NO814075L - NEW 2-HALOGENACETAMIDES AND HERBICIDE PREPARATIONS CONTAINING LIKE - Google Patents

Description

This invention relates to new 2-haloacetamides

and herbicidal preparations containing such.

It is known in the art to use various 2-haloacetamides as herbicides, either individually or together with other herbicides.

Among the known herbicidal compounds are 2-haloacetamides which in varying arrangements and substituent combinations have alkyl-, cycloalkyl-, alkenyl-, cycloalkenyl-, alkoxy-, halogen-, haloalkyl-, aryl,- aralkyl,-N-, 0- and/ or S-containing heterocyclyl groups and

similarly on the nitrogen atom, which substituents may be further substituted with other radicals.

Illustrative of the known compounds which are relevant to the compounds according to the invention, are the compounds which have azolylmethyl groups on the acetamide nitrogen atom. However, such compounds require that the nitrogen atom is also substituted with aromatic groups. Examples of such N-azolylmethyl-substituted 2-halo-acetanilide compounds are those described in German patent applications Nos. 2,704,281, 2,648,008 and 2,744,396. In other publications, compounds with 1-cycloalken-1-yl groups on the nitrogen atom are described, but such compounds also require other non-heterocyclic radicals bound to the nitrogen atom, see US Patent Nos. 3,574,746 and 3,586,496.

Other representatives of the state of the art refer to 2-haloacetamides with 1-alken-1-yl groups substituted on the nitrogen atom, but such compounds require alkoxyethyl, alkoxypropyl, alkyl or alkenyl radicals substituted on the nitrogen atom, see South African patent document no. 753,918.

Perhaps the most relevant previous publications

known to the inventor, are the publications that describe 2-haloacetamides with simultaneous substitution of 1-cycloalken-1-yl or acyclic-1-alken-1-yl groups and a nitrogen

containing heterocyclic radical on the acetamide nitrogen atom. IN

US Patent No. 4,155,744 thus describes such 2-haloacetamides which contain the 1-cycloalken-1-yl and N-heterocyclyl groups. 2-Haloacetamides containing decyclic 1-alken-1-yl and N-heterocyclyl groups require that when a heterocyclic radical attached to said nitrogen atom is present, the 1-alken-1-yl group must have a different substituent

tuent than hydrogen, alkyl or alkenyl. When the 2-haloacetamids referred to in said US Patent No. 4,155,744 contain a nitrogen-containing heterocyclyl radical, the nitrogen atom must be substituted with a non-cyclic group selected from hydrogen, C5_7cycloalken-1-yl and cycloalkadienyl groups and saturated and unsaturated heterocyclic radicals.

It will thus be understood that the most relevant of the known 2-haloacetamides are different from the new 2-haloacetamides according to the invention.

The present invention relates to new compounds with herbicidal action and herbicidal preparations containing these compounds as active ingredients.

The compounds according to the invention include those of the formula:

where X is chlorine, bromine or iodine,

R is an acyclic 1-alkenyl-1-yl radical with up to 12 carbon atoms, preferably up to 8 carbon atoms, a Cr_ 7

1-cycloalken-1-yl radical or one of these radicals substituted with one or more C^_^alkyl groups, and

A is an unsubstituted C 1-4 alkyl-substituted pyrazolyl, imidazolyl, triazolyl, or tetrazolyl group.

Preferred compounds according to the invention are those compounds of the above formula where A is a pyrazolyl, triazolyl or imidazolyl group bound to the methylene group■ through a nitrogen atom, preferably a pyrazol-1-yl group, and where R is a 1-cyclohexene -1-yl group, any of these groups may be substituted with a C^_^ alkyl group. Specific preferred compounds according to the invention are: N-[2-methyl-1-(1-m.ethylethyl)-1-propenyl]-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

N-(1,2-dimethyl-1-propenyl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-1,2,4-triazol-1-ylmethyl)-2-chloroacetamide.

N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-imidazol-1-ylmethyl)-2-chloroacetamide.

