triazole, 3,5~dichloro-1,2,4-triazole, 3,5-dibromo-1,2,ll-trlazole, 3(5)-chloro-5(3)-cyano-1,2,4-triazole, 3(5)-chloro-5(3)--phenyl-1,2,4-triazole, 3(5)-chloro-5t3)-carbomethoxy-1~2,4-tri-azole, 3(5) methylthio-1,2,4-triazole, 4(5)-methyl-1,2,3-tri-azole, 4,5-dimethyl-1,2,3-triazole, 4(5)-phenyl-1,2,3-triazole, 4(5)-chloro-1,2,~-triazole, 1,2,3-triazol-4(5)-yl-carboxylic acid ethyl ester, 1,2,3-triazol-4,5-yl-dicarboxylic acid di-methyl ester, 5-methyltetrazole, 5-chlorotetrazole, and tetra-zolyl-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 saltlike manner to one of the usual strong inorganic or organic acids, e.g., hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoboric acid, fluo~ul~onic acid~ and 2C formic acid, a halogenated carboxylic acid, e.g., trichloroac~tic acid, an alkanesulronic acid, e.~., methanesulfonic acid, a halogenated alkanesulfonic acid, e.g., trifluoromethanesulfonic acid and perfluorohexanesu~fonic acid, and an arylsulfonic acid, e.g. dodecylbenzenesulfonic acid.
Preferred acetanilides are those which bear methyl or ethyl in the 2- and 6-po3ition3 on the phenyl ring and hydrogen, methyl or ethyl in the 3-position; suitable azoIes are pyrazole~
imidazole, triazole and tetrazole, which are unsubstituted or ~4L'7~0 sub~tituted by lower alkyl~ alkoxy, alkylthio, carbalkoxy, cyano or halogen.
In particular, the herbicidal agents according 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-pyraæol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-~3(5)-methylpyrazol-1-yl)-acetanilide 3 2-chloro-2'~
6t-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2',6'-dimethyl-N-(1,2,4-triazol-1-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-21,6'-di-ethyl-N-~3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acet-.
anilide, 2-chloro-2',6'-diethyl-N-(4-methylpyraæol-1-yl-m~thyl)-2C -acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4-methylpyrazol--1-ylmethyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(4-me-thylpyrazol-l~yl-methyl)-~cetanilide 3 2-chloro-2' 6'-dimethyl--N-(3 (5)-methylpyrazol-1-yl-methyl)-acetanilide, 2-chloro~
-2~,6~-diethyl-N-(3-(5)-methylpyrazol-1-yl-methyl) acetanilide, 2-chloro 2',6'-dimethyl-N-(4-methoxypyrazol-1-yl-methyl)-acet~
anilide, 2-chloro-2',6'-diethyl~N-(pyrazol-1 yl-methylj-acet-anilide, 2~chloro-2',6'-dimethyl~N-(4,5-dichloroimidazol-1-yl--methyl)-acetanilide~ 2-chloro~2' meShyl~6' ethyl-N~(4,5-di-477C~
chloroimidazol~l~yl-methyl)-acetanilide~ 2 c~loro,2'~methyl--6'-ethyl-N-(2~ethyl-4,5-dichloroimidazol-1-yl~methyl)-acet-anilide, 2-chloro-2',6'-diethyl-N ~4,5-dichloroimidazol l~yl--methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-~-(1,2,4-tri-a~ol--1-yl-me-thyl)-acetanilide, 2-chloro-2',6'~diethyl-N-(1,2,4--triazol-l-yl~methyl)~ace-tanilide and 2~chloro-2',3',6'-tri-methyl-N-(1,2,4-triazol-1-yl-methyl)-acetanillde.
The acetanilides of the formula I are disclosed in Germain laid-Open Application published under DE-OS 2,648,008 and Canadian Patent Application n 312,376 filed on September 29, 1978. They may be obtained by reaction of 2-halo-N-halo-methylacetanilides ~f the formula V with a lH-azole of the for-mula H-A in accordance with the following equation:
R R
- N ~ 2 + H-A ~ ~ ~ / 2 A +
~ ~ ~ CO-CH2 X ,~ \~0-CH2-X
V
R, Rl, R2 and X have the above meanings and A denotes an azole linked via a ring nitrogen atom and which may be mono- or poly-substituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms.
Suitable antagonistic agents are tetrahydro-1,3 -oxazines of the formula II in which the substituents Rl to R5 are identical or different and each denotes~hydrogen or alkyl of up to 3 carbon atoms, especially hydrogen or methyl.
and R7 . ..
4~7~
denote hydrogen or alkyl of up to 8 carbon atom~, such a~
methyl, ethyl, n-yropyl, isopropyl, butyl, hexyl, heptyl and octyl.
R may also denote alkoxyalkyl o~ up to 6 carbon atoms or dialkoxyalkyl of up to 8 carbon atoms, e.g., methoxymethyl and dimethoxymethyl. R and R7 may together form a methylene chain o~ 4 or 5 carbon atomsO R denotes haloalkyl of up to 3 carbon atoms, preferably chloroalkyl3 and especially chloro-methyl and dichloromethyl.
Preferred tetrahydro-1,3-oxazines are N-dichloroacetyl-4g4--dimethyltetrahydro-1,3-oxazine and N-dichloroacetyl-4,4,6-tri-methyltetrahydro-1,3-oxa~ine, These tetrahydro-1,3 - oxazines o~ the formula IX are obtained by reaction of a compound of the formula R2 ~,1 R4 ~ NH . . III, where R1, R2~ R3, R4, R5, R6 and R7 have the above meanings, with an acid chloride o~ the formula 2C R-CO-Cl IV, where R has the above meanings9 in the presence of an agenk which binds hydrogen chloride and in an inert solvent or diluent.
Examples o~.agent~ which bind hydrogen chloride are inorganic bases~ such aq alkali metai carbonates, alkali metal bicarbonate3 and alkali metal hydroxides, and organic bases, e.g., tertiary amine~, such a~ trialkylamines, and especially triethylamine~
Suitable inert solvents or diluents are hydrocarbon~, such as toluene, xylene~ ligroin and cyclohexane 3 halogenated hydro-7~
carbon~, such as dichloromethane, chloro~orm and carbon tetra-chloride, and ethers, such a~ diethyl ether, diisopropyl ether, tetrahydrofuran~ dioxane and ani~ole.
The following example illu~trates the production of the tetrahydro-1,3-oxazines. Park~ by weight bear the s~ne relationship to parts by volume as kilogram~ to liters.
