CA1114824A - N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine, a process for its preparation and its use for preventing damage to crop plants by herbicides - Google Patents

N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine, a process for its preparation and its use for preventing damage to crop plants by herbicides

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CA1114824A
CA1114824A CA330,709A CA330709A CA1114824A CA 1114824 A CA1114824 A CA 1114824A CA 330709 A CA330709 A CA 330709A CA 1114824 A CA1114824 A CA 1114824A
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alkyl
compound
formula
methyl
acetanilides
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Hans-Jochem Riebel
Rudolf Thomas
Ludwig Eue
Wilfried Faust
Robert R. Schmidt
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Bayer AG
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/26—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C243/34—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a carbon skeleton further substituted by nitrogen atoms
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/08—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms with acylated ring nitrogen atom
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    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
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    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles

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  • Nitrogen Condensed Heterocyclic Rings (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Abstract The new compound N-dichloro-acetyl-1,2,3,4-tetrahydro-quinaldine of the formula (I) is outstandingly suitable for protecting crop plants against herbicidal damage by thiolcarbamates and/or acetanilides. The compound of the formula (I) is prepared by reacting 1,2,3,4-tetrahydro-quinaldine of the formula

Description

B2~

The present invention relates to new compound N-dichloro-acetyl-1,2,3,4-tetrahydro-quinaldine, to a process for its preparation and to its use as an antidote ~or preventing damage to crop plants by herbicides.
In the present context, by "antidotes" ("safeners") there are to be understood substances which are capable of specific antagonisation of harmful actions of herbicides on crop plants, that is to say which are capable of protecting crop plants without thereby noticeably in-fluencing the herbicidal action on the weeds to be com-bated.
It is known that when certain thiol-carbamates and acetanilides are used for combating weeds in maize and other crops, they cause damage, to a greater or lesser extent, to the crop plants.
It is furthermore known that compounds such as, for example, N-dichloroacetyl-2-methyl-indoline and N-dichloroacetyl-cis/trans-decahydroquinoline are suitable for preventing damage to crop plants by acetanilides (see DE-OS (German Published Specification) 2,218,097).
However, the activity of these substances as antidotes is not always completely satisfactory.
The present invention now provides, as a new compound3 N-dichloroacetyl-1,2,394-tetrahydro-quinaldine, which has the formula C~
C~13 ~I).
~=C-CHC12 The invention also provides a process for the pre-paration of N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine, of the formula (I), in which 1,2,3,4-tetrahydro-quinaldine 3 of the formula Le A 18 886 ` - 2 ~ 24 (II) ~1 is reacted with dichloroacetyl chloride, if appropriate in the presence of an acid-binding agent and i~ appropriate in the presence of a diluent.
It has also been found that N-dichloroacetyl-lg2,3,4-tetrahydro-quinaldine o~ the formula (I) is outstandingly suitable for protecting crop plants against herbicidal damage by thiol-carbamates and/or acetanilides.
Surprisingly, herbicidal damage, caused by thiol-carbamates or acetanilides, to crop plants is better suppressed by also using N-dichloroacetyl-1,2,3,4-tetra hydro-quinaldine than by using N-dlchloroacetyl-2-methyl-indoline or N-dichloroacetyl-cis/trans-decahydro-quinoline, which are compounds known from the state of the art and are substances of the same type of action which are the most sirnilar chemically. The substance according to the invention thus represents a valuable enrichment of the art.
The preparation of N-dichloroacetyl 1,2,3,4-tetra--hydroquinaldine by reacting 1,2,3,4-tetrahydro-quinaldine with dichloroacetyl chloride can be illustrated by the equation which follows:

~\CH + C12HC CO Cl HCl ~CH3 H O=C-CHC 12 The 1,2,3,4-tetrahydro-quinaldine of the formula (II) required as a starting substance for carrying out the pro-cess according to the invention can be prepared by hydrogen-ating quinaldine with gaseous hydrogen in the presence of a catalyst, such as Raney nickel or ruthenium on a support, and if appropriate in the presence of a diluent, such as Le A 18 886 ,, 32~

methanol or etharlol~ at temperatures between 100C and 250 C, preferably between 150C and 200C. The hydrogen pressure can be varied within a substantial range. In general, the hydrogenation is carried out under pressures between 100 and 220 bars, preferably between 150 and 190 bars. The hydrogenation of quinaldine is preferably carried out in the absence of additional diluents, using ruthenium ~ aluminium oxide as the catalyst.
Possible acid binding agents ror carrying out the process according to the invention are all the customary acid acceptors, preferably alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate and sodium bicarbonate, and lower tertiary amines, such as triethylamine, dimethylbenzylamine, pyridine and diazabicyclooctane. However, 1,2,3,4-tetrahydro-quinaldine of the formula (II) employed in excess can also simulta-neously function as the acid-binding agent; in this case, use of an additional acid-binding agent is superfluous.
Water and inert organic solvents can be used as the diluent in the reaction according to the invention. Pre-ferred organic solvents include ketones, such as diethyl ketone and such as methyl isobutyl ketone; nitriles, such as propionitrile and acetonitrile; ethers, such as tetra-hydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; esters, such as ethyl acetate; and formamides, such as, in particular, dimethylformamide.
The reaction temperatures can be varied within a sub-stantial range in the process according to the invention.
In general, the reaction is carried out at from 0 to 60C, preferably from 20 to 50C.
In carrying out the process according to the invention, 1 mole of dichloroacetyl chloride and 1 mole of acid-binding agent are preferably employed per mole of 1,2,3,4-tetrahydroquinaldine of the formula (II). Isolation of Le A 18 886 . .

the reaction product is effected by customary methods.
In general, a procedure is rollowed ln which the reaction mixture is poured into water, after the reaction has ended, and the mixture is extracted by shak;ng with an organic solvent which is sparingly soluble in water, for example methylene c~loride, the combined organic phases are washed successively with dilute hydrochloric acid and water, then dried and evaporated and the residue is subjected to fractional distillation.
The preparation of the N-dichloroacetyl-1,2,3,4-tetra-hydro-quinaldine according to the invention is illustrated by ~he examples which follow.
Example 1 ,~
~ ~N'~CH3 (I) 14.8 g (0.1 mol) of dichloroacetyl chloride were added to a solution of 29.4 g (0.2 mol) of l~2~3~4-tetrahydro-quinaldine in 200 ml of acetonitrile at room temperature, whilst stirring. Thereafter, the mixture was stirred at 40C for a further 2 hours. The reaction mixture was then allowed to cool and was poured into water. The mixture which formed was extracted several times with ~ethylene chloride. The combined organic phases were washed successively with dilute hydrochloric acid and water, dried over sodium sulphate and concentrated under reduced pressure. The residue was subjected to fractional dis-tillation. 20 g of N-dichloroacetyl~132/3,4-tetrahydro-quinaldine were obtained in this manner.
Refractive index: n20= 1.5728 ys s: C12Hl~ONC12 Calculated: 55.83% C; 5.08% H; 27.47% Cl; 5.43% Cl Found: 55.6% C; 5.1 % H; 27.3 % Cl; 5.3 % Cl Le A 18 886 Exam~le 2 (II~

, C~13 15 g o~ a catalyst mixture consisting of ruthenium on aluminium oxide were added to 143 g (1 mol) of quinaldine and the quinaldine was hydrogenated ~or 2 hours at 195C
under a hydrogen pressure of 170-190 bars. Thereafter, the reaction mixture was filtered and the filtrate was sub-jected to fractional distillation. 123 g of 1,2,3,l~-tetrahydro-quinaldine were obtained in this manner.
Boiling point: 75C/l mm Hg.
As already mentioned~ N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of the formula (I) is suitable for protecting crop plants against damage by herbici~ally active thiol-carbamates or acetanilides without noticeably influencing their action on weeds.
Preferred herbicidally active thiol-carbamates are those of the general formula ,R2 Rl-S-C-N ~ 3 (III) in which R1 represents Cl-C4 alkyl, benzyl, chlorobenzyl or C1C~-2alkoxy benzyl~ and R and R3, independently of one another, each represent alkyl with 2 to 4 carbon atoms or cyclohexyl, or R2 and R3, together with the adjacent nitrogen atom, represent a five-membered to seven-membered hetero-cyclic ring.
Specific examples of thiol-carbamates of the formula (III) which may be mentioned are: S-ethyl N,N-dipropyl-thiocarbamate, S-ethyl N,N-diisobutylthiocarbamate3 S-propyl N-butyl-N-ethylthiocarbamate, S-propyl N,N-diiso-propylthiocarbamate~ S ethyl N,N-diethylthiocarbamate, Le A 18 886 .