N-(2,5-dimethyl-1-cyclopenten-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

Other specific compounds according to the invention will be described below.

Examples of the applicability of the herbicidal preparations according to the invention are given in tables II and III below.

The new 2-haloacetamides according to the invention

can conveniently be prepared by reacting the suitable heterocyclic azole compound with the corresponding N-halomethyl-N-(1-alken-1-yl)-el.(1-cycloalken-1-yl)-2-chloro-acetamide to replace the halogen of the halomethyl group with the appropriate azolyl group. The N-halomethyl-2-haloacetamides used as starting materials can be prepared according to

a new method which involves the reaction of a concentrated hydrogen halide with the corresponding N-(alkoxymethyl)-2-haloacetamide to replace the alkoxy group with the halogen atom. Mentioned N-Alkoxymethylamides can conveniently be prepared by the N-alkylation process described in US patent 4,258,196.

Example 1

This example describes the preparation of a new compound according to the invention. Part (a) describes the preparation of the N-(Alkoxymethyl)-2-halogenacetamide which was used for the preparation of the corresponding N-halogenmethyl-2-halogenacetamide. Part (b) describes the reaction of the amide produced under part (a) with a hydrogen halide to produce said N-halogenmethyl compound, and part (c) describes the reaction of the N-halogenmethylamide with the selected azole compound to produce the compound according to the invention. (a) This section describes the use of a multiphase system to form the anion of the desired secondary 2-haloacetamide and the alkylation of this anion, preferably in the presence of a phase transfer catalyst, to produce the corresponding desired tertiary 2-haloacetamide.

A mixture of 400 g of the secondary amide, namely N-(2,6-dimethyl-1-cyclohexen-1-yl)-2-chloroacetamide, with a melting point of 114-115°C, in 760 ml of methylene chloride and 300 ml of chloromethyl methyl ether was mixed with 2 g of benzyl triethyl ammonium bromide. The mixture was cooled to 10°C and then,

over 30 minutes added in a thin stream to a vigorously stirred mixture of 1100 ml of 50% sodium hydroxide, 300 ml of methylene chloride and 9 g of benzyltriethylammonium bromide contained in a 5 liter 4-necked round bottom flask. External cooling in a bath of ice and acetone was necessary to keep the temperature below 25°C. The mixture was stirred for a further hour. Gas-liquid chromatography showed that 78% of the tertiary amide and 22% of the corresponding O-alkylated by-product O-(methoxymethyl)-N-(2,6-dimethyl-1-cyclohexen-1-yl) had been formed )-2-chloroacetimidate. The reaction mixture was separated, and the organic layer was given a simple wash with 5% HCl solution to transfer the imidate to the secondary amide used as starting material. To the washed mixture in methylene chloride was added a further 120 ml of chloromethyl methyl ether and 5.0 g of the quaternary ammonium phase transfer catalyst, after which 350 ml of 50% NaOH was added with stirring. After separation of the layers and further washing with water, the product was filtered through clay. The methylene chloride solvent was evaporated and the residue was heated to 85°C (0.55 mm Hg) and then filtered through clay to purify the product. The product was extracted in approx. 99% yield and had a boiling point of 127°C (0.15 mm Hg).

Calculated for C12H2Q<C>1N02%:C=58.65; H=8.20; N=5.70;

Found: C=58.48; H=8.22; N=5.62.

The product was identified as N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(methoxymethyl)-2-chloroacetamide.

The method described above can be carried out

without formation of imidate, thereby avoiding acid-catalyzed regeneration of secondary amide, if smaller amounts,

namely up to 50 g of the secondary amide is used, the catalyst concentration is increased up to 20-50% of the amount of secondary amide used and the base, NaOH, is added in one portion.

The structure of the products obtained in this example

and in the following examples was confirmed by mass spectrography, gas-liquid chromatography, nuclear magnetic resonance analysis and/or elemental analysis.