At ~10 C and while stirring, 23.2 parts by weight of dichloro-acetyl ehloride in 100 part~ by ~olume o~ toluene i~ dripped into 23.0 part~ by weight of 4,4-dimethyltetrahydro-1,3~oxazine and 20.7 part~ by weight of triethylamine in 100 parts by volume of tolue~e. After the mixture has been stirred for 2 hours at room temperature, there are added 150 parts by volume of methylene chloride and enough water for 2 clear phases to be formed. The organic phase is separated and washed twice, each time with 50 part~ by ~olume of water. After drying and evaporation o~ the solvents under reduced pressure, there is isolated 41 parts by weight of N-dichloroacetyl-4,4-dimethyl-tetrahydro~ oxazine o~ melting point 105-106C, which melts, 2C after recrystallization from methanol, at 106-107C~
a 13 2 2 2 MW: 226 calc.: C 42.5 H 5.8 N 6.19 found: C 42.6 H 5~8 N 6.2 The following compounds may be prepared analo~ously:
'77~
R4 ~ N-C0-R
'J~0 ~ R7 No. R R1 R2 R3 R4 R5 R6 R7 m.p./b.p./~
, 1 CH~Cl CH3 CH3 H H H H H b-p 0.067 mbar 2 CH2Cl CH3~ CH3 H H CH3 H H
3 CHCl2 CH3 CH3 . H H H H H m.p.: 108C
4 CHC12 CH3 CH3 H H H CH3 H oil
.. .
4-methyl-3,5-biscarbethoxypyrazole, 4-cyanopyrazole, 4-methoxy--3,5-dichloropyrazole, 4,5-dichloroimidazoleg 2-ethyl-4,5-di-chloroimidazole, 2-methyl-4,5-dichloroimidazole, 3(5)-methyl--1,2,4-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--1,2,4-triazole, 3,5~dichloro-1,2,4-triazole, 3,5-dibromo-1,2,ll-trlazole, 3(5)-chloro-5(3)-cyano-1,2,4-triazole, 3(5)-chloro-5(3)--phenyl-1,2,4-triazole, 3(5)-chloro-5t3)-carbomethoxy-1~2,4-tri-azole, 3(5) methylthio-1,2,4-triazole, 4(5)-methyl-1,2,3-tri-azole, 4,5-dimethyl-1,2,3-triazole, 4(5)-phenyl-1,2,3-triazole, 4(5)-chloro-1,2,~-triazole, 1,2,3-triazol-4(5)-yl-carboxylic acid ethyl ester, 1,2,3-triazol-4,5-yl-dicarboxylic acid di-methyl ester, 5-methyltetrazole, 5-chlorotetrazole, and tetra-zolyl-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 saltlike manner to one of the usual strong inorganic or organic acids, e.g., hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoboric acid, fluo~ul~onic acid~ and 2C formic acid, a halogenated carboxylic acid, e.g., trichloroac~tic acid, an alkanesulronic acid, e.~., methanesulfonic acid, a halogenated alkanesulfonic acid, e.g., trifluoromethanesulfonic acid and perfluorohexanesu~fonic acid, and an arylsulfonic acid, e.g. dodecylbenzenesulfonic acid.
Preferred acetanilides are those which bear methyl or ethyl in the 2- and 6-po3ition3 on the phenyl ring and hydrogen, methyl or ethyl in the 3-position; suitable azoIes are pyrazole~
imidazole, triazole and tetrazole, which are unsubstituted or ~4L'7~0 sub~tituted by lower alkyl~ alkoxy, alkylthio, carbalkoxy, cyano or halogen.
In particular, the herbicidal agents according 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-pyraæol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-~3(5)-methylpyrazol-1-yl)-acetanilide 3 2-chloro-2'~
6t-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2',6'-dimethyl-N-(1,2,4-triazol-1-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-21,6'-di-ethyl-N-~3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acet-.
anilide, 2-chloro-2',6'-diethyl-N-(4-methylpyraæol-1-yl-m~thyl)-2C -acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4-methylpyrazol--1-ylmethyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(4-me-thylpyrazol-l~yl-methyl)-~cetanilide 3 2-chloro-2' 6'-dimethyl--N-(3 (5)-methylpyrazol-1-yl-methyl)-acetanilide, 2-chloro~
-2~,6~-diethyl-N-(3-(5)-methylpyrazol-1-yl-methyl) acetanilide, 2-chloro 2',6'-dimethyl-N-(4-methoxypyrazol-1-yl-methyl)-acet~
anilide, 2-chloro-2',6'-diethyl~N-(pyrazol-1 yl-methylj-acet-anilide, 2~chloro-2',6'-dimethyl~N-(4,5-dichloroimidazol-1-yl--methyl)-acetanilide~ 2-chloro~2' meShyl~6' ethyl-N~(4,5-di-477C~
chloroimidazol~l~yl-methyl)-acetanilide~ 2 c~loro,2'~methyl--6'-ethyl-N-(2~ethyl-4,5-dichloroimidazol-1-yl~methyl)-acet-anilide, 2-chloro-2',6'-diethyl-N ~4,5-dichloroimidazol l~yl--methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-~-(1,2,4-tri-a~ol--1-yl-me-thyl)-acetanilide, 2-chloro-2',6'~diethyl-N-(1,2,4--triazol-l-yl~methyl)~ace-tanilide and 2~chloro-2',3',6'-tri-methyl-N-(1,2,4-triazol-1-yl-methyl)-acetanillde.
The acetanilides of the formula I are disclosed in Germain laid-Open Application published under DE-OS 2,648,008 and Canadian Patent Application n 312,376 filed on September 29, 1978. They may be obtained by reaction of 2-halo-N-halo-methylacetanilides ~f the formula V with a lH-azole of the for-mula H-A in accordance with the following equation:
R R
- N ~ 2 + H-A ~ ~ ~ / 2 A +
~ ~ ~ CO-CH2 X ,~ \~0-CH2-X
V
R, Rl, R2 and X have the above meanings and A denotes an azole linked via a ring nitrogen atom and which may be mono- or poly-substituted by halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of up to 4 carbon atoms in the alkoxy, or alkanoyl of up to 4 carbon atoms.
Suitable antagonistic agents are tetrahydro-1,3 -oxazines of the formula II in which the substituents Rl to R5 are identical or different and each denotes~hydrogen or alkyl of up to 3 carbon atoms, especially hydrogen or methyl.
and R7 . ..
4~7~
denote hydrogen or alkyl of up to 8 carbon atom~, such a~
methyl, ethyl, n-yropyl, isopropyl, butyl, hexyl, heptyl and octyl.
R may also denote alkoxyalkyl o~ up to 6 carbon atoms or dialkoxyalkyl of up to 8 carbon atoms, e.g., methoxymethyl and dimethoxymethyl. R and R7 may together form a methylene chain o~ 4 or 5 carbon atomsO R denotes haloalkyl of up to 3 carbon atoms, preferably chloroalkyl3 and especially chloro-methyl and dichloromethyl.