S-ethyl N-ethyl-N-cyclohexylthiocarbamate, S-ethyl hexa-hydro-azepine-l-thiocarbamate, S-~-methoxybenzyl N,N-diethylthiocarbamate, S-~-chlorobenzyl N,N-diethylthio-carbamate, S-benzyl N,N-diethylthiocarbamate, S~benzyl N,N-di-sec.-butylthiocarbamate and S-propyl N-ethyl-N-butylthiocarbamate.
The thiol-carbamates of the formula (III) and their herbicidal activity are already known (see U.S. Patent Specifications 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314).
Preferred herbicidally acSive acetanilides are those of the general formula X

~ ~ (IV) y C0 - CHz - Z

in which R represents an optionally substituted N-containing heterocyclic radical, X and Y, which may be identical or different, each represent alkyl, Z represents halogen and n represents 0, 1 or 2, and herbicidally active acid-addition salts and metal salt complexes thereof.
Preferred acetanilides of the formula (IV) are those in which R represents a pyrazol-l-ylg imidazol-l-ylg 1,2,4-triazol-1-yl, 1,2~3-triazol-l-yl9 1,3,4 triazol-l-yl, 1~2,3,4-tetrazol-1-yl or pyrrol-l-yl radical which is optionally substituted, the preferred substituents being halogen ~especially fluorine~ chlorine or bromine) and alkyl with 1 to 4 carbon atoms, X and Y, which may be identical or different, each represent straight chain or branched alkyl with 1 to 4 carbon atoms; and Z represents chlorine or bromine.
Further preferred herbicidally active acetanilides are those of the general formula Le A 18 886 ~5 R6 R ~ ~ ~ - C0 - R7 (V) m in which R represents alkyl, halogen, halogenoalkyl, alkyl-thio, alkylsulphonyl, aminosulphonyl, cyano or nitro, R5 and R6, which may be identical or different, each represent hydrogerl, alkyl, halogen, halogeno-alkyl or optionally ~ubstituted phenyl, R represents alkyl or optionally substituted phenyl and m represents l 1~ 2, 3, 4 or 5.
Preferred acetanilides of the formula (IV) are those in which R4 represents straight-chain or branched alkyl with 1 to 6 (especially 1 to 4) carbon atoms, fluorine, chlorine, bromine, halogenoalkyl with up to 3 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine and chlorine and tri-fluoromethyl being mentioned as an example), alkylthio with 1 to 4 carbon atoms9 alkylsulphonyl with 1 to 4 carbon atoms, aminosulphonyl, cyano or nitro, R5 and R6, which may be identical or different, each represent hydrogen~ straight-chain or branched alkyl uith 1 to 4 carbon atoms, fluorine, chlorine, bromine, halogenoalkyl with up to 3 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine and chlorine) or phenyl which is optionally monosubstituted or polysubstituted, the preferred sub-stituents being alkyl with 1 to 6(especially 1 to 4) carbon atoms, fluorine, chlorine, bromine, halogenoalkyl with up to 3 carbon atoms and up to 5 identical or di~ferent halogen atoms (preferred halogens being fluorine and chlorine and trifluoromethyl being mentioned as an example), Le A 18 886 .
- -: ' ~: , ' ' '~

, 8 ~ g ~ ~

alkylthio with 1 to Ll carbon atoms, alkylsulphonyl with1 to 4 carbon atoms, aminosulphonyl, cyano and nitro;
R represents straight-chain or branched alkyl with 1 to 6 (especlally 1 to 4) carbon atoms or phenyl which is optionally monosubstituted or polysubstituted, the preferred substituents being alkyl with 1 to 6 (especially 1 to 4) carbon atoms, fluorine, chlorine, bromine, halogeno-alkyl with up to 3 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine and chlorine and trifluoromethyl being mentioned as an example), alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms D aminosulphonyl cyano, nitro, phenyl and phenoxy, which last two sub-stituents can themselves also be substituted by alkyl with 1 to 6 (especially 1 to 4) carbon atoms, fluorine, chlorine, bromine, halogenoalkyl with up to 3 carbon atoms and up to 5 identical or different halogen atoms (pre~erred halogens being fluorine and chlorine and trifluoromethyl being mentioned as an example), alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms, aminosulphonyl, cyano, or nitro.
Yet further preferred herbicidally active acetanilides are those of the general formula 8 ~ R10 R (VI) R p C0 ~ CH2 _ ~12 in which A represents oxygen, sulphur or the grouping >NR13, R10 represents hydrogen or alkyl, Rll represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkynyl, cycloalkyl, halogen, optionally 3 substituted aryl3 optionally substit~ted aralkyl or the grouping -OR14 sRl4 NR13R14 R13 represents hydrogen) alkyl or optionally sub-stituted aryl, Le A 18 886 g R14 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkynyl, cycloalkyl or optionally substi-tuted aralkyl, R8 represents alkyl, R9 represents alkyl or halogen, R12 represents halogen and p represents 0, 1 or 2.
Preferred acetanilides of khe formula (VI) are those in which A represents oxygen, sulphur or the grouping ~ R13, wherein R13 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms oraryl with 6 to 10 carbon atoms (especially phenyl) 3 it being possible for the aryl radical to carry one or more substituents selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, cyano~ nitro and halogenoalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms (halogens which may be mentioned being, in particular, fluorine and chlorine);
R10 represents hydrogen or methyl, Rll represents hydrogen, straight chain or branched alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 3 carbon atoms and up to 5 identical or different halogen atoms (preferred halogerls being fluorine and chlorine and trifluoromethyl being mentioned as an example), alkenyl or alkynyl with in either case 2 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, fluorine, chlorine, bromine or aryl with 6 to 10 carbon atoms (especially phenyl), it being possible for the aryl radical to carry one or more substituents selected from halogen, alkyl with 1 to l~ carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, cyano, nitro and halogenoalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine or chlorine and trifluoromethyl being mentioned as a specific example of halogenoalkyl), or Rll represents aralkyl with 6 Le A 18 886 , ., ~ ~ ' .

to 10 carbon atoms in the aryl part and 1 to ll carbon atoms in the alkyl part (especially benzyl), it being possible for the aralkyl radical to carry one or more substituents in the aryl part selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms9 cyano~
nitro and halogenoalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine and chlorine and trifluoromethyl being mentioned as a specific example of halogenoalkyl), or Rll represents the grouping -oR14, -SR14 or -NR13R14, wherein R13 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms or aryl with 6 to 10 carbon atoms (especlally phenyl), it being possible for the aryl radical to carry one or more substituents selected from halogen 3 alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio witb 1 or 2 carbon atoms, cyano, nitro and halogenoalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms (halogens which may be mentioned being, in particular~ fluorine and chlorine) and R14 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, halogenoalkyl with up to 3 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine and chlorine and trifluoromethyl being mentioned as an example), alkenyl or alkynyl with in either case 2 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms or aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part (especially benzyl), it being possible for the aralkyl radical to carry one or more substituents in the aryl part selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, cyano, nitro and halogenoalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine or chlorine and trifluoromethyl being mentioned as a specific example of halogenoalkyl);
Le A 18 886 `` ~ 324 R~ represent~ straight-chain or branched alkyl with 1 to 4 carbon atoms;
R represents straight-chain or branched alkyl with 1 to 4 carbon atoms, fluorine, chlorine or bromine;
and R12 represents chlorine, bromine or iodine.
Specific examples of acetanilides of the formula (IV) and acid-addition salts derived therefrom are:
2-methyl-6-ethyl-N-(pyrazol-1-yl-methyl)-chloroacetanilide, 2,6-diethyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide, 2,6-diethyl-N-(1,2,4-triazol l-yl-methylj-chloroacetanilide, 2,6-dimethyl-N-(1,2,4-triazo:L-l-yl-methyl)-chloroacetanilide, 2-methyl-N-(pyrazol-l-yl-methyl)-chloroacetanllide~
2,5-dimethyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide, 2 9 3-dimethyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide, 2-methyl-6-ethyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide hydrochloride, 2,6-diethyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide hydrochloride, 2,6-diethyl-N-[(335-dimethyl-pyrazol-l-yl)-methyl]-chloroacetanilide, 2,6-diethyl-N-E(3-chloro-1,2,4-triazolyl)-methyl]-chloro-acetanilide, 2-methyl-6-ethyl-N-[(3,5-dimethyl-pyra~.ol-l-yl)-methyl]-chloroacetanilide, 2-tert.-butyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide, 2-methyl-6-ethyl-N-[(3-bromo-5-methyl-pyrazol l-yl)-methyl]-chloroacetanilide~
2-methyl-6-ethyl-N-[(4-chloro-pyrazol-1-yl)-methyl]-chloroacetanilide, 2-methyl-6-ethyl-N-[(3-chloro-1,2,4-triazolyl)-methyl]-chloroacetanilide and 2,6-diethyl-N-[(4-chloro-pyrazol-1-yl)-methyl]-chloroacetanilide.
Specific examples of acetanilides of the formula (V) are: 296 dimethyl-N-(benzoyl-methyl)-chloroacetanilide, 2,6-dimethyl-N-(4-chlorobenzoyl-methyl)-chloroacetanilide and 2-methyl~6 ethyl-N-(benzoyl-methyl)-chloroacetanilide Specific examples of acetanilides of the formula (VI) are: 2,6-diethyl-N-[(2-methyl-1,3,4-oxadiazol-5-yl~-methyl]-chloroacetanilide~ 2,6-dimethyl-N-[(2-methyl-133,4-oxacliazol-5-yl)-methyl~-chloroacetanilide, 2-ethyl-6-methyl-N-~(2-methyl-1,3,4-oxadiazol-5 yl)-methyl~-chloroacetanilide and 2-tert.-butyl-N-[(2-methyl-1,3,4-Le A 18 886 - 1.2 -oxadiazol 5-yl)-methyl]-chloroacetanilide.
Moreover, N-dichloroacetyl-l,2,3,4-tetrahydro-quinaldine of the formula (I) can also preferably be used as an antidote with the ~ollowing herbicidally active acetanilides: N-(2'-methoxyethyl)-2,6-dimethyl-chloro-acetanilide, N-(2'-allyloxyethyl)-2,6-dimethyl-chloro-acetanilide, N-(2'-n-propoxyethyl)-2,6-dimethyl-chloro-acetanilide, N (2'-isopropoxyethyl)-2,6-dimethyl-chloro-acetanilide, N-(2'-methoxyethyl)-2-methyl-6-ethyl-chloro-acetanilide, N-(2'-methoxyethyl)-2,6-diethyl-chloro-acetanilide, N-(2'-ethoxyethyl)-2-methyl-6-ethyl-chloro-acetanilide~ N-(l'-ethoxycarbonyl-ethyl)-2,6-dimethyl-chloroacetanilide, N-(3'-methoxy-prop-2'-yl)-2-methyl-chloroacetanilide, N-(3'-methoxy-prop-2'-yl)-2,6-dimethyl-chloroacetanilide, N-(3'-methoxy-prop-2'-yl)-2 methyl-6-ethyl-chloroacetanilide, N-(3'-methoxy-prop-2'-yl)-2,6-diethyl-chloroacetanilide, N-(3'-methoxy-prop-2~-yl)-2-ethyl-chloroacetanilide, N-(2'-ethoxyethyl)-296-diethyl-chloroacetanilide, N-(2~-n-propoxyethyl)-2-methyl-6-ethyl-chloroacetanilide, N-(2'-n-propoxyethyl)-2,6-diethyl-chloro-acetanilide, N-(2'-isopropoxyethyl)-2-methyl-6-ethyl-chloro-acetanilide, N-chloroacetyl-2,6-dimethylanilino-acetic acid ethyl ester and methyl ester, ~-(N-chloroacetyl-2,6-dimethyl-anilino)-propionic acid methyl ester, -(N-chloroacetyl-2-methyl-6-ethyl-anilino)-propionic acid ethyl ester, N-(3~-methoxy-prop-2'-yl)-2,3-dimethyl-chloroacetanilide, N-(2'-ethoxyethyl)-2-methyl-6-chloro-chloroacetanilide, N-(2'-methoxyethyl)-2-methyl-6-chloro-chloroacetanilide and N-(2l-methoxyethyl)-2-methyl~6-methoxy-chloroacetanilide.
~0 The herbicidally active acetanilides of the formula (I~) and acid addition salts and metal salt complexes thereof have not hitherto been described in the literature.
However, they can be prepared by (a) reacting N-halogenomethyl-halogenoacetanilides of the general formula l,e A 18 886 - 1 3 - ~' ~ ~ CH2 - Hal (VII) y CO ~ CH2 - Z