(b) 1.0 g of the product obtained in part (a) was placed in 10 ml of CCl 2 , and the mixture was stirred for 2 hours with 10 ml. 37% HC1. After completion of the reaction, as indicated by NMR (Nuclear Magnetic Resonance), the formed layers were separated

apart, 5 ml of fresh HCl added and the mixture stirred for one hour. After separation of the layers, the organic layer was vacuum stripped to 75°C/0.2 mm Hg, whereby 0.8 g (93% yield) of an oil was obtained.

Analysis calculation for

The product was identified as N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(chloromethyl)-2-chloroacetamide. (c) To 8.9 g (0.036 mol) of the amide prepared in part (b) dissolved in toluene was added 4.9 g (0.072 mol) of pyrazole. This mixture was heated at 90°C with stirring for 7 hours. The following day, the toluene solution was decanted, washed twice with water and then vacuum distilled to remove the solvent and traces of moisture. The residue was 9.1 g of an oil which crystallized on standing. A sample of the product was recrystallized from heptane/methylcyclohexane, whereby a solid product with a melting point of 83-84°C was obtained in 89% yield.

The product was identified as (N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

Example 2

2 g of N-(methoxymethyl)-N-[2-methyl-1-(1-methylethyl)-1-propen-1-yl]-2-chloroacetamide dissolved in 20 ml CCl^ were brought into contact with 20 ml 37 % HC1 and shaken in a separatory funnel. Then NMR analysis of the lower layer indicated that the reaction

was completed, the material was vacuum stripped at approx. 50°C/

0.05 mm Hg, whereby 1.6 g of product was obtained.

The product, whose structure was confirmed by NMR, was identified as N-(chloromethyl)-N-[2-methyl 1-1-(1-methylethyl)-1-propen-1-yl]-2-chloroacetamide. The nuclear magnetic characteristics of this product are as follows: (CDC13)£" 0.95, 1.1 CH(CH3)2 (2 doublets, 3H each, J=7Hz);

2.7, 2.84 (2 singlets, 3H each) = C(CH3)2; & 3.95, (CH3)2CH-(heptet 1H, J= 7 Hz) ; & 4.02, Cl CH_2 CO (S, 2H) ;

f= 5.38, N-CH 2 Cl (AB quartet, 2H, J= 8.5 Hz).

To 1.4 g (0.0059 mol) of the N-(chloromethyl)-2-chloroacetamide prepared above, 0.8 g (0.012 mol) of pyrazole was added, and the mixture was heated for approx. 20 ml of toluene at 80-90°C for approx. 6-7 hours. The material was decanted, washed with 10% caustic soda and then with water, stripped and recrystallized from methyl-cyclohexane to give 1.0 g (63% yield) of a white solid, mp 101.0-101 .5°C.

The product, the structure of which was confirmed by NMR, was identified as N-[(2-methyl-1-(1-methylethyl)-1-propenyl^j -N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

Example 3

Proceeding according to the general procedure described in Example 2, 2.0 g of N-(methoxymethyl)-N-(1,2-dimethyl-1-propenyl)-2-chloroacetamide was dissolved in 20 ml of CCl ^and shaken in a small separatory funnel together with 25 ml of 37% HC1. The lower organic layer was taken out,

and it appeared by NMR analysis that the reaction was complete. The solvent was evaporated on a water bath (60°C) under pump pressure, whereby 1.2 g (57% yield) of product was obtained.

The product was identified as N-(chloromethyl)-N-(1,2-dimethyl-1-propen-1-yl)-2-chloroacetamide. The characteristic properties of this product with respect to nuclear magnetic resonance are as follows: (CDCl^^<1>.65, 1 .8, 1 .95 (3=C-CH3, 9 protons, each a broad singlet with partial multiplicity) : =4.0, C1CH2CO (singlet, 2H) ; $ =5.35, C1CH_2N (AB quartet, 2H, J = 9 Hz).