Preferred tetrahydro-1,3-oxazines are N-dichloroacetyl-4g4--dimethyltetrahydro-1,3-oxazine and N-dichloroacetyl-4,4,6-tri-methyltetrahydro-1,3-oxa~ine, These tetrahydro-1,3 - oxazines o~ the formula IX are obtained by reaction of a compound of the formula R2 ~,1 R4 ~ NH . . III, where R1, R2~ R3, R4, R5, R6 and R7 have the above meanings, with an acid chloride o~ the formula 2C R-CO-Cl IV, where R has the above meanings9 in the presence of an agenk which binds hydrogen chloride and in an inert solvent or diluent.
Examples o~.agent~ which bind hydrogen chloride are inorganic bases~ such aq alkali metai carbonates, alkali metal bicarbonate3 and alkali metal hydroxides, and organic bases, e.g., tertiary amine~, such a~ trialkylamines, and especially triethylamine~
Suitable inert solvents or diluents are hydrocarbon~, such as toluene, xylene~ ligroin and cyclohexane 3 halogenated hydro-7~
carbon~, such as dichloromethane, chloro~orm and carbon tetra-chloride, and ethers, such a~ diethyl ether, diisopropyl ether, tetrahydrofuran~ dioxane and ani~ole.
The following example illu~trates the production of the tetrahydro-1,3-oxazines. Park~ by weight bear the s~ne relationship to parts by volume as kilogram~ to liters.
At ~10 C and while stirring, 23.2 parts by weight of dichloro-acetyl ehloride in 100 part~ by ~olume o~ toluene i~ dripped into 23.0 part~ by weight of 4,4-dimethyltetrahydro-1,3~oxazine and 20.7 part~ by weight of triethylamine in 100 parts by volume of tolue~e. After the mixture has been stirred for 2 hours at room temperature, there are added 150 parts by volume of methylene chloride and enough water for 2 clear phases to be formed. The organic phase is separated and washed twice, each time with 50 part~ by ~olume of water. After drying and evaporation o~ the solvents under reduced pressure, there is isolated 41 parts by weight of N-dichloroacetyl-4,4-dimethyl-tetrahydro~ oxazine o~ melting point 105-106C, which melts, 2C after recrystallization from methanol, at 106-107C~
a 13 2 2 2 MW: 226 calc.: C 42.5 H 5.8 N 6.19 found: C 42.6 H 5~8 N 6.2 The following compounds may be prepared analo~ously:
'77~
R4 ~ N-C0-R
'J~0 ~ R7 No. R R1 R2 R3 R4 R5 R6 R7 m.p./b.p./~
, 1 CH~Cl CH3 CH3 H H H H H b-p 0.067 mbar 2 CH2Cl CH3~ CH3 H H CH3 H H
3 CHCl2 CH3 CH3 . H H H H H m.p.: 108C
4 CHC12 CH3 CH3 H H H CH3 H oil
5 CHC12 CH3 CH3 H H H C2H5 H 1.5152
6 CHC12 CH3 CH3 H H Hn C3H7 H 1~5010
7 ~HCl2 CH3 CH3 H H H i C3H7 H
8 CHC12 CH3 CH3 H H H 3 3 11 -CHCl2 CH3 CH3 H H CH3 H H m.p.: 56C
12 CHCl2CH3CH3 H 3 3 H 1.4918 - 13 CHC12CH3CH3 H H CH3C2H5 H 1.4949 2C 14 CHC12CH3CH3 H H CH3n-C3H7 H 1.4915 15 CHC12CH3~H3 H H CH3 3 7 1.4945 16 CHC12H 3 3 H Hm.p.: 64C
17 CHC12H H CH~ CH3 H 3 m.p: 80C
la CHCl2 H H CH3 ~CH3 H - 2 5 H
19 CHC.12 H H CH3 CH3 H i-C3H7 H - m.p: 84C
CHCl2 H H CH3 CH3 CH3 H H
-- 11 ~
7~
.
No. R R1 R2R3 R4 R5 R6 R7 m,p./b,p /n25 . ~ .. ..... . . . _ 21 CHCl2 H HCH3 CH3 CH3 3 23 CHCl2 H HCH3 C~3 CH3i C3H7 24 CHGl2 H 3 H3 H H3 CH3 26 CHC12 CH3 CH3H H CH3 CH-nC4H9 H 1.4849 ~7 CHC12 CH3 CH3H H CH3 CH3 CH3 28 CHC12 CH3 CH3H H CH3 CH3~ C2H5 29 CHC12 CH3 CH3H H CH3 H CH(OCH3)2 oil CHC12 CH3 CH3H H CH3 CH3 CH30CH2 oil 31 CHC12 CH3 CH3H H CH3 ~ (C~l2)~i oil 32 CHC12 CH3 CH3H H CH3 (C~2)5 oil 33 CC13 CH3 CH3H H H H H m.p.: 103C
35 CH~-CH2Cl CH3 CH3 H H H H H
36 CH2-CH2Cl CH3 CH3 H H CH3 H H
Some of the starting materials of the formuIa III needed the preparation of the tetrahydro- 1,3 _ oxazines are known from Rec. trav. chim. P.B., 78, 315, 1959 and J. Org. Chem., 38, 36, 1973. They may be ~repared by conventional methods, (Tetrahedron, 309 3315, 1974; Rec. trav. chim. P.B., 78, 315, 1959? in accordance with the following eq~uation:
.
; ~4~L770 R4 ~ NH2 ~ O=C ~R6 -H O ~ ~
R5 OH 2 R5~0 R
III
, The ~ollowing example illustrate~ the preparation Or the starting materials. Part~ by weight bear the same relation~hip to part~ by volwne as kilo~rams to liters.
1,170 ~art3 by weight of 2-methyl-2 aminopentan-4-ol is placed in a stirred flask. With external cooling, 440 part~ by weight of acetaldehyde is run in over a period of about 40 minutes at 15-20C. The reaction mixture is ~tirred for a further - 15 minutes at 20C. After the addition of 600 parts by volume of toluene, 182 parts by weight of water is separated off over a period of 2 hours by azeotropic distillation. The reaction product is subjected to fractional distillation. After removal o~ the solvent there is obtained 1j3'12 parts by weight of 2~4,4,6-tetramethyltetrahydro-1,3-oxazine with a purity 2C (according to gas chromatography) of 98%,equivalent to a yield of 94% of theory, based on 2-methyl-2-aminopentan-4 ol~
Boiling point (13 mbars): 53-54C.
nD: 1.4340.
The following compound~ of the formula III are prepared in 'he same ~ay, ' ~ 13 -.
7~1~
,R2 R3 ~ ~ ~H
Rl R2 ~3 R4 R5 R6 R7 n20 b.p,(mbars) Cc]
~ _ . ~ . .