in which X, Y, Z and n have the meanings stated above and Hal represents halogen, especially chlorine or bromine, with heterocyclic compounds of the general formula R-M (VIII), in which R has the meaning stated above and M represents hydroKen or an alkali metal, if appropriate in the presence of a diluent and of an aci~b~ding agent, and then optionally adding on an acid or a metal salt.
If 2,6-diethyl-N-chloromethyl-chloroacetanilide and pyrazole are used as starting substances, the co~rse o~ the reaction in process (a) can be represented by the equation which follows:

CH~-Cl ~ + ~ase ~ C0-CH2Cl \N - HCl C2H, ~ ~ C0-CH~Cl The N-halogenomethyl-halogenoacetanilides of the formula (VII), to be used as starting materials in process (a) 9 are known, or they can be prepared by known methods (see U.S. Patent Speci~ications 3,630,715 and 3,637,847).
They are obtained, for example, by reacting corresponding Le A 18 886 - 1 Lt ~ 4 anilines with paraformaldehyde in the presence of catalytic amounts of potassium hydroxide~ and adding a halogenoacet~l halide, for example chloroacetyl chloride, to the phenylazomethines formed.
The N-halogenomethyl-halogenoacetanilides of the formula (VII) can also be obtained by a new process, by reacting known halogenoacetanilides of the general formula ~ - N
n C~) - CH2 - Z (IX) in which X, Y, Z and n have the meanings stated above, with, per mole, at least 1 mole of formaldehyde or a substance which releases formaldehyde, for example parafor~aldehyde, and a halogenoating agent, such as a hydrogen halide acid or an inorganic or organic acid halide, and a water-binding agent, for example sodium sulphate, in a manner which is in itself known, at tempera-tures between -10C and 150C, preferably between 10 and 70C, if appropriate in the presence of an inert organic solvent, for example toluene (see German Offen-legungsschriften (German Published Specifications) 2,119,518 and 2,210,603). ~hen inorganic acid halides, for example thionyl chloride, are employed~ the use of a specific water-binding agent can be dispensed with (see also the prepar~tive examples herein).
The formula (VIII) provides a general definition of the heterocyclic compounds also to be used as starting substances. In this formula, M preferably represents hydrogen, sodium or potassium.
The heterocyclic compounds of the formula (VIII) are generally known compounds of organic chemistry.
Preferred diluents for the reaction according to process (a) are inert organic solvents, espec~ally ketones, such as diethyl ketone, and in particular methyl isobutyl ketone~ nitriles, such as propionitrile, and Le A 18 886 in particular acetonltrile; ethers, such as tetrahydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, or halogenated hydrocar~)ons, such as methylene chloride, carbon tetra-chloride, chloroform or chlorobenzene, esters, suchas ethyl acetate; and formamides, such as, in particular, dimethylf`ormamide.
Acid-binding agents which can be employed in process (a) are all the inorganic and organic acid acceptors which can customarily be used, especially alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, and furthermore lower tertiary alkylamines, aralkylamines, aromatic amines or cycloalkylamines, for example triethylamine, dimethyl-benzylamine, pyridine and diazabicyclooctane. It isalso possible to use an appropriate excess of azole, by which there is to be understood, in the present case, a compound of the formula (VIII).
The reaction temperatures can be varied within a substantial range in process (a). In general, the re-action is carried out between 0 and 120C, preferably between 20 and 80C.
In carrying out process (a), 1 to 2 moles of the heterocyclic co~pound of the formula (VIII) and 1 mole Of ac~-binding agent are preferably employed per mole of the compounds of the formula (VII). In order to isolate the compounds of the formula (IV), the reaction mixture is filtered and the filtrate is washed with water, dried and concentrated. The residue is purified, 3o if appropriate, by fractional crystallisation or dis-tillation.
In a particular form of working up, the reaction mixture is cooled to about 0C and filtered and hydrogen chloride is passed into the filtrate at 5 to -15C.
The chloride salts which have precipitated are filtered off, washed with an organic solvent, for example ethyl acetate, and partitioned in a mixture of an organic solvent, ~or example ethyl acetate, and water, with a Le A 18 886 ~ . .

- 16 ~ 24 p~l value of about 12. The organic phase is separated of~ and the compounds of the ~ormula (IV) are isolated in the customary manner~
All the acicls which lead to physiologically accep table salts can be used for the preparation o~ acid-addi-tion salts of the compounds of the formula (I~). Preferred acids include the hydrogen halide acids tfor example hydro-bromic acid and especially hydrochloric acid), phosphoric acid9 nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and h~droxycarbo~ylic acids (for example acetic acid, maleic acid, succinic acid, fumaric acid, tartar_c acid, citric acid, salicylic acid, sorbic acid and lactic acid), and sulphonic acids (~or example, ~-toluene-sulphonic acid and 1,5-naphthalene-disulphonic acid).
The salts o~ the compounds of the ~ormula (IV) canbe obtainei in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I-~) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtration, and i~ appropriate purified by washing with an inert organic solvent.
Salts of metals of main groups II to IV and of su~roups I and II and IV to VIII of the Periodic Table are preferably used for the preparation of metal salt complexes o~ the compounds of the formula (IV), examples of metals which may be mentioned being copper, zinc, manganese, magnesium7 tin, iron and nickel. Possible anions of these salts are those which are derived from acids~which lead to physiologically acceptable sal-ts, pre~e-rably the hydrogen halide acids (for example hydrochloric acid and hydrobromic acid) 9 phosphoric acid, nitric acid and sulphuric acid.
The metal salt complexes of the compounds of the formula (IV) can be obtain~d in a simple manner by customary ~rocesses, thus~ fo~ example; by dissolving the metal salt in alGohol, for example ethanol, and adding the solution to the compound of the formula Le A 18 886 ' ~ 2 (IV)~ The metal salt complexes can be isolated in a known manner, for example by filtration, and if approp-riate purified by recrystallisation.
The preparation of acetanilides of the form~la (IV) is illustrated in the examples which follow.
Exam~le_3 C2H3 ~
CH2 -N~ =J

C0 ~ CH2 - Cl ~2H, A mixture of 68 g (1 mole) of pyrazole and 106 g (1.05 moles) of triethylamine in 150 ml of anhydrous ethyl acetate were added to 274.2 g (1 mole) of 2,6-diethyl-N-chloromethyl-chloroacetanilide in 250 ml of anhydrous ethyl acetate, whilst stirring, during whi~h the temperature rose to 30C. The mixture was subsequently stirred at room temperature for 1 hour.
Two possibilities for the working up were as follows:
(1) The reaction mixture was filtered and the filtrate was washed with water until neutral, dried over sodium sulphate and evaporated in vacuo. After fractional crystallisation of the residue with ligroin, 171 2 g (56% of theory) of 2,6-diethyl-N-(pyrazol-l-yl-methyl)-chloroacetanilide of melting point 67C were obtained in the form of colourless crystals.
(2) The reaction mixture was cooled to 0C and filtered and the residue on the filter was rinsed with 10 ml of cold ethyl acetate. 50 g (1.4 moles) of dry hydrogen chloride were passed into the filtrate at 0 to -10C.
The hydrochloride salts which had precipitated were then filtered off and rinsed with 50 ml of cold ethyl acetate and the solid residue was partitioned between 0.5 litre of ethyl acetate and 0.5 litre of aqueous sodium hydroxide solution with a pH value of 12. The organic phase was separated off, washed twice with 0.5 litre of sodium chloride solution each time, dried over Le A 18 886 ., .