0.54 g (0.008 mol) pyrazole and 0.8 g (0.0038 mol)

of the N-chloromethyl-2-chloroacetamide prepared above was mixed in toluene and heated at 90°C. When worked up as described in example 1, 0.6 g (62% yield) of an amber colored oil was obtained. 1.5607,

25

The product, whose structure was confirmed by NMR, was identified as N-(1,2-dimethyl-1-propen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

N-(methoxymethyl)-N-(acyclic-1-alken-1-yl)-2-chloroacetamide which was used for the preparation of the corresponding N-(chloromethyl)-2-chloroacetamides used as starting materials

in Examples 2 and 3, were prepared in a similar manner to the analogous N-(methoxymethyl)-N-(1-cycloalken-1-yl)-2-chloroacetamides, as exemplified in Example 1(a). The starting material N-(Alkoxymethyl)-amide, which was used in example 3, is prepared in the following way:

16.0 g (0.1 mol) of N-(1,2-dimethyl-1-propen-1-yl)-2-chloroacetamide, 4.0 g of benzyl-triethylammonium chloride and 16 ml of bromomethylmethylether are added to 200 ml of CH2Cl2. The mixture is cooled to 10°C, and 100 ml of 50% NaOH is added in one portion. After aqueous work-up, 4.0 g (19.5% yield) of the corresponding N-(methoxymethyl)-2-chloroacetamide are obtained, with a boiling point of 110-120°C/0.05 mm Hg (Kugelrohr).

The product was identified as N-(methoxymethyl)-N-(1,2-dimethyl-1-propen-1-yl)-2-chloroacetamide.

Examples 4-10

Using essentially the same procedures as those described in Examples 1-3, but using the appropriate starting materials and reaction conditions, other 2-haloacetamide compounds according to the above general formula were also prepared. The same or equivalent solvents, catalysts, etc., along with appropriate reaction times and temperatures, can readily be used in equivalent embodiments of the process. Typical compounds prepared according to the above procedures are listed in Table I, along with certain physical properties.

The compounds according to the invention have been shown

to exhibit herbicidal action both before and after germination, and they can therefore be used in both ways. However, the compounds are preferably used before germination, as will be explained in more detail below.

The herbicidal action before germination of representative compounds according to the invention is determined by the following method: A top soil of good quality is placed in an aluminum tub and compressed to a depth of from 9.5 to 12.7 mm from the tub's upper edge. A number of seeds or vegetative propagules of different plant species are placed on the soil layer. The amount of soil required to fill the tubs to the brim after sowing or adding vegetative propagules is weighed out in a tub. The soil and a known amount of the active ingredient, which is added in a solvent or as a suspension of a wettable powder, are thoroughly mixed and used to cover the prepared vessels. After treatment, the tubers are moved to greenhouse benches, after which watering is carried out from below as needed to ensure suitable humidity for germination and growth. Observations are made approx.

2-3 weeks after sowing and treatment.

Tables II and III summarize the results of tests carried out to determine the pre-germination herbicidal activity of the compounds of the invention. The assessment of the herbicidal effect was carried out using a fixed scale based on the percentage damage of.

each plant species. The assessment was made according to the following scale:

The plant species that were used in an experimental series, for which data are listed in Table II, are identified by letters as follows:

The compounds were further tested using the method described above on the following plant species:

A summary of the results is listed in Table III.

Other representative compounds according to the invention include those corresponding to the general formula given above, where X is bromine or iodine, and the C^_^alkyl substituents on the links R and A include methyl, ethyl and the isomeric propyl and butyl groups. Other compounds that are included within the scope of the invention are those compounds within the scope of the above general structural formula where the terms A and R may be substituted with one or more additional groups, such as halogen, nitro, cyano, amino, trifluoromethyl, other lower halogen alkyl groups, lower alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, polyalkoxy, thioalkyl or alkylthioalkyl with up to 8 carbon atoms, C-^- in cycl°alkyl or cycloalkenyl or aryl, aralkyl or alkaryl with up to 10 carbon atoms and the like. Other examples of compounds are given in Table IV.