CH3 CH3 H H H H H 1-4290 b.p.(l53) 87 3 3 H H H CH3 1.4372 b-p-(20) 42-43 3 3 H H HC2H5 1.4392 b-p-(2606) 9 ; CH3 ~H3 H H H Hnc3H7 1-4371 b-p-(26.6) 9 7 lOCH3 CH3 H H H HiC3H7 1-4391 b-p-(26~6) 9 CH3 CH3 H H H H CH 4 9 1.4442 b.p.~0,27~ 54 55 CH3 CH3 H H CH3 H H 1-4394 b~p-(13 3) 47-48 CH3 3 H H CH3 H CH3 1.434Q b.p.(13.3) 5 CH3 CH3 H H CH3 HC2H5 1.4345 b~p-(13.3) 3 3 H CH3 Hnc3H7 1-4380 b-P-(0.27) CH3 CH3 H H CH3 -HiC3H7 1.4341 b-p~(13.3) 5 CH3 CH3 H H CH3 HC ~ C H 1.4451 b-p-(0.27) 5 55 2C CH3 CH3 H 3 2 5 1.4451 b.p.(20~ 59-60 CH3 CH3 H H CH3CH3 CH30~H2 1.4415 b-p-(26.6) CH3 CH3 H H H- (CH2)4- 1.4689 b-p-(26.6) 97 98 3 3 3 ~(CH2)4 - 1-4651 b-p (o 2 ) 47-48 CH3 CH3 H H CH - (CH2)5 - 1-4690 b-p-(0.27) H H CH~ CH3 H H H
H ' H CH3 CH3 H i-C3H7 H
77(~
Herbicidal active ingredients and antagonistic compounds may be incorporated into the soil either together or separately and before or after sowing. With acetanilide~, the commone~t method is to apply them to the surface of the soil immediately after sowing, or in the period between sowing and emergence of the young plants. It is also possible to apply them during emergence. In each instance, the antagonistic agent may be .
applied simultaneously with the herbicidal active ingredient.
It is also possible to apply the compounds separately - either the antagonist rirst and then the herbicidal active ingredient, or vice versa - provided that, if the herbicidal active ingre-dient is applied first~ not too much time elapses before 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 form, and may be formulated together or separately. It is also ~easible to treat the seed with the antagonist before sowing. The herbicidal active ingredient is then applied on its own in the usual manner.
2C Varying amounts of antagonistic compound are required for the ~ame herbicidal acetanilide when it is used in different crops. The ratio of acetanllide to tetrahydro~ oxazine may be varied within a wide range; it is dependent on the structure of the anilide and o~ the tetrahydro-193-oxazine, and on the crop in which they are used. Suitable ratios of herbicidal active ingredient to antagonist are from 1:2 to 1:0.05 parts by weight.
The herbicidal agents according to the i~ven-tion may contain, in a~dition to acetanilide and tetrahydro-1,3-oxazine, other herbicidal or growth-regulating active ingredients Or different chemical structure, e.g., 2-chloro-4-ethylamino-6~isopropylamino-1,3,5--triazine, without the antagonistic effec~ being impaired.
The agents according ~o the invention, or, when applied ; separately, the herbicidal active ingredients and the antidote are applied ~or instance in the form of directly sprayable solution~, powders, suspensions ~including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil diqpersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms o~ application depend entlrely on the purpose for which the agents are being used; in any case they should ensure as ~ine a distribution o~ the active ingredient as possible, For the preparation Or solutions, émulsions, pastes and oil dispersions to be sprayed direct, mineral oil ~ractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, 2C aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, pararfin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol~
propanol, butanol, chloro~orm, carbon tetrachloride~ cyclo-hexanol, cyclohexanone, chlorobenzene~ isophorone3 etc., and strongly polar solvents such as dimethylrormamide, dimethyl-sulfoxide, N-methyIpyrrolidone, water, etc. are suitable.
- 16 ~
, Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions~ pastes and oil disper~ions the herbicidal active ingredient and/or antidote as ~uch or dissolved in an oil or solvent may be homogenized in water by means o~ wetting or dispersing agents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be prepared from herbicidal active ingredient and/or antidote, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oll.
Example~ of surfactants are: alkali metal, alkaline earth metal and ammonium salts o~ ligninsulfonic acid, naphthalene-sulfon.ic acids, phenol~ulfonic acids, alkylaryl sulfonates, alkyl sulfatesj and alkyl sulfonates, alkali metal and alkaline earth metal salts o~ dibutylnaphthalenesulfonic acid, lauryl ether sulrate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sul~ated hexadecanols, heptadecanols, and octadecanols, salt~ of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-2C lene and naphthalene derivatives with formaldehyde, conden-sation products of naphthalene or naphthalenesulfonic acids with phenol and ~ormaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol~ ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tri-butylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, ~atty alcohol ethylene oxide condensatesj ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxyl-ated polyoxypropylene, lauryl alcohol polyglycol ether acetal, .
77~;) sorbitol esters, lignin, sul~lte waste liquors and methyl cellul~e.
Powders, dusts and broadcasting agent3 may be prepared by mixing or grinding the herbicidal active ingredient and/or anti-dote with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carrier~. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, taIc, kaolin, lG Attaclay, lime~tone, lime, chalk~ bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulrate, mag-nesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium pho~phate, ammonium nitrate, and ureas, and ve~etable products such as grain flours, bark meal, wood meal~
- and nutshell meal, cellulosic powders, etc.
The formulations contain from Ool to 95, and prererably 0.5 to 90, ~ by weight of herbicidal active ingredient and antidote. Application rates of the herbicidal active ingredient are from 0.2 to 5 kg of active ingredient per hectare. The 2C herbicidal active ingredient is applied either together with or separately from the antidote in such a manner that the ratio o~ herbicidal active ingredient to antagonist is from 1:2 to 1:0.05 parts by weightO
Example~ of formulations are given below.
I. 40 part~ by weight o~ a mixture of 4 part~ by weight o~ 2-chloro-2' 9 6'-dimethyl-N-~pyrazol-1-yl-methyl)-acet-anilide and 1 part by weight Or M-dichloroacetyl-4,4-di-methyltetrahydro-193-oxazine i~ intimately mixed with .
4~77~
10 parts of the sodium salt of a phenolsulronic acid-ure~--formaldehyde condensate, 2 parts Or silica gel and 48 parts Or water to give a stable aqueous diqper~ion~ Dilution in 100,000 parts by weight Or water gives an aqueous di~persion contalning 0.04 wtZ o~ active ingredient ~ antidote.
II. 3 parts by weight of a mixture o~- 1 part by weight of 2-chloro-2',6'-dimethy]-N-(pyrazol-1-yl-methyl)-acetanilide and 1 part by weight of N-dichloroacetyl-4,4,6-trimethyltetra-hydro-1~3-oxazine is intimately mixed with 97 parts by wei~ht of particulate kaolin. A dust i~ obtained containing 3% by wei~ht Or active ingredient + antidote.