,' ' ~ : ' . ' :

-sodium sulphate and evaporated in vacuo. 60 ml of benzine ._ were added to the colourles~ oily res:idue, whereuponthe residue crystallised. 220.2 g (72% of theory) of 2~6-diet}~yl-N-(pyrazol-l-yl-methyl)-chloroacetanilide of melting point 67C were obt;ained in the form of colour-le~.~ crystals.
~ 'he compounds listed in the table which follo~rs were p~?pared in an ~llalogous manner:
T a t, ] e ~ ~ CHz - R (IV) ~/ CO - CH2 - Z

Ex- Melting ample ~ (8C~t 4 C2 ~c2 H5 Cl 1~ 2, 4-Tria~ol-l-yl 112 i-C~ H7 6-i-C~ H~ ClPyrazol ~ l-yl 1~4 6 CH3,6-C2 Hg Cl 1, 2, 4-Trlazol l-yl 92 7 CH36-C2H5 Cl Pyrazol-l-yl 57 B C2H~4,6-(CH3 )2 Cl Pyrazol-l-yl 82 g CH~ ~ 4,6-(CH,)2 Cl Pyrazol-l-yl 92 C2~5 4-CH~, Cl Pyrazol-l-yl 78 6-C2H, 11 i-C3 H7 6~1-C, H~ Cl l, 3, 4-Triazol-l-yl 196 2012 i-~ H7 6-1 C3~ H7 Cl 1, 2, 4-Trlazol l-yl 13B

Le A 18 886 ~' T a b l e 1 (con-tinued) Ex- Mblting ample point No. X Yn Z R (C) 13 C2~15 6-C2H5 Cl Pyrrol-l-yl Oil 14 3 7 Cl 1,2,4-I'riazol-l-yl 118 C~13 6-C2H5 Cl 1,2,3,4-Tetrazol-l-yl Oil 16 3 7 Cl Pyrazol-l-yl Oil 17 C2H5 - Cl 1,2,4-Triazol l-yl 81 18 CH3 6-C~13 Cl Pyrazol-l-yl 82 19 CH3 6-C~13 Cl 1,2,4-1'riazol-1-yl 110 OE 3 5 C~13 Cl 1,2,4-Triazol-l-yl oil 21 CH3 - Cl Pyrazol-l-yl 56 22 CH3 - Cl 1,2,4-Triazol-l-yl 88 23 CH3 5-CH3 Cl Pyrazol-l-yl Oil 24 CH3 3-CH3 Cl 1,2,4-Triazol-l-yl 114 CH3 3-CH3 Cl Pyrazol-l-yl 102 26 C2H5 6-CH3 Cl Pyrazol-l-yl (xHCl) 87 27 C2H5 6-C2~5 Cl Pyrazol-l-yl (xHCl) 67 28 C2~15 6-C2H5 Cl 3,5-Dimethyl- 111 pyrazol-l-yl 29 C2H5 6-C2H5 Cl Bromo-methyl- 145 pyrazolyl 2 5 6-C2H5 Cl 3-Chloro-1,2,4- 110 triazol-l-yl 31 C~13 6-C2H5 Cl 3,5-Dimethyl 90 pyrazol-l-yl 32 C2H5 6-C2H5 Cl 3-Methyl- 89 pyrazol-l-yl i~

:

z~

T a b 1 e 1 (continued) Ex- Mblting ample point No. X Yn Z R (C) 2 5 6-CE13Cl 3-Methyl- 113 pyrazol-l-yl 34 C(CH3)3 - Cl Pyrazol-l-yl Oil 35C(CH3)3 - Cl 1,2,4-Triazol-l-yl 118 36 C2H5 6-C~13Cl Bromo~methyl- 80 pyrazolyl 37 CH3 6-C2~I5 Cl 4-Chloro- 91 pyrazol l-yl 38 c~l3 6-C2H5Cl 3-Chloro-1,2,4- 121 -triazol-l-yl 2 5 6-C~I3Cl 2,4,5-Trichloro- 158 imidazol-l-yl 2 5 6-C2H5Cl 4-Chloro- 110 pyrazol-l-yl 41 C2H5 6-C2H5Cl 1,2,3,4-Tetrazol- 110 l-yl 42 C2H5 6-C2II5 Br Pyrazol-l-yl 68 43 CH3 6-C2H5Br Pyrazol-l-yl 67 2 5 2 5Cl Imidazol-l-yl Oil 2 5 6-C2H5Br 1,2,4-Triazol-l-yl 90 46 CH3 6-C2H5Br 1,2,4-Triazol-l-yl 78 ~' ', : :
. ~

~, ' ,' :
.
.

Preparation of the starting materials .
Example 3a ~ - N / 2 (Variant ~) 45 g (1.5 moles) of paraformaldehyde were added to a solution of 225.7 g (1 mole) of 2,6-diethyl-chloroacetanilide in 1.5 litres of toluene. I'he mixture was warmed to 40C and 179 g (1.5 moles) of thionyl chloride were added dropwise, whilst stirring, whereupon vlgorous evolution of gas started. The mix-ture was subsequently stirred at 40C until the evolution o-f gas had ended.
Thereafter, it was filtered and the filtrate was concentrated in vacuo. After degassing the residue under a high vacu~m, 268.7 g (98% of theory) of 2,6-diethyl-N-chloromethyl-chloroacetanilide were obtained as a colourless oil.
(Variant ~) 45 g (1.5 moles) o-f parafornaldehyde and 100 g of anhydrous sodium sulphate were added to a solution of 225.7 g (1 mole) of 2,6-diethyl-chloro-a oe tanilide in 1.5 litres of anhydrous toluene. Dry hydrogen chloride was passed into the mixture, whilst stirring and warming to 50 &, until the miIky suspension of the para-formaldehyde had disappeared. Thereafter, a further 100 g of anhydrous sodium sulphate were a~ded and the mixture was subsequently stirred at 50C for one hour and filtered. The filtrate was concentrated m vacuo. After degassing the residue, 263.2 g (96Po of theory) of 2,6-diethyl-chloroacetanilide were obtained as a colourless oil.
The ccmpounds in Table 2 which follows were obtained analogously to Example 3a.

2~

T a b 1 e 2 / CH -Hal n ~ N~ 2 (VII~

Melting point (&) E3xample or refrac-No. X Y Z Hal tive index n ~
5 a 3 7 6-i-C H Cl Cl not isolated 6 a CH3 6-C2~15 Cl Cl 91 8 a C2El5 4,6-(CH3)2 Cl Cl not isolated 9 a CH3 4,6-(CH3)2 Cl Cl "
lOa C2H5 4-CEl3 Cl Cl "
6 C2~15 14a 3 7 Cl Cl 90 17a C2H5 - Cl Cl not isolated 18a C~3 6-C~13 Cl Cl 88 - 21a -~ .

.
. . ' : .
' ' ' ~ ' . ~

(continued) Melting Example point (C) No. X Yn z Hal or refrac-_ _ 20a CH3 5-CH3 Cl Cl not isolated 24a CH3 3-C~3 Cl Cl 40 5 34a ( 3)3 Cl Cl not isolated 42a C2H5 6-C2H5 Br Br "
~3a CH3 6-C2H5 Br Br n The acetanilides of the formula (IV) display powerful herbicidal actions, in particular against grasses. They 10 can therefore be employed for selectively combating weeds, in particular graminaceous weeds.
The herbicidally active acetanilides of the formula (~) likewise have not hitherto been described in the literature. However3 they can be prepared by reacting 15 (b) N-acylmethylanilines of the ~eneral formula C-Co_R7 (X) ~ m in which R4~ R5, R6, R7 and m have the meanings stated above, with chloroacetyl chloride in the presence of a diluent.
If 2,6-dimethyl-N-benzoylmethyl-aniline and chloro-acetyl chloride are used as starting substances, the course of the reaction in process (b) can be represented by the equation which follows:
c~3 N-cH2-co ~ 2Cl HC

Le A 18 886 - 23 ~ 2 4 ~H3 ~N-CH2 -CO~) C0-CH~Cl The N-acylmethyl-anilines of the formula (X) are known (see, inter alia, Chem. Ber. 25, 2865 (1892) and Chem Soc. 1943, 63)~ or they can be prepared by known methods. They are obtained, for example, by reacting anilines with -halogenoketones in the presence of an organic solvent, for example ethanol (see also the preparative examples herein).
Preferred diluents for the reaction according to process (b) are inert organic solvents, especially ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone; nitriles~ such as propionitrile, and in particular acetonitrile; ethers, such as tetra-hydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene;
halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.
The reaction temperatures can be varied within a substantial range in carrying out process (b). In general a the process is carried out between 0 and 120C, preferably between 20 and 100C.
In carrying out process (b), l to 3 moles of chloro-acetyl chloride are preferably employed per mole of the compound of the formula (X). Isolation of the compounds of the formula (V) is effected in the customary manner.
The preparation of acetanilides of the formula (V) is illustrated in the examples which follow:
Example 47 CO~ ~ ~H~ - C0 - ~ Cl ~H~ ~0 - ~H2Cl - Le A 18 886 ' ,~ ' ~- . .

.. . . .