The herbicidal preparations according to the invention,

including concentrates that require dilution before use, contain at least one active ingredient and an auxiliary substance in liquid or solid form. The preparations are made by mixing the active ingredient with an auxiliary substance including diluents, extenders, carriers and conditioners, and preparations can be made in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. The active ingredient can thus be used together with an auxiliary substance, such as a finely divided solid substance, a liquid of organic origin, water, a wetting agent, a dispersing agent,

an emulsifier or any suitable combination thereof.

The preparations according to the invention, especially liquids

and wettable powders, preferably contain as a conditioning agent one or more surfactants in a sufficient quantity to make a given preparation easily dispersible in water or oil. The inclusion of a surfactant in the preparations makes the preparations far more effective. The term "surfactant" means that this includes wetting agents, dispersing agents, suspending agents and emulsifying agents. Anionic, cationic and non-ionic agents can be used with equal convenience.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkylphenols (especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the monoesters of higher fatty acids and hexitolanhydrides (eg sorbitan). Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate and polymethylene bisnaphthalene sulfonate.

Wettable powders are preparations which are dispersible in water, and which contain one or more active ingredients, an inert, solid extender and one or more wetting and dispersing agents. The inert, solid extenders are usually of mineral origin, such as the natural clay species, diatomaceous earth and synthetic minerals derived from silicic acid and the like. Examples of such extenders are kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powders according to the invention usually contain from 0.5 to 60 parts (preferably from 5 to 20 parts) active ingredient, from 0.25 to 25 parts (preferably from 1 to 15 parts) wetting agent, from 0.25 to 25 parts ( preferably from 1.0 to 15 parts) dispersant and from 5 to 95 parts (preferably from 5 to 50 parts) inert, solid extender, all parts being calculated on a weight basis. If necessary, from 0.1 to 2.0 parts of the solid, inert extender may be replaced with a corrosion inhibitor and/or an antifoam agent.

Other preparations include dust concentrates, comprising from 0.1 to 60% by weight of the active ingredient on a suitable extender. These dust preparations can be diluted for application in concentrations in the range from 0.1 to 10% by weight.

Aqueous suspensions or emulsions can be prepared by stirring an aqueous mixture of a water-insoluble active ingredient and an emulsifier until the mixture is uniform, after which the mixture is homogenized to form a stable emulsion of very fine particles. The resulting concentrated aqueous suspension is characterized by an extremely small particle size, so that when it is diluted and sprayed, the coverage is very even and good. Suitable preparations of this type contain from 0.1 to 60% by weight, preferably 5 to 50% by weight, of active ingredient, the upper limit being determined by the limit of solubility of the active ingredient in the solvent.

In another type of aqueous suspensions, a water-immiscible herbicide is encapsulated, so that a micro-encapsulated phase dispersed in an aqueous phase is formed. In one embodiment, tiny capsules are formed by combining an aqueous phase containing a lignin sulphonate as an emulsifier with a water-immiscible chemical and polymethylene-poly-phenyl isocyanate, after which the water-immiscible phase is dispersed in the aqueous phase, and then added a multi-functional amine. The isocyanate and the amine react with each other to form a solid urea shell around particles of the water-immiscible chemical, so that micro-capsules are formed of this. Usually the concentration of the micro-encapsulated material will be from 480 to 700 g/litre of the total preparation, preferably from 480 to 600 g/litre. The microencapsulation process discussed here is described in more detail in US Patent No. 4,280,833.

Concentrates are usually solutions of the active ingredient in water-immiscible or partially water-immiscible solvents, together with a surfactant. Suitable solvents for the active ingredient according to the invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters and ketones. However, other strong liquid concentrates can also be prepared by dissolving the active ingredient in a solvent. Dilution to spray concentration is carried out e.g. with the kerosene.

The concentrated preparations contain from 0.1 to 95 parts (preferably from 5 to 60 parts) of active ingredient, from 0.25 to 50 parts (preferably from 1 to 25 parts) of surfactant and, if necessary, from: -4 to 94 parts solvent, all parts being parts by weight calculated on the basis of the total weight of the emulsifiable oil.