III. 30 parts by weight of a mixture of 1 part by weig~t of 2 chloro 2'-methyl-6'-eth~l-N-(1,2,4-trizaol-1-yl-methyl)-acet anilide and 2 parts by weight of N-dichloroacetyl-2-ethyl--4,4,6-trimethyltetrahydro-1,3-oxazine is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of para~fin oil which has been sprayed onto the surface o~ this silica gel. A formulation is obtained having good adherence.
2C IV. 20 parts by weight of a mixture Or 8 parts by weight of 2-chloro-2'-methyl-6'-ethyl-N-(pyrazol-1-yl-methyl)-acetanilide and 1 par~ by weight of N-dichloroacetyl-2-n-propyl-4,4,6-tri-methyl-1~3-tetrahydro-1?3-oxazine is intimate~ly mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the ~odium salt of a phenolsulfonic acid-urea-formaldehyde conden-sate and 68 parts of a paraffinic mineral oil, A stable oily dispersion is obtained.
-- 19 _ , ` 13~4~77C3 V. 20 part~ by weight Or a mixture of 10 part~ by weight of 2-chloro 2',6'-dimethyl-N-(4~5-dichloroimidazol-1-yl--methyl)-acetanilide and 1 part by weight Or N-dichloroacetyl--4,4-dimethyltetrahydro-1,3-oxazine is dissolved in a mixture con~isting of 40 part~ by weight o~ cyclohexanone, 30 parts by weight Or isobutanol, 20 part~ by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight Or the adduct of 40 moles of ethylene oxide to 1 mole o~ castor oil. By pouring the ~olution into 100,000 p~rts by weight of water and finely di~tributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient + antidote.
The influence of various representatives of the agents according to the invention (herbicidal active ingredient + anta-gonist) on the growth of unwanted and crop plants compared with that of agents con3i~ting o~ the same herbicidal active ingre-dients and an already.known antagonistic compound having a : chemical structure similar to that Or the antagonist8 in the agent~ accoL~ding to the invention is demonstrated in the following 2C biological examples. The experiments show that tolerance of the herbicidal acetanilides is improved, without the herbicidal action bein~ impaired, when they are combined with the ~e~rallydro--1,3-oxazines.
The series Or experiment~ were carried out in the greenhou~e and in the open.
I. Greenhouse_~periment :Plastic boxes 51 cm long, 32 cm wide and 6 cm deep were filled with loamy sand (pH:6) containlng about 1.5~ humus.
: : -~4770 Indian corn (Zea mays) or wheat (Triticum aestivum) were so~n ~hallow, in row~, in this ~ubstrate. Echinochloa cru~-galli and Alopecurus were scattered at random a unwanted plants. The non-sterilized soil also additionally contained viable weed seed~ which contributed to the weed population. A ~ield with crop plant~ growing in it and infe~ted with weed~ was thus simulated.
The active-ingredients and antagonists were applied separately and in the mixtures given below. They were emulsified or suspended in water as vehicle and the liquor ~prayed through finely distributing nozzles onto the soil surface, either imW
mediately a~ter sowing or prior to emergence Or the test plants.
In some cases, the agents were also incorporated into the soil before the crop plants were sown. After sowing and treatment the boxes were sprinkler-irrigated and covered with transparent plastic hoods until the plants emerged. These measures en~ured that the plants germinated and took root uniformly. The boxes were set up in the green~louse at from 18 to 30C.
These greenhouse experiments were monitored until 3 to 2C 5 Indian corn leaves had developedg No more damage due to the herbicidal agents was to be expected af~er this stage, a fact which was confirmed by the experiments in the open. The scale for assessing the act1on of the agents was 0 to 100, 0 denoting normal emergence and development of the plant~, with reference to the untreated control, and 100 denoting non-germination or withering of the plants. It ~hould be borne in mind here that,~
for instance in Indian corn, odd crippled or retarded plants may occur even under completely normal condition~ and without any chemical treatment.
'70 .. . . .
II, Ex~eriments in the open These experiments wererun o~ snall plots in loamy sand and loam (pH: S to 63 with a humus content of 1 to ~5%. Pre-; emergence treatment took place either immediately after the crop plants had been sown, or at the late~t 3 day~ later.
The weed flora was mad~ up of various species and was naturally occurring. However, only the dominating representatives have been included in the tables. Active ingredients and antagoni~t~, and combination~ thereof, were emulsified or suspended in water as vehicle and applied by means of a motor-driven plot spray mounted on a tractor. Where no rain fell, the plots were sprinkled to ensure normal emergence of the crop plants and weeds. All the experiments were run for several months, thus enabling the development o~ the crop plant up to seed formation to be observed. Assessment of the action of the agents was ; also made on the 0 to 100 scale.
Results As a result of the shallow sowing Or the crop plants and the more favorable conditîons for herbicidal activity, the damage 2C caused by the herbicidal active ingredients in the greenhouse was much greater,than in the open. The test conditions ror the antagonistic compounds were there~ore severer in the green-house than in the open.
, Where the antagonistic -tetrahyd;rc;-l, 3~oxazines are applied on their own9 they have a scarcely perceptible effect~
if at all, on the germination and growth of the unwanted and crop plants. This is also apparent at application rates sub~
stantially higher than those required ror antagonstic ef~ects.
~ 22 -` ` 114~47~0 .' .
However, the -tetrahydro-1,3,,oxazines :reduce t~le ~hyto~oxicity of the herbicidal acetanilides Or the ~ormula I to crop plants such as Indian corn and cereals to a con~iderable extent and in some cases eliminate it completely. It was ~ound that in the case of herbicidal compounds ~Ihich are less aggressive to crop plants it is suf~icient to add smaller amounts of anta-gonistic compounds or antagoni~tic compounds having a lesser antagonistic action.
Table 1 List of plant name3 10 Botanical name Abbreviation in Common name tables AlopeGurus myosuroides slender foxtail Chenopodium album lambsquarters Echinochloa crus galli Echinochloa c.g. barnyardgrass Galinsoga spp. gallant soldier Hordeum vulgare barley Matricaria Anthemis spp. chzmomile Triticum aestivum wheat Zea mays Indian corn .