- 2L! -16 ml (0.2 mole) of chloroacetyl chloride wereadded dropwise to a solution of 18.5 g (o.o68 mole) of 2,6-dimethyl-N-(4-chloro-benzoylmethyl)-aniline in 150 ml of benzene. Thereafter, the mixture was stirred under reflux for 15 hours and concentrated by distilling off the solvent and excess chloroacetyl chloride in vacuo The residue was triturated with an ether/
petroleum ether mixture (1:3) and the crystalline residue which formed was filtered off and dried. 17.7 g (75%
of theory) of 2,6-dimethyl-N-(4-chlorobenzoylmethyl)-chloroacetanilide of melting point 128C were obtained.
Preparation of the starting material 0 ~- C~

~H~
46.7 g (0.2 mole) of ~-bromo-4-chloroacetophenone in 40 ml of ethanol were added to 48.4 g (0.4 mole) of 2,6-dimethylaniline in 40 ml of ethanol and the mixture was warmed to 50C for 20 minutes. Thereafter, it was cooled to 0C and the crystals which had formed were filtered off and rinsed with a little ethanol. 30 g t55% of theory) of 2,6-dimethyl N-(4-chlorobenzoyl-methyl)-aniline of melting point 82C were obtained.
Examp_e 48 G~ ~ CH~ - ~0 -- N~
~0 C~ .
23.3 g (0.1 mole) of 2-ethyl-6-methyl-N-pivaloyl-methyl-aniline were dissolved in 100 ml of benzene, and 24 ml (0.3 mole) of chloroacetyl chloride were added.
Thereafter, the mixture was stirred under reflux for 15 hours and concentrated by distilling off the solvent and excess chloroacetyl chloride in vacuo. The oily Le A 18 886 L~4L~32~
residue was ~;tirrecl with petroleurll ether, the product phase ~,Jas decanted, stirred with active charcoal and riltered and the filtrate was concentrated in vacuo.
The residue was stirred with n-hexane and the resul'ing 5 solid was filtered O~r and dried. 13.7 e ( 45% of theory) Or 2-ethyl-6-methyl-N-pivaloylmethyl chloroacetanilide Or melting point 86C were obtained.
Preparation of the startin~$ material ~ ~ N CBII CO ~ C(CHJ )~

cd~

10 108 g (().8 mole) of 2-ethyl-6-methyl-aniline and 53.8 g (0.4 rnole) of monochloropinacolin were heated to 110C in 300 ml of toluene for 25 hours. The mixture was allowed l;o cool and was filtered and the filtrate was washed with water, dried over sodium sulphate and concentrated by distilling orf the solvent in vacuo.
The residue was subjected to fractional distillation.
24.1 g (26% Or theory) of 2-ethyl-6-methyl-N-pivaloylmethyl-aniline of boiling point 138 to 150C/0.7 mm Hg and with a refractive index of n20 = 1.5168 were obtained.
The compounds listed in Table 3 which follows were prepared in a manner analogous to Example 47 or 48.
T a ~ 1 e 3 R~ ~R ~

4~ ~C - ~ 0 - R7 (V) Le A 18 886 .. , ' , a b 1 e 3 ( continued) amp le Me 1 tingO
No . or re frac -~4 ~5 R,"f ~? tndeex _ _~ ___ __ 49 2-C~I H H ~ l~a S0 2-CH~ H H ~Cl 140 51 2,~ CeH, )~ H H ~C:L 134 52 2,~-(C8~;9 )2 H }~ ~ 116 53 2-Cl H H ~Cl 124 54 2, 6- ( CH~ t H H ~ ~00 SS 4-Cl H H ~Cl 114 56 2,6-~CH~ 3 ~ CH3 H C}~ 104 5~ 2~,6 t~c~Hr )8 H H ~Cl 200 58 2~6~.~CIH~ H H ~ 112 5~ 2~6~t~C~HT)~ ~ ~ ~ 140 2,6~C~ )~ H ~ 90 6~ 6 g~ l 70 62 2~6~ ig )2 E ~ ~OC~ 114 63 2~ ) H H OE~ n~-1"5580 S~ 2 3 6- t ~ H ~ 104 2~496~(~ 33 ~g H ~Cl 134 Le A 18 886 T a b l e 3 (continued) Ex- Melt n NamOp~ R~m R 5 R6 R7 refractive _ ___ ~

66 2,4,6~(CH3)3 H H ~ na ~ 1~5610 67 2,6-(CH~)2 H ~ ~ Cl 149 68 2,6 ~CH3)2 H CH3 ~ 84 The compounds li~ted in Table 4 which follows could be obtained in an analogous manner.
T a b l e ll /
C-Co~R7 (V) R4m --CO-C~12Cl Ex-ample No. R4m R5 R6 R7 _ ~__ 69 3,5~t::F~ ~2 H H ~Cl j ~,6 (C~3 )2 H ~i ~N~2 71 2,6-(CH~ )2 H H ~CN
72 296~CH~ )2 H H ~C(CH3 ), 73 2,6-(CH~2. H H ~ Cl 74 2-Cl,6-CHj~ H H ~ Cl 7S : 2-C2H9~6-CH~ CHj~ ~H~

Le A 18 886 . .

~ 28 -T a b 1 e 4 (continued) ___ ample Rllm R5 R6 R7 76 2-C2H"6-CH, CH, CH
77 2-C2H, ,~ H3 CH3 CH~ ~0~
5 78 2-C2H~ ,6-CH~ H!, CHI ~Cl 79 2 -C,~ H!" 6-CH!, CHI CH~ ~Cl 2-C2H3 ~6-CH, H CH~ 4Cl 81 ~-C2 H!" 6-GH3 H C:H9 ~Cl 82 2, 6- (CH, )~, H ~Cl -~Cl lOB3 2,6-(CH~ )2 H ~F -~Cl 84 2,6-(CH~ )2 H -~-CH3 ~) 2,6-(CH3 )2 OE~ ~
86 2,6-(CH~ )2 H ~Cl ~

87 2,6~ H~ ~8 H CH~ Cl The acetanilides of the formula (V) have powerful herbicidal properties. They are therefore suitable for combating weeds. In particular, they can be employed for selective combating of broad leaved weeds and graminaceous weeds.
The herbicidally active acetanilides of the formula (VI) likewise have not hitherto been described in the literature. However, they can be prepared by (c) reacting N-azolylalkylanilines of the general formula 9 RlO N~
~ ,, CH - ~ ~ (XI) R8p Le A 18 886 in which R , R9, R10, Rll~ A and p have the meanings stated above, with halogenoacetic acid chlorides or anhydrides of the formula R12-CH2-G0-Cl (XIIa) or (R -CH2-C0)20 (XIIb) in which 10R12 has the meaning stal;ed abovea in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
If 2,6 diethyl;^N-(3-methylthio 4-methyl 1,214-triazol-5-yl-methyl)-aniline and chloroacetyl chloride are used as starting substances) the course of the reaction of process (c) can be represented by the equation which folIows:

CH N~ ~

C H N - N

\ C~, ~aH~

COCHa Cl The N-azolylalkylanilines of the formula (XI) required as starting substances in process (c) have not yet been described in the literature. They are obtained when (d) anilines of the general formula P~9 . ~ (XIII) R8p ~ ~--NH2 - Le A 18 886 . , ~ .

in which R8, R9 and ~ have the meanings stated above, are reacted with azole derivatives of the general formula R 1o ~ N ~~ (XIV) Hal' - CH - ~ ~ R

in which A3 RlO and Rll have the meanings stated above and Hal' represents chlorine or bromine, in the presence of an acid-binding agent, for example potassium carbonate or sodi.um carbonate, and in the presence of an inert organic solvent, for example dimethylformamide or toluene, at temperatures between 20 and 160C, an excess of the aniline of the formula tXIII) preferably being employed (see also the preparative examples herein)~ or (e) hydrazine derivatives of the general formula ~ CH - C0 - ~H N~

in which R8, R9, RlO and p have the meanings stated above, are reacted with isocyanates or isothiocyanates of the general formula Rl3-N=C=B (XVI) in which B represents oxygen or sulphur and R~3 has the meaning stated above~
in the presence of an organic solvent, for example an alcohol, ether or hydrocarbon, at temperatures between 0 and 80C, the compounds formed~ of the general formula Le A 18 886 , '.~ ~, .' ' . : ' . .
: ' :

' p ~ CH~CO-NH-NH-C~ NH~13 in which B, R8, R9, R10, R13 and p have the meanings stated above, are cyclised in the presence of a strong base, for example sodium hydroxide solution or potassium hydroxide solution, and in the presence of a solvent, for exarnple ethanol or water, at temperatures between 20 and 100C, and the triazolones or triazoleth.iones formed, of the general formula R8 H R13 (XVIII) P
in which B, R8, R9, R10, R13 and ~ have the meanings stated above;
are reacted with halides of the general formula Hal~_R15 ~XIX) in w.hich Hall represents chlorine or bromine and R15 represents one of the radicals of the substituent R14, with the exception of hydrogen, in the presence of a strong base, for example sodium hydroxide solution, and in the presence of an inert organic solvent, for example toluene or methylene chloride, at temperatures between 20 and 80C, it also being possible to carry out the reaction under phase-transfer catalysis and with other alkylating reagents, for example dimethyl sulphate (see also the preparative examples~, or Le A 18 886 ~ 2 (f) hydrazine derivatives of the formula (XV) are reacted with formic acid or acid chlorides or acid anhydrides of the general formula R16-C0-Cl (XXa) or (R16-C0-)20 (XXb) in which R16 represents alkyl, halogenoalkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aryl or optionally substituted aralkyl, in the presence of an inert organic solvent, such as an ether, hydrocarbon or halogenated hydrocarbon, at temperatures between 0 and 50C, and the compounds formed9 of the general formula 9 ~10 R8 ~ ~ CH-C0-NH-NH-C0-R~6 (XXI) in which R8, R9, R10, R16 and p have the meanings stated above, are either cyGlised with diphosphorus pentasulphide in a manner which is in itself known (see Chem. Ber.
32, 797 (1899) and J. prakt. Chemie 69, 145 (1904)) to give thiadiazole derivatives, or are reacted, also in a known manner, with customary reagents which split off water, to give oxadiazole derivatives (in this context~
see Elderfield, Heterocyclic Compounds3 volume 7 (1961))~
or (K) hydraæine derivatives of the general formula (XV) are reacted with nitriles of the general for~ula R17-C--N (XXII) - Le A 18 886 : -. . . .