Granules are physically stable particulate preparations comprising an active ingredient that adheres to or is distributed in a base material consisting of an inert, finely divided, particulate extender. In order to facilitate the leaching of the active ingredient from the particles, a surface-active agent, such as one of those indicated above, may be present in the preparation. Naturally occurring clay species, pyrophyllite, illite and vermiculite are examples of applicable particulate mineral extenders. The preferred extenders are the porous, absorbent, preformed particles, such as preformed and screened particulate attapulgite or heat-expanded particulate vermiculite, or the finely divided clays.

such as kaolin clay, hydrated attapulgite or bentonite clay. These extenders are sprayed on or mixed with the active ingredient to form the herbicide granules.

The granular preparations according to the invention can contain from 0.1 to 30 parts by weight, preferably from 3 to 20 parts by weight, of active ingredient per 100 parts by weight of clay and from 0 to 5 parts by weight of superfiateactive agent per 100 parts by weight particulate clay.

The preparations according to the invention may also contain other additives, e.g. fertilisers, other herbicides, other pesticides, safety enhancing agents and the like, which are used as auxiliaries or together with any other of the auxiliaries mentioned above. Chemicals that are useful together with the active ingredients according to the invention are e.g. triazines, urea compounds, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like, such as: Heterocyclic nitrogen/sulphur derivatives

2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis-(isopropylamino)-s-triazine

2-chloro-4,6-bis-(ethylamino)-3-triazine

5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone

3- isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxyd 3-methyl-4-amino-6-phenyl-1,2,4-triazin-5-one

3-amino-1,2,4-triazole

6,7-dihydrodipyrido-(1,2-a:2',1'-c)-pyrazidiirium salt 5-bromo-3-isopropyl-6-methyluracil

1,1'-dimethyl-4,4'-bipyridinium salt

Urea compounds

N'-(4-chlorophenoxy)-phenyl-N,N-dimethylurea

N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea

3-(3,4-dichlorophenyl)-1,1-dimethylurea

1,3-dimethyl-3-(2-benzothiazolyl)-urea

3-(p-chlorophenyl)-1,1-dimethylurea

1-butyl-3-(3,4-dichlorophenyl)-1-methylurea

Carbamater/ Thiolcarbamater 2-chloroallyl-diethyldithiocarbamate S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate

isopropyl N-(3-chlorophenyl)-carbamate

S-2,3-dichloroallyl-N,N-diisopropylthiolcarbamate j ethyl-N,N-dipropylthiolcarbamate i S-propyl-dipropylthiolcarbamate i

i Acetanides acetanilides/ Anilines/ Amides j 2-chloro-N,N-diallylacetamide ; N,N-dimethyl-2,2-diphenylacetamide N-(2,4-dimethyl-5-[ [ (trifluoromethyl)-sulfonyl]-amino]-phenyl)-acetamide f N-isopropyl-2-chloroacetanilide

2•,6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl 1-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacet-

anilide α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide >

Acids/ Esters/ Alcohols 2,2-dichloropropionic acid [ 2- methyl-4-chlorophenoxyacetic acid 1

2,4-dichlorophenoxyacetic acid

methyl 1-2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionate 3-amino-2,5-dichlorobenzoic acid

2-Methoxy-3,6-dichlorobenzoic acid

2 , 3 , 6-trichlorophenylacetic acid

N-1-naphthylphthalanir..Gyre

sodium 5-[1-(chloro-4-(trifluoromethyl)-phenoxy]-2-nitrobenzoate 4,6-dinitro-o-sec-butylphenol

N-(phosphonomethyl)-glycine and its C.,_ 6 monoalkylamine- and

. alkali metal salts and combinations thereof

Ether

2,4-dichlorophenyl-4-nitrophenyl ether

2-chloro-tf, OL, <* -trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether

Various

2,6-dichlorobenzonitrile

Acidic monosodium methanearsonate

disodium methanearsonate

Fertilizers that can be used together with the active ingredients are e.g. ammonium nitrate, urea, pot ash and superphosphate. Other useful additives are materials in which plant organisms can take root and grow, such as compost, dung, humus, sand and the like.