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12 CHCl2CH3CH3 H 3 3 H 1.4918 - 13 CHC12CH3CH3 H H CH3C2H5 H 1.4949 2C 14 CHC12CH3CH3 H H CH3n-C3H7 H 1.4915 15 CHC12CH3~H3 H H CH3 3 7 1.4945 16 CHC12H 3 3 H Hm.p.: 64C
17 CHC12H H CH~ CH3 H 3 m.p: 80C
la CHCl2 H H CH3 ~CH3 H - 2 5 H
19 CHC.12 H H CH3 CH3 H i-C3H7 H - m.p: 84C
CHCl2 H H CH3 CH3 CH3 H H
-- 11 ~
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No. R R1 R2R3 R4 R5 R6 R7 m,p./b,p /n25 . ~ .. ..... . . . _ 21 CHCl2 H HCH3 CH3 CH3 3 23 CHCl2 H HCH3 C~3 CH3i C3H7 24 CHGl2 H 3 H3 H H3 CH3 26 CHC12 CH3 CH3H H CH3 CH-nC4H9 H 1.4849 ~7 CHC12 CH3 CH3H H CH3 CH3 CH3 28 CHC12 CH3 CH3H H CH3 CH3~ C2H5 29 CHC12 CH3 CH3H H CH3 H CH(OCH3)2 oil CHC12 CH3 CH3H H CH3 CH3 CH30CH2 oil 31 CHC12 CH3 CH3H H CH3 ~ (C~l2)~i oil 32 CHC12 CH3 CH3H H CH3 (C~2)5 oil 33 CC13 CH3 CH3H H H H H m.p.: 103C
35 CH~-CH2Cl CH3 CH3 H H H H H
36 CH2-CH2Cl CH3 CH3 H H CH3 H H
Some of the starting materials of the formuIa III needed the preparation of the tetrahydro- 1,3 _ oxazines are known from Rec. trav. chim. P.B., 78, 315, 1959 and J. Org. Chem., 38, 36, 1973. They may be ~repared by conventional methods, (Tetrahedron, 309 3315, 1974; Rec. trav. chim. P.B., 78, 315, 1959? in accordance with the following eq~uation:
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; ~4~L770 R4 ~ NH2 ~ O=C ~R6 -H O ~ ~
R5 OH 2 R5~0 R
III
, The ~ollowing example illustrate~ the preparation Or the starting materials. Part~ by weight bear the same relation~hip to part~ by volwne as kilo~rams to liters.
1,170 ~art3 by weight of 2-methyl-2 aminopentan-4-ol is placed in a stirred flask. With external cooling, 440 part~ by weight of acetaldehyde is run in over a period of about 40 minutes at 15-20C. The reaction mixture is ~tirred for a further - 15 minutes at 20C. After the addition of 600 parts by volume of toluene, 182 parts by weight of water is separated off over a period of 2 hours by azeotropic distillation. The reaction product is subjected to fractional distillation. After removal o~ the solvent there is obtained 1j3'12 parts by weight of 2~4,4,6-tetramethyltetrahydro-1,3-oxazine with a purity 2C (according to gas chromatography) of 98%,equivalent to a yield of 94% of theory, based on 2-methyl-2-aminopentan-4 ol~
Boiling point (13 mbars): 53-54C.
nD: 1.4340.
The following compound~ of the formula III are prepared in 'he same ~ay, ' ~ 13 -.
7~1~
,R2 R3 ~ ~ ~H
Rl R2 ~3 R4 R5 R6 R7 n20 b.p,(mbars) Cc]
~ _ . ~ . .
CH3 CH3 H H H H H 1-4290 b.p.(l53) 87 3 3 H H H CH3 1.4372 b-p-(20) 42-43 3 3 H H HC2H5 1.4392 b-p-(2606) 9 ; CH3 ~H3 H H H Hnc3H7 1-4371 b-p-(26.6) 9 7 lOCH3 CH3 H H H HiC3H7 1-4391 b-p-(26~6) 9 CH3 CH3 H H H H CH 4 9 1.4442 b.p.~0,27~ 54 55 CH3 CH3 H H CH3 H H 1-4394 b~p-(13 3) 47-48 CH3 3 H H CH3 H CH3 1.434Q b.p.(13.3) 5 CH3 CH3 H H CH3 HC2H5 1.4345 b~p-(13.3) 3 3 H CH3 Hnc3H7 1-4380 b-P-(0.27) CH3 CH3 H H CH3 -HiC3H7 1.4341 b-p~(13.3) 5 CH3 CH3 H H CH3 HC ~ C H 1.4451 b-p-(0.27) 5 55 2C CH3 CH3 H 3 2 5 1.4451 b.p.(20~ 59-60 CH3 CH3 H H CH3CH3 CH30~H2 1.4415 b-p-(26.6) CH3 CH3 H H H- (CH2)4- 1.4689 b-p-(26.6) 97 98 3 3 3 ~(CH2)4 - 1-4651 b-p (o 2 ) 47-48 CH3 CH3 H H CH - (CH2)5 - 1-4690 b-p-(0.27) H H CH~ CH3 H H H
H ' H CH3 CH3 H i-C3H7 H
77(~
Herbicidal active ingredients and antagonistic compounds may be incorporated into the soil either together or separately and before or after sowing. With acetanilide~, the commone~t method is to apply them to the surface of the soil immediately after sowing, or in the period between sowing and emergence of the young plants. It is also possible to apply them during emergence. In each instance, the antagonistic agent may be .
applied simultaneously with the herbicidal active ingredient.
It is also possible to apply the compounds separately - either the antagonist rirst and then the herbicidal active ingredient, or vice versa - provided that, if the herbicidal active ingre-dient is applied first~ not too much time elapses before 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 form, and may be formulated together or separately. It is also ~easible to treat the seed with the antagonist before sowing. The herbicidal active ingredient is then applied on its own in the usual manner.
2C Varying amounts of antagonistic compound are required for the ~ame herbicidal acetanilide when it is used in different crops. The ratio of acetanllide to tetrahydro~ oxazine may be varied within a wide range; it is dependent on the structure of the anilide and o~ the tetrahydro-193-oxazine, and on the crop in which they are used. Suitable ratios of herbicidal active ingredient to antagonist are from 1:2 to 1:0.05 parts by weight.
The herbicidal agents according to the i~ven-tion may contain, in a~dition to acetanilide and tetrahydro-1,3-oxazine, other herbicidal or growth-regulating active ingredients Or different chemical structure, e.g., 2-chloro-4-ethylamino-6~isopropylamino-1,3,5--triazine, without the antagonistic effec~ being impaired.
The agents according ~o the invention, or, when applied ; separately, the herbicidal active ingredients and the antidote are applied ~or instance in the form of directly sprayable solution~, powders, suspensions ~including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil diqpersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms o~ application depend entlrely on the purpose for which the agents are being used; in any case they should ensure as ~ine a distribution o~ the active ingredient as possible, For the preparation Or solutions, émulsions, pastes and oil dispersions to be sprayed direct, mineral oil ~ractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, 2C aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, pararfin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol~
propanol, butanol, chloro~orm, carbon tetrachloride~ cyclo-hexanol, cyclohexanone, chlorobenzene~ isophorone3 etc., and strongly polar solvents such as dimethylrormamide, dimethyl-sulfoxide, N-methyIpyrrolidone, water, etc. are suitable.
- 16 ~
, Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions~ pastes and oil disper~ions the herbicidal active ingredient and/or antidote as ~uch or dissolved in an oil or solvent may be homogenized in water by means o~ wetting or dispersing agents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be prepared from herbicidal active ingredient and/or antidote, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oll.