:~. ' ' ' ~ ' . , . ,~ ' ' ' ,. ' ~ 33 -in which R17 represents alkyl, halogenoalkyl, or optional-ly substituted aryl, in a manner whlch is in itself known to give triazole derivatives (see Chem. Ber. ;96, 1064 (1963)), or ~h) hydrazine derivatives of the formula (XIV) are reacted with imino ethers of the general formula R16_c 18 X HCl (XXIII) in which R16 represents alkyl, halogenoalkyl, alkenyl, alkynyl, cycloalkyl3 optionally substituted aryl or optionally substituted aral}cyl and R18 represents methyl or ethyl, in a manner which is in itself known, under reflux and in the presence of an inert organic solvent, for example ethanol, to give oxadiazole derivatives~ or (j) anilines of the general formula (XIII) are reacted with azole-aldehydes of the general formula ~C _ ~ A ~ R11 (XXIV) in which Rll has the meaning stated above, in the presence of an inert organic solvent, for example toluene, at temperatures between 80 and 120C~ and the compounds formed, of the general formula ~ N = CH ~ A ~ R (XXV) in which A, R8, R9, Rll and p have the meanings stated above, are reduced in a generally known manner; ~or example Le A 18 886 by reaction with complex hydrides, such as sodium boro-hydride, if appropriate in the presence of a polar organic solvent, such as methanol, at temperatures between 0 and 80C.
The compounds of the formulae (XIII) and (XIV) required as starting substances in process (d) are known, or they can be prepared by process~s which are known in principle (see Helv. Chim. Acta 55, 199 et seq. (1972), Chem. Ber. 32, 797 et ~. (1899) and Chem. Ber. 96~ 1049 et ~. (1963)).
The starting æubstances of the formula (XV) re-quired in process (e) have not yet been described in the literature. However, they can be prepared by known processes, by reacting known esters (see7 inter alia, DT-OS (German Published Specification) 2~350,944 and 2,513,730) of the general formula R8p ~ \ H (XXVI) in which R8, R9, R10 and p have the meanings stated above and R18 represents methyl or ethyl J
with hydrazine hydrate, preferably in the presence of an organic solvent, for example ethanol, dioxan or dimethylformamide, at temperatures between 20 and 120C
(see also the preparative examples herein).
The reactants of the formulae (XVI) and (XIX) required in process (e) are generally known compounds of organic chemistry.
The compounds of the formulae (XXa~, (XXb), (XXII) and (XIII~ required as reactants in processes (f) 9 (g~
and (h) are likewise known.
The azole-aldehydes o~ the formula (XXIV) to be used as reactants in process (j) are likewise known, or they can be prepared by processes which are known Le A 18 886 ~ 2 - 35 ~
in principle (see Rlderfield, "Heterocyclic Compounds"
volume 7 (1961) and "Advances in Heterocyclic Chemi~try'l, volume 2 (1968)).
The halogenoacetic acid chlorides and anhydrides of the formulae (XIIa) and (XIIb) also required as starting materials in process (c) are generally known compounds of organic chemi~tr;y.
Preferred diluents for reaction (c) are inert organic solvent~, especially ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone; nitriles, such as propionitrile, and in particular acekonitrile;
ethers9 such as tetrahydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.
If appropriate, process (c) can be carried out in the presence of acid-binding agents (hydrogen chloride acceptors). All the customary acid-binding agents can be used as these agents, especially organic bases, such as tertiary amines, for example triethylamine, or such as pyridine; and inorganic bases, for example alkali metal hydroxides and alkali metal carbonates.
The reaction temperatures can be varied within a substantial range in carrying out process (c). In general, the process is carried out between 0 and 120C, preferably between 20 and 100C.
In carrying out process (c), 1 to 1.5 moles of halogenoacetylating agent and 1 to 1.5 moles of acid-binding agent are preferably employed per mole of thecompound of the formula ~XI). Isolation of the compounds of the formula (VI) is effected in the customary manner.
The preparation of acetanilides of the formula (VI) is illustrated in the examples which follow.

Le A 18 886 Exarnple 88 CHa _ ~ J _ CH

~ H~ C0 ~ CH~l 16.3 g (0.07 mole) of 2-ethyl 6-methyl-N-[(2-methyl-1,3,4-oxadiazol-6-yl)-methyl]-aniline and 6 ~ (o.o76 mole) of anhydrous pyridlne wlere heated to the boil in 100 ml of absolute tetrahydrofuran, whilst stirring, and a solution o~ 8 g (0.07 mole) of chloroacetyl chloride in 20 ml of tetrahydrof~ran was added dropwise. When the dropwise addition had ended, the mixture was sub-10 sequently stirred for 10 minutes and concentrated bydistilling off the solvent and the residue was stirred with 150 ml of water. The reaction product which crystal-lised out was filtered of~, washed with water and dried.
18.7 g (87% of theory) of beige-coloured crystals of 15 2cethyl-6-methyl-N-[(2-methyl-1,3,4-oxadiazol-5-yl)-methyl]-chloroacetanilide of melting point 67 to 70C
were obtained.
Preparation o~ the starting material --N ~ 2 ~ ~ CH3 C~H, A mixture of 101.2 g (0.76 mole) of 2-ethyl-6-methyl aniline~ 40 g (0.3 mole) of 2-methyl-5-chloromethyl-1,3,4-oxadiazole, 41.4 g (0.3 mole) of powdered potassium carbonate and 76 ml of dimeth~lformamide was heated to 100C for 5 hours, whilst stirring. Therea~ter, the 25 reaction mixture was filtered and the filtrate was diluted with methylene chloride and washed several times with water. The methylene chloride phase was dried over sodium Le A 18 886 .

.. ..
. . .

.
: . :

2~L
~ 37 -sulphate and concentrated in vacuo by distilling off the solvent. The residue was distilled in vacuo. 46.8 g (67.5% of theory) of a yellowish oil consi~ting of 2~ethyl-6-methyl-N-[(2-methyl-1,3,4-oxadiazol-5 yl)-methyl]-aniline of boiling point 140 to 142C/G.l mm Hg and with a purity of 94% (determined by gas chroma-tography) were obtained.
Example 89 - N ~ ~ ~ SCH~

~aH~ C0-CH2Cl 5 g (0.017 mole) of 2,6-diethyl-N-[(l-methyl-2-methyl-thio-1,3,4-triazol-5-yl)-methyl]-aniline and 1.6 g (0.02 mole) of pyridine were stirred in 100 ml of absolute tetràhydrofuran, and 2.3 g (0.02 mole) of chloroacetyl chloride were added dropwise at room temperature, during which the temperature rose to about 30C. The mixture was stirred for 2 hours and partly concentrated by distil-ling off the solvent, and water was added. The product which crystallised out was filtered offg dried and re-crystallised from diisopropyl ether/ethyl acetate. 5 g (80% of theory) of 2,6-diethyl-N-[(l-methyl-2-methylthio-1,3,4-triazol-5-yl)-methyl]-chloroacetanilide of melting point 121 to 123C were obtained.

(a~ N~ ~/~J_SCH~

13.9 g (0.05 mole) of 2,6-diethyl-N-[(l-methyl-2-thiono-1,3~4-triazol-5-yl)-methyl]-aniline were stirred rapidly in a two-phase mixture of 150 ml of toluene and 40 ml of 50% strength sodium hydroxide solution at room Le A 18 886 temperature, 1.5 g of` triethyl-benzylammonium chloride (TEBA) being added as a catalyst, and 6.3 g (0.05 mole) of dimethyl sulphate were added dropwise, during which the ternperature rose to about 35C. The mixture was stirred for 5 hours and the toluene phase was separated off, washed several times with water, dried over sodium sulphate and concentrated by distilling off the solvent.
The oil which remained was made to crystallise by adding petroleum ether. After recrystallisation from petroleum ether, 6.7 g (40% of theory) of 2,6-diethyl-N-[(l-methyl-2-methylthio-l~3~4-triazol-5-yl)-methyl]-aniline of melting point 65 to 67C were obtained.

C2H, N -- -NH

(b) ~ ~ CH~ ~ J

29.6 g (0.1 mole) of 1-methyl-4-[(2,6-diethylanilino)-acetyl]-thio8emicarbazide were suspended in 150 ml of ethanol and, after adding 7 g of potassium hydroxide in 20 ml of water~ the mixture was heated under reflux for 1 hour. Thereafter, most of the solvent was distilled off and 250 ml of water were added to the residue.
After acidifying the mixture to pH 5 with glacial acetic acid, the precipitate which formed was filtered off and washed thoroughly with water. After drying, 27 g (97%
of theory) of 296-diethyl-N-[(l-methyl 2-thiono-1,3,4-triazol-5-yl)-methyl]-aniline of melting point 117 to 121 C were obtained.
C~ ~s (c) ~ ~ CH~-CO~NH-~H-CS-NHCH

"' Ca H~

44.2 g (0.2 mole) of 2,6-diethyl-anilino-acetic Le A 18 886 acid hydrazide and 14.8 g (0.2 mole) Or methyl isothio-cyanate were dissolved in 250 ml Or ethanol and the solution was heated to the reflux temperature for one hour.
After subsequently cooling the mixt~re to room temperature, the precipltate which had formed was filtered off and rinsed twice with 50 ml of ethanol each time. After drying, 46 g (78% of theory) of 1-methyl-4-[(2,6-diethyl-anilino)-acetyl~-thiosemicarbazide were obtained in the form of a colourless crystalline substance of melting point 166C.