In the following, some examples of embodiments of the herbicidal preparations described above are given.

In Emulsifiable preparations

II Liquid concentrates

III Wettable powders

Weight percentage IV Dust preparations (dusters)

V Granules

Effective amounts of the acetanilides according to the invention are applied to the soil containing the plants, or they are incorporated into aqueous media in any suitable manner. The application of liquid preparations and particulate solid preparations to the soil can be carried out in any conventional manner, e.g. using dust spreaders, boom spreaders and hand spreaders and pre-dusting spreaders. The preparations can also be applied from airplanes as a dust or as a shower, because they are effective in small quantities. The application of the herbicidal preparations to aquatic plants is usually carried out by adding the preparations to the aqueous medium in the area where control of the aquatic plants is desired.

Applying an effective amount of the compounds according to the invention at the place where the unwanted weeds occur is of decisive importance in the utilization of the invention. The exact amount of active ingredient that should be used in each individual case may depend on a number of factors, including the plant species and the plants' stage of development, the type of soil and its condition, the amount of rainfall and the specific acetanilide used. When selectively applied before germination to the plants or to the soil, an amount of from 0.02 to 11.2 kg/ha, preferably from 0.04 to 5.60 kg/ha or most preferably from 1.12 to 5.6 kg/ha of acetanili-det. Smaller or larger quantities may be desirable in certain cases. A person skilled in the art will easily be able to determine the optimal amount in any given case from this description.

The terms "soil" and "soil" used in this description are to be understood in the broadest sense and include all conventional types of soil as defined in Webster's New International Dictionary, Second Edition, Unabridged (1961). The terms thus refer to any substance or medium in which plants can take root and grow and thus includes not only soil, but also compost, dung, humus, sand and the like adapted for plant growth.

Claims (15)

1. New 2-haloacetanilides, characterized in that they have the formula where X is chlorine, bromine or iodine, R is an acyclic 1-alkenyl-1-yl group with up to 8 carbon atoms, a C 1 -7 1-cycloalken-1-yl group or one of these groups substituted with one or more C 1 -4 alkyl groups, and A is an unsubstituted or C^_^ alkyl-substituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl group. 2. Compounds according to claim 1, characterized in that R is an unsubstituted or C 1 -4 alkyl-substituted acyclic 1-alken-1-yl group. 3. Compounds according to claim 2, characterized in that A is a pyrazolyl group. 4. Compound according to claim 3, characterized in that it is N-(1,2-dimethyl-1-propen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide. 5. Compound according to claim 3, characterized in that it is N-[2-methyl-1-(1-methylethyl)-1-propen-1-yl] -N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide . 6. Compounds according to claim 1, characterized in that R is an unsubstituted or C| _4 alkyl-substituted C 1 _7 cycloalken-1-yl group. 7. Compounds according to claim 6, characterized in that A is a pyrazolyl group. 8. Compound according to claim 7, characterized in that it is N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide. 9. Compounds according to claim 6, characterized in that A is a triazolyl group. 10. Compound according to claim 9, characterized in that it is N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-1,2,4-triazol-1-ylmethyl)-2- chloracetamide. 11. Compounds according to claim 6, characterized in that A is an imidazolyl group. 12. Compound according to claim 11, characterized in that it is N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-imidazol-1-ylmethyl)-2-chloroacetamide. 13. Compounds according to claim 6, characterized in that A is a tetrazolyl group. 14. Compound according to claim 7, characterized in that it is N-(2,5-dimethyl-1-cyclopenten-1-yl)-2-chloroacetamide. 15. Herbicidal preparation containing as active ingredient a 2-halogenacetanilide, characterized in that it contains as active ingredient one or more 2-halogenacetanilides according to claims 1-14.