Example~ of surfactants are: alkali metal, alkaline earth metal and ammonium salts o~ ligninsulfonic acid, naphthalene-sulfon.ic acids, phenol~ulfonic acids, alkylaryl sulfonates, alkyl sulfatesj and alkyl sulfonates, alkali metal and alkaline earth metal salts o~ dibutylnaphthalenesulfonic acid, lauryl ether sulrate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sul~ated hexadecanols, heptadecanols, and octadecanols, salt~ of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated naphtha-2C lene and naphthalene derivatives with formaldehyde, conden-sation products of naphthalene or naphthalenesulfonic acids with phenol and ~ormaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol~ ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tri-butylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, ~atty alcohol ethylene oxide condensatesj ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxyl-ated polyoxypropylene, lauryl alcohol polyglycol ether acetal, .
77~;) sorbitol esters, lignin, sul~lte waste liquors and methyl cellul~e.
Powders, dusts and broadcasting agent3 may be prepared by mixing or grinding the herbicidal active ingredient and/or anti-dote with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carrier~. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, taIc, kaolin, lG Attaclay, lime~tone, lime, chalk~ bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulrate, mag-nesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium pho~phate, ammonium nitrate, and ureas, and ve~etable products such as grain flours, bark meal, wood meal~
- and nutshell meal, cellulosic powders, etc.
The formulations contain from Ool to 95, and prererably 0.5 to 90, ~ by weight of herbicidal active ingredient and antidote. Application rates of the herbicidal active ingredient are from 0.2 to 5 kg of active ingredient per hectare. The 2C herbicidal active ingredient is applied either together with or separately from the antidote in such a manner that the ratio o~ herbicidal active ingredient to antagonist is from 1:2 to 1:0.05 parts by weightO
Example~ of formulations are given below.
I. 40 part~ by weight o~ a mixture of 4 part~ by weight o~ 2-chloro-2' 9 6'-dimethyl-N-~pyrazol-1-yl-methyl)-acet-anilide and 1 part by weight Or M-dichloroacetyl-4,4-di-methyltetrahydro-193-oxazine i~ intimately mixed with .
4~77~
10 parts of the sodium salt of a phenolsulronic acid-ure~--formaldehyde condensate, 2 parts Or silica gel and 48 parts Or water to give a stable aqueous diqper~ion~ Dilution in 100,000 parts by weight Or water gives an aqueous di~persion contalning 0.04 wtZ o~ active ingredient ~ antidote.
II. 3 parts by weight of a mixture o~- 1 part by weight of 2-chloro-2',6'-dimethy]-N-(pyrazol-1-yl-methyl)-acetanilide and 1 part by weight of N-dichloroacetyl-4,4,6-trimethyltetra-hydro-1~3-oxazine is intimately mixed with 97 parts by wei~ht of particulate kaolin. A dust i~ obtained containing 3% by wei~ht Or active ingredient + antidote.
III. 30 parts by weight of a mixture of 1 part by weig~t of 2 chloro 2'-methyl-6'-eth~l-N-(1,2,4-trizaol-1-yl-methyl)-acet anilide and 2 parts by weight of N-dichloroacetyl-2-ethyl--4,4,6-trimethyltetrahydro-1,3-oxazine is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of para~fin oil which has been sprayed onto the surface o~ this silica gel. A formulation is obtained having good adherence.
2C IV. 20 parts by weight of a mixture Or 8 parts by weight of 2-chloro-2'-methyl-6'-ethyl-N-(pyrazol-1-yl-methyl)-acetanilide and 1 par~ by weight of N-dichloroacetyl-2-n-propyl-4,4,6-tri-methyl-1~3-tetrahydro-1?3-oxazine is intimate~ly mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the ~odium salt of a phenolsulfonic acid-urea-formaldehyde conden-sate and 68 parts of a paraffinic mineral oil, A stable oily dispersion is obtained.
-- 19 _ , ` 13~4~77C3 V. 20 part~ by weight Or a mixture of 10 part~ by weight of 2-chloro 2',6'-dimethyl-N-(4~5-dichloroimidazol-1-yl--methyl)-acetanilide and 1 part by weight Or N-dichloroacetyl--4,4-dimethyltetrahydro-1,3-oxazine is dissolved in a mixture con~isting of 40 part~ by weight o~ cyclohexanone, 30 parts by weight Or isobutanol, 20 part~ by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight Or the adduct of 40 moles of ethylene oxide to 1 mole o~ castor oil. By pouring the ~olution into 100,000 p~rts by weight of water and finely di~tributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient + antidote.
The influence of various representatives of the agents according to the invention (herbicidal active ingredient + anta-gonist) on the growth of unwanted and crop plants compared with that of agents con3i~ting o~ the same herbicidal active ingre-dients and an already.known antagonistic compound having a : chemical structure similar to that Or the antagonist8 in the agent~ accoL~ding to the invention is demonstrated in the following 2C biological examples. The experiments show that tolerance of the herbicidal acetanilides is improved, without the herbicidal action bein~ impaired, when they are combined with the ~e~rallydro--1,3-oxazines.
The series Or experiment~ were carried out in the greenhou~e and in the open.
I. Greenhouse_~periment :Plastic boxes 51 cm long, 32 cm wide and 6 cm deep were filled with loamy sand (pH:6) containlng about 1.5~ humus.
: : -~4770 Indian corn (Zea mays) or wheat (Triticum aestivum) were so~n ~hallow, in row~, in this ~ubstrate. Echinochloa cru~-galli and Alopecurus were scattered at random a unwanted plants. The non-sterilized soil also additionally contained viable weed seed~ which contributed to the weed population. A ~ield with crop plant~ growing in it and infe~ted with weed~ was thus simulated.
The active-ingredients and antagonists were applied separately and in the mixtures given below. They were emulsified or suspended in water as vehicle and the liquor ~prayed through finely distributing nozzles onto the soil surface, either imW
mediately a~ter sowing or prior to emergence Or the test plants.
In some cases, the agents were also incorporated into the soil before the crop plants were sown. After sowing and treatment the boxes were sprinkler-irrigated and covered with transparent plastic hoods until the plants emerged. These measures en~ured that the plants germinated and took root uniformly. The boxes were set up in the green~louse at from 18 to 30C.
These greenhouse experiments were monitored until 3 to 2C 5 Indian corn leaves had developedg No more damage due to the herbicidal agents was to be expected af~er this stage, a fact which was confirmed by the experiments in the open. The scale for assessing the act1on of the agents was 0 to 100, 0 denoting normal emergence and development of the plant~, with reference to the untreated control, and 100 denoting non-germination or withering of the plants. It ~hould be borne in mind here that,~
for instance in Indian corn, odd crippled or retarded plants may occur even under completely normal condition~ and without any chemical treatment.
'70 .. . . .