~C2H5 (d) ~ -NH-C~2-C-NH~H2 58.7 g (0.25 mole) of 2,6-diethyl anilino-acetic acid ethyl ester and 25 g of hydrazine hydrate were left to stand in 200 ml of ethanol for 24 hours Thereafter, the mixture was concentrated by distilling off the solvent and the residue was extracted by stirring with water.
After drying, 50.5 g (91% of theory) of colourless crystals of 236-diethyl-anilino-acetic acid hydrazide of melting point 71 to 73C were obtained.
The compounds listed in Table 5 were obtained in a manner corresponding to Examples 88 and 89.
T a b 1 e 5 p R / = _ ~ ~ _ R

Le A 18 886 ~o -T a b 1 e 5 (continued) Ex- Melting ample (8C)nt R10 ~ 9 R~p A R 2 H CH~ C~ 6~ Cz H" 0 Cl 79-82 91 H CH3 CH" 6-C~ 0 Cl 91- 93 92 H CH~ C~CI~ ~ O Cl 102-04 93 H -S-CH2 -CHnCH 2 C2 H~ 6-c2 H~ ~~ Cl 67-70 94 H ~ CH,~ s ~H3 115-20 H C2 H~ CH~ 6-C2 H9 0 Cl 57-59 96 1~ C2 H5 C~ H~ 6~ H~ 0 C:l 43 47 97 H i-C~}17 CH~ 6~ 2H9 0 Cl viscous 98 H CH, CH3 3~ N Cl o 1 ~CH solid 99 ~1 CN3 ~2~5 ~-~ 2H5 C~ B~ 30 1~ H C~3 C~3 ~ C2~5 Br 92-94C
101 H CH3 1-~:38~ 6-1-C3H7 o Cl 135-37 The starting materials listed in the table which follows were obtained by one or more of the processes described in the present specification.
T a b 1 e 6 ~9 ~1~ N~ N

R8 ~ ~ 8 Le A 18 886 :
:.

, ~14BZ4 - 41 _ T a b 1 e 6 (continued) Ex- ~10 Rll R9 R8 A MeltingO
ample P or refrac-No _ _ - - ~ tive index XI-1 H CH3 C2H5 S-C2H n2a ~ 1,540 XI-2 H c~3 CH3 6-C2H O n~2 1,547 XI-3 H C~3 C~3 6-C~3 D2 ~ 1~552 XI-4 H ~H3 ~~CH3)31 _ O 52-55 XI-5 H ~H3 1~C3H7 6-i-C~ , 0 22 XI-6 H C2~s C2H5 6-Ca!HS ~? " 1 "53q Xl-7 H~2H5 C~3 6r~ O ~ ~ 19542 XI-8 H1-~3H7 CH3 6-C~5 o D1 ~ 1.531 XIJ9 HSCH3 C2HS 6~5 `~N S-57 XI 10 H S~CH2~ C~5 ~-C~5 ,~ 3 nD ~ 1,577 XI 11 H S-CH2 ~ CH3 ~ 5 ,N~CH3 viscous oil 9I-12 H CH3 CH3 3-C83 ,~ ~ 1~2-143 The acetanilides of the formula (VI) have powerful herbicidal properties9 in particular selective herbicidal properties. They are therefore suitable for combating weeds. In particular, they can be employed for selectively combating broad-leaved weeds and graminaceous weeds.
Their selectivity is not always satisfactory.
The antidote according to the invention, that is to say N-dichloroacetyl-1,2,394-tetrahydro-quinaldine of the formula (I), is particularly suitable for prote~ting import-ant crop plants, such as maize, soya beans, cotton, sugar beet, cereals~ rice and cane sugar, against herbicidal damage by thiol-ca~ amates and acetanilides, in particular against damage by herbicidal active compounds of the formulae (IV), (V) and (VI).

Le A 18 886
3~

- ~12 -The antidote according to the present invention can be used in combination with a herbicidally active thiol-carbamate or acetanilide for the purpose of si~ultaneous application.
The active compound combinations according to the invention exhibit an action against broad-leaved weeds and graminaceous weeds in numerous crops of useful plants. They can therefore be used for selectively combating weeds in numerous crops of useful plants.
By weeds, in the broadest sense, there are to be understood in this context all plants which grow in locations where they are undesired.
The active compound combinations according to the invention can be used, for example, to combat the following plants:
dicotyledon weeds of the genera ~ , Le~'id'ium, Galium~ Stellaria, Matricaria, Anthemis,'Gali~so~a3 'Ch'e'no . - ~
, IJrtica, Senecio, Amsranthus, Portulaca,' Xant~ium, Convolvulus, Ipomoea, ~ , Sesbania, AmbroRia, Cir 20 ' Carduus, Sonchus, Solanum, Rori~,'Rotala,' Lind Lamium, Veronica,' Abutilon, Emex, Datura, ~iola,' Ga'leop'sis ' ~ and Cen ~ and monocotyledon weeds of the genera ~ , Setaria, Panicum~ ~ , Phleum,''Poa,' Fest'uca, Eleusine, ~raohlaria, Lolium, Bromus, 'Avena, ~ ' ~ ? Agr~o--p~on,' Cynodon,' Monochoria,' ~ ~ ~? Eleo charis, Scirpus, ~ , IRchaemlm, ~ ,' octenium, Agrostis, ~ and ~ .
The active-compound combinations according to this invention ~ay be used, for example, as selective herbicides in the following cultures:
dicotyledon cultures of the genera ~ , , Beta, Dauc'us, 'Pha'se'olus,''Pis'um,'S'o'lanum,'Li'num, Ipomoea,'Vicia,' Nicot'i'ana,'' ~ 3''Arach'is,' ~raaslca, Lactuca, Cucumis and Cucurb'ita, and ~ . . . _ monocotyledon cultures of the genera ~ ? Zea, Triticum, Horde'um,''Avena, Secale~' ~ ,''P'a , Sacch'a-rum, Anana~, Aspara~ and Allium.

Le A 18 886 The antidote which can be used according to the invention can be converted, if appropriate as a mixture with the herbicidal active compounds with which it is employed3 into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances~
These formulations are produced in known manner, for example by mixing the antidote which can be used according to the invention, if appropriate as a mixture with the herbicidal active compounds with which it i8 employed3 with extenders, that is to say liquid or solid diluents or carriers, optio~-ally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main~ aromatic hydrocarbons, such as xyleneg toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes~ chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
As solid carriers there may be used ground natural Le A 18 886 - 41~ _ minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for gran~les there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks As emulsifying and/or foam-forming agents there may be used non-ionic and an;onic emulsi~iers, such as polyoxyethylene-fatty acicl esters, polyoxyethylene-fatty alcohol ethers 3 for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sul-phonates as well as albumin hydrolysis products. Dis-persing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate~ can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestxffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dye-stxffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95% by weight of antidote or antidote and herbicidal active compound, preferably from 0.5 to 90%
The antidote which can be used according to the invention, as such or in the form of its formulations, can also be employed as mixtures with herbicidal active compounds, finished formulations or tank mixing being possible Mixtures with other known active compounds, such as fungicides, insecticides, acaricides9 nematicides9 bird repellants, growth factors, plant nutrients and Le A 18 886 ~$~ 4 agents which improve soil structure are al~o possible.
The antidote which can be used according to the invention or mixtures of the antidote which can be used according to the invention and a herbicid~l active compound can be employed as such, in the form of their formulations or in the use forms prepared there~rom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders and granules. They may be used in the customary manner, for example by watering, spraying, atomising;, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
The antidote which can be used according to the invention can be applied by methods customary for antidotes of this type. Thus, the antidote which can be used according to the invention can be applied either before or after the herbicide, or can be applied together with the herbicide. If the herbicide is used berore or after sowing, crop plants can also be protected against damage by treating the seed with the antidote before sowing (dressing), A further possible way of using the antidote is to apply it to the seed furrow during sowing.
If the plants are seedlings, these can be treated with the antidote before being transplanted.
When the antidote which can be used according to the invention is employed, the amounts customarily used, at the location, of the particular herbicides are applied.
The amounts of herbicidal active compound in general will vary between 0.1 and 5 kg/ha. The amount of antidote used is independent of the herbicide and of the amount of herbicidal active compound used. In general , the applied amounts of antidote which can be used according to the invention are between 0.1 and 5 kg~ha in the case of treatment of the soil surface 5 pre~erably between 0.2 and 4 kg/ha. In the case o~ seed treatment, the applied amounts of antidote which can be used according to the invention are in general between 10 and 300 g per kilogram of seed, preferably between 25 and 200 g Le A 18 886 ~L~
- 1~6 -per kilogram of seed.
The weight ratios o~ antidote to herbicidal active compound in the active compound combinations according to the invention can vary within relatively wide limits.
In general, 0.05 to 1.0 part by weight, preferably 0.1 to 0,5 part by weight~ of ant;idote of the formula (I) is pre~ent per part by weight of herbicidal active compound of the formula (IV), (V) or (VI).
The present invention also provides a composition for protecting crop plants against damage by herbicidally active thiol-carbamates and acetanilides, containing a~
active ingredient the compound of the present invention in admixture with a solid or lique~ied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of pro-tecting crop plants against damage by herbicidally active thiol-carbamates and acetanilides, which comprises applying to the plants, or to a habitat thereof, the compound of the present invention alone or in the form of a composition containing as active ingredient the com-pound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by herbicidally active thiol-carbamates and acetanilides by being grown in areas in which immediately prior to and/or during the time of the growing the compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The good activity of the antidote which can be used according to the invention and of the active compound combinations according to the invention can be seen from the example which follows.
.
Pre-emergence test Solvent: 5 parts by weight of acetone Le A 18 886 f~ 4 - 1~7 -mulsifier: l part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of herbicidal active compound or anti-dote, or of a mixture of antidote and herbicidal activecompound, was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the con-centrate was diluted with water to the desired concen-tration.
Seeds Or the test plants were sown in normal soil and, after 24 hours, watered with the herbicide pre-paration or antidote preparation or with the preparation of antidote and herbicidal active compound. It was expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation was of no importance, only the amount of active compound applied per unit area being decisive.
After three weeks, t;he degree of damage to the plants was rated in % dama~e in comparison to the development of the untreated control. The figures denote:
0% = no action (like untreated control) 100% = total destruction The active compounds 3 amounts used and results can be seen from the table which follows:

Le A 18 886 B~4
- 4~ -h O 0 0 8 r~
n ~ o o 8 rl O

U~ bO ' ct7 ~ O ~ ) a~ s:: ~rdrC O ~
a) . r~ ~ ~, ~ .
1l1 a~ . _~ 7 E~l Vo ~ cl ~5 8 ~ , bO
h ~ 7 S
g S ~ ~ ~rl ~Go.
5 n~

Le A 18 886 i~ 324 _ 1l9 _ ta s 8 8 s s _ ~ 8 al :
:~: o o o , ~
." ~ .
~q o o ~ r~>
.
ClO ~ ~

_l, ~ b~

,l~ oSj o- ~ o~ ~i o-~rl ~ Z ~ ~Z
0~ ~ ~ V

Le A 18 886 .

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. N-Dichloroacetyl-1,2,3,4-tetrahydro-quinaldine of the formula (I).
2. A process for the preparation of N-dichloroacetyl-1,2,3,4-tetra-hydro-quinaldine, characterised in that 1,2,3,4-tetrahydro-quinaldine, of the formula (II), is reacted with dichloroacetyl chloride.
3. A process according to claim 2, characterised in that the reac-tion is effected in the presence, as a diluent, of water or of an inert organic solvent.
4. A process according to claim 3, characterised in that the reac-tion is effected in the presence, as an acid-binding agent, of an alkali metal hydroxide, an alkali metal carbonate, a tertiary amine or an excess of the compound (II).
5. A process according to claim 2, 3 or 4, characterised in that the reaction is effected at from 0° to 60°C.
6. A process according to claim 2, 3 or 4, characterised in that the reaction is effected at from 20° to 50°C.
7. A process according to claim 2, 3 or 4, characterised in that 1 mole of dichloroacetyl chloride and 1 mole of acid-binding agent are used per mole of the compound (II).
8. A method of protecting crop plants against damage by herbicidally active thiol-carbamates and acetanilides, which comprises applying to the plants, or to a habitat thereof, a protective amount of the compound accord-ing to claim 1.
9. A method according to claim 8 wherein the compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.
10. A method according to claim 9 in which the said compound is applied to an area of crop-plant cultivation in an amount of 0.1 to 5 kg per hectare.
11. A method according to claim 10 in which the said compound is applied in an amount of 0.2 to 4 kg per hectare.
12. A method according to claim 8 or 9, in which the said compound is applied to seed in an amount of 10 to 300 g per kg of seed.
13. A method according to claim 8 or 9, in which the said compound is applied to seed in an amount of 25 to 200 g per kg of seed.
14. A method according to claim 8, 9 or 11 in which the said compound is applied simultaneously with the herbicidally active compound.
15. A composition for protecting crop plants against damage by herbicidally active thiol-carbamates and acetanilides, comprising (1) as herbicidally active ingredient, at least one compound selected from (a) acetanilides of the general formula (IV) in which R represents an optionally substituted N-containing heterocyclic radical, X and Y, which may be identical or different, each represent alkyl, Z represents halogen and n represents 0, 1 or 2, and herbicidally active acid-addition salts and metal salt complexes thereof;
(b) acetanilides of the general formula (V) in which R4 represents alkyl, halogen, halogenoalkyl, alkylthio, alkyl-sulphonyl, aminosulphonyl, cyano or nitro, R5 and R , which may be identical or different, each represent hydrogen, alkyl, halogen, halogenoalkyl or optionally substituted phenyl, R7 represents alkyl or optionally substituted phenyl and m represents 0, 1, 2, 3, 4 or 5;

(c) acetanilides of the general formula (VI) in which A represents oxygen, sulphur or the grouping >NR13, R10 represents hydrogen or alkyl, R11 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkynyl, cycloalkyl, halogen, optionally substituted aryl, optionally substituted aralkyl or the grouping -OR14, -SR14 or NR13R14, R13 represents hydrogen, alkyl or optionally substituted aryl, R14 represents hydrogen, alkyl, halogenoalkyl, alkenyl, alkynyl, cycloalkyl or optionally substituted aralkyl, R8 represents alkyl, R9 represents alkyl or halogen, R12 represents halogen and p represents 0, 1 or 2;
(d) an acetanilide of the formula ;and (e) thiolcarbamates of the general formula (III) in which R1 represents C1-C4-alkyl, benzyl, chlorobenzyl or C1-C4-alkoxy benzyl, and R2 and R3, independently of one another, each represent alkyl with 2 to 4 carbon atoms or cyclohexyl, or R2 and R3, together with the adjacent nitrogen atom, represent a five-membered to seven-membered heterocyclic ring;
and (2), as an antidote against damage to crop plants, N-dichloroacetyl-1,2,3,4 tetrahydroquinaldine of the formula (I).
CA330,709A 1978-06-28 1979-06-27 N-dichloroacetyl-1,2,3,4-tetrahydro-quinaldine, a process for its preparation and its use for preventing damage to crop plants by herbicides Expired CA1114824A (en)

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DE19782828293 DE2828293A1 (en) 1978-06-28 1978-06-28 N-DICHLORACETYL-1,2,3,4-TETRAHYDROCHINALDINE, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF FOR THE PREVENTION OF HERBICIDE DAMAGE TO CULTURAL PLANTS
DEP2828293.1 1978-06-28

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JP (1) JPS557281A (en)
AT (1) ATE273T1 (en)
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BG (2) BG30323A3 (en)
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DD (1) DD144350A5 (en)
DE (2) DE2828293A1 (en)
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PL (2) PL115642B1 (en)
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EP0230871A2 (en) * 1985-12-31 1987-08-05 Monsanto Company Haloacyl 1-substituted-1,2,3,4-tetrahydroisoquinolines as herbicide antidotes

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DE2854598A1 (en) * 1978-12-18 1980-07-03 Basf Ag N-SUBSTITUTED CARBONIC ACID ANILIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES
DE2930448A1 (en) * 1979-07-26 1981-02-26 Bayer Ag COUNTERPROTECTOR FOR THE PROTECTION OF CULTURAL PLANTS FROM HERBICIDE DAMAGE
DE2930451A1 (en) * 1979-07-26 1981-02-19 Bayer Ag N-( ALPHA -CHLOROPROPIONYL)-1,2,3,4- TETRAHYDRO-QUINALDINE, PROCESS FOR ITS PRODUCTION AND ITS USE AS AN ANTIDOTE FOR THE PROTECTION OF CROPS FROM HERBICIDE DAMAGE
FR2479197A1 (en) * 1980-03-25 1981-10-02 Monsanto Co Halomethyl-halo:acetanilide derivs. prepn. - including new cpds., useful as herbicide intermediates
DE3014157A1 (en) * 1980-04-12 1981-10-22 Hoechst Ag, 6000 Frankfurt FUNGICIDAL, HETEROCYCLICALLY SUBSTITUTED THIOGLYCOLIC ACID ANILIDES
US4322553A (en) * 1981-02-02 1982-03-30 Monsanto Company Process for producing N-(halomethyl)acylamides
US4601745A (en) * 1983-12-12 1986-07-22 Ciba-Geigy Corporation Composition for the protection of cultivated plants against the phytotoxic action of herbicides
MX159669A (en) * 1983-12-12 1989-08-02 Ciba Geigy Ag PROCEDURE FOR THE PREPARATION OF ACILAMIDE DERIVATIVES
US4618361A (en) * 1983-12-12 1986-10-21 Ciba-Geigy Corporation Acylamides and compositions for the protection of cultivated plants against the phytotoxic action of herbicides
SU1510711A3 (en) * 1984-05-28 1989-09-23 Циба-Гейги Аг (Фирма) Weed-killer
US5215570A (en) * 1988-10-20 1993-06-01 Ciba-Geigy Corporation Sulfamoylphenylureas
JPH07173137A (en) * 1991-04-10 1995-07-11 Nippon Bayeragrochem Kk Tetrahydroquinolin-1-ylcarbonyl chloride derivative and its production
LT3943B (en) 1993-12-23 1996-05-27 Ciba Geigy Ag Remedy for cultured plants protection, use of sulphamoyl-phenyl-carbamides for cultured plant protection, herbicidal preparation, process for preparing sulphamoyl-phenyl-carbamides
US20040258563A1 (en) 2003-06-23 2004-12-23 Applera Corporation Caps for sample wells and microcards for biological materials

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GB1052308A (en) * 1964-08-25
CA1174865A (en) * 1971-04-16 1984-09-25 Ferenc M. Pallos Thiolcarbamate herbicides containing nitrogen containing antidote
FR2310348A1 (en) * 1975-05-07 1976-12-03 Ugine Kuhlmann NEW HETEROCYCLIC DERIVATIVES ANTIDOTES AGAINST HERBICIDES

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0230871A2 (en) * 1985-12-31 1987-08-05 Monsanto Company Haloacyl 1-substituted-1,2,3,4-tetrahydroisoquinolines as herbicide antidotes
US4755218A (en) * 1985-12-31 1988-07-05 Monsanto Company Haloacyl 1-substituted-1,2,3,4-tetrahydro-isoquinolines as herbicide antidotes
EP0230871A3 (en) * 1985-12-31 1988-12-14 Monsanto Company Haloacyl 1-substituted-1,2,3,4-tetrahydroisoquinolines as herbicide antidotes

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PL116411B1 (en) 1981-06-30
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CS204050B2 (en) 1981-03-31
DE2828293A1 (en) 1980-01-10
JPS557281A (en) 1980-01-19
EP0006540B1 (en) 1981-10-07
DK272679A (en) 1979-12-29
PT69788A (en) 1979-07-01
PL115642B1 (en) 1981-04-30
DD144350A5 (en) 1980-10-15
BR7904071A (en) 1980-03-11
ES481980A1 (en) 1980-02-16
ATE273T1 (en) 1981-10-15
IL57651A0 (en) 1979-10-31
EP0006540A1 (en) 1980-01-09
AU4826679A (en) 1980-02-07
BG30323A3 (en) 1981-05-15
BG30618A4 (en) 1981-07-15
IL57651A (en) 1982-11-30
ZA793212B (en) 1980-08-27

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