II, Ex~eriments in the open These experiments wererun o~ snall plots in loamy sand and loam (pH: S to 63 with a humus content of 1 to ~5%. Pre-; emergence treatment took place either immediately after the crop plants had been sown, or at the late~t 3 day~ later.
The weed flora was mad~ up of various species and was naturally occurring. However, only the dominating representatives have been included in the tables. Active ingredients and antagoni~t~, and combination~ thereof, were emulsified or suspended in water as vehicle and applied by means of a motor-driven plot spray mounted on a tractor. Where no rain fell, the plots were sprinkled to ensure normal emergence of the crop plants and weeds. All the experiments were run for several months, thus enabling the development o~ the crop plant up to seed formation to be observed. Assessment of the action of the agents was ; also made on the 0 to 100 scale.
Results As a result of the shallow sowing Or the crop plants and the more favorable conditîons for herbicidal activity, the damage 2C caused by the herbicidal active ingredients in the greenhouse was much greater,than in the open. The test conditions ror the antagonistic compounds were there~ore severer in the green-house than in the open.
, Where the antagonistic -tetrahyd;rc;-l, 3~oxazines are applied on their own9 they have a scarcely perceptible effect~
if at all, on the germination and growth of the unwanted and crop plants. This is also apparent at application rates sub~
stantially higher than those required ror antagonstic ef~ects.
~ 22 -` ` 114~47~0 .' .
However, the -tetrahydro-1,3,,oxazines :reduce t~le ~hyto~oxicity of the herbicidal acetanilides Or the ~ormula I to crop plants such as Indian corn and cereals to a con~iderable extent and in some cases eliminate it completely. It was ~ound that in the case of herbicidal compounds ~Ihich are less aggressive to crop plants it is suf~icient to add smaller amounts of anta-gonistic compounds or antagoni~tic compounds having a lesser antagonistic action.
Table 1 List of plant name3 10 Botanical name Abbreviation in Common name tables AlopeGurus myosuroides slender foxtail Chenopodium album lambsquarters Echinochloa crus galli Echinochloa c.g. barnyardgrass Galinsoga spp. gallant soldier Hordeum vulgare barley Matricaria Anthemis spp. chzmomile Triticum aestivum wheat Zea mays Indian corn .
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Claims (7)
1. A herbicidal agent comprising, as herbicidal active ingredient, 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 azole which is attached via a ring nitrogen 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 of up to 4 carbon atoms, or A denotes salts of azoles containing 2 or 3 nitrogen atoms, and, as antagonistic agent, at least one tetrahydro-1,3-oxazine of the formula II, where R denotes linear or branched haloalkyl of up to 3 carbon atoms, R1, R2, R3, R4 and R5 are identical or different and each denotes hydrogen or linear or branched alkyl of up to 3 carbon atoms, R6 denotes hydrogen or linear or branchcd alkyl of up to 8 carbon atoms, R7 denotes hydrogen, linear or branched alkyl of up to 8 carbon atoms, alkoxyalkyl of up to 6 carbon atoms or dialkoxyalkyl of up to 8 carbon atoms, and R6 and R7 amy together form a methylene chain of 4 to 5 carbon atoms.
2. A herbicidal agent as claimed in claim 1, comprising 2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide as herbicidal active ingredient and N- dichloro-acetyl-4,4-dimethyltetrahydro-1,3-oxazine as antagonistic agent.
3. A herbicidal agent as claimed in claim 1, comprising 2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide as herbicidal active ingredient and N-dichloro-acetyl-4,4,6-trimethyltetrahydro-1,3-oxazine as antagonistic agent.
4. A herbicidal agent as claimed in claim 1, wherein the ratio of acetanilide to tetrahydro-1,3-oxazine, applied separately or together, is from 1:2 to 1:0.05 parts by weight.
5. A process for the selective control of unwanted plants, wherein a substituted acetanilide of the formula I
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 azole which is attached via a ring nitrogen 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 of up to 4 carbon atoms, or A denotes salts of azoles containing 2 or 3 nitrogen atoms; and a tetrahydro-1,3-oxazine of the formula II
II, where R denotes linear or branched haloalkyl of up to 3 carbon atoms, R1, R2, R3, R4 and R5 are identical or different and each denotes hydrogen or linear or branched alkyl of up to 3 carbon atoms, R6 denotes hydrogen or linear or branched alkyl of up to 8 carbon atoms, R7 denotes hydrogen, linear or branched alkyl of up to 8 carbon atoms, alkoxyalkyl of up to 6 carbon atoms or dialkoxyalkyl of up to 8 atoms, and R6 and R7 may together form a methylene chain, of 4 or 5 carbon atoms;are applied simultaneously before, during or after sowing of the crop plants or before or during emergence of the crop plants.
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 azole which is attached via a ring nitrogen 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 of up to 4 carbon atoms, or A denotes salts of azoles containing 2 or 3 nitrogen atoms; and a tetrahydro-1,3-oxazine of the formula II
II, where R denotes linear or branched haloalkyl of up to 3 carbon atoms, R1, R2, R3, R4 and R5 are identical or different and each denotes hydrogen or linear or branched alkyl of up to 3 carbon atoms, R6 denotes hydrogen or linear or branched alkyl of up to 8 carbon atoms, R7 denotes hydrogen, linear or branched alkyl of up to 8 carbon atoms, alkoxyalkyl of up to 6 carbon atoms or dialkoxyalkyl of up to 8 atoms, and R6 and R7 may together form a methylene chain, of 4 or 5 carbon atoms;are applied simultaneously before, during or after sowing of the crop plants or before or during emergence of the crop plants.
6. A process for the selective control. of unwanted plants, according to claim 5, wherein the crop plant seed is treated with one or several tetrahydro-1,3-oxazines of the formula II.
7. A process as claimes in claims 5 or 6 wherein the crop plant is Indian corn or a cereal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000397642A CA1144770A (en) | 1978-07-27 | 1982-03-04 | Herbicidal agents containing haloacetanilides and tetrahydro-1,3-oxazines |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782832890 DE2832890A1 (en) | 1978-07-27 | 1978-07-27 | HERBICIDAL AGENTS |
| DEP2832890.7 | 1978-07-27 | ||
| CA331,488A CA1133902A (en) | 1978-07-27 | 1979-07-10 | Tetrahydro-1,3-oxazines |
| CA000397642A CA1144770A (en) | 1978-07-27 | 1982-03-04 | Herbicidal agents containing haloacetanilides and tetrahydro-1,3-oxazines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144770A true CA1144770A (en) | 1983-04-19 |
Family
ID=27166326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000397642A Expired CA1144770A (en) | 1978-07-27 | 1982-03-04 | Herbicidal agents containing haloacetanilides and tetrahydro-1,3-oxazines |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1144770A (en) |
-
1982
- 1982-03-04 CA CA000397642A patent/CA1144770A/en not_active Expired
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