LU83237A1 - N-HYDROCARBYLOXYMETHYL-2-HALOACETANILIDE COMPOUNDS AND HERBICIDE COMPOSITIONS CONTAINING THEM - Google Patents

Description

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1.

The present invention relates to the field of 2-haloacetanilides and to their use in agronomic techniques, for example as herbicides.

The prior art relating to the present invention includes numerous descriptions of 2-haloacetanilides which may be unsubstituted or substituted by a large number of substituents on the nitrogen atom of anide and on the anilide nucleus , comprising alkyl, alkoxy, alkoxyalkyl, halogen, etc. radicals

As a prior art relating to the compounds of the present invention, which are characterized in that they have an alkoxymethyl radical on the anilide nitrogen, an alkoxy radical in an ortho position and a specific alkyl radical in the In another ortho position, the closest prior art known to the applicant is represented by US Pat. Nos. 3,442,945 and 3,547,620. The most interesting descriptions in US Pat. Nos. 3,442,945 and 3,547,620 are the compounds consisting of 2'-t-butyl-2-chloro-N-20 methoxymethyl-6'-methoxyacetanilide and its brominated analogue (examples 18 and 34 of American patent n ° 3,547,620 and examples 18 and 36 of American patent n ° 3,442,945, respectively).

American patents n ° 4.070.389 and n® 2.

4,152,137 describe a generic formula which includes compounds of the type described in US Patent Nos. 3,442,945 and No. 3,547.Ç20. However, the only compound of the species described having an alkyl radical in an ortho position and an alkoxy radical in the other ortho position has an alkoxyethyl radical on the anilide nitrogen atom; compounds of this type are described in more detail below.

Other less interesting prior art documents are the Belgian patent no. 810,763 and the published German patent application no. 2,402,983; the compounds of these references include the compounds of the type described in US Pat. Nos. 4,070,389 and 4,152,137 and are characterized in that they have an alkoxyalkyl radical having 2 (or more) carbon atoms between l atom of 15 anilide and the oxygen atom of the alkoxy part. The most interesting specific descriptions in Belgian patent no. 810,763 and in published German patent application no. 2,402,983 appear to be the compounds having an ethoxyethyl radical on the anilide nitrogen atom, a 2o methoxy radical or ethoxy in one ortho position and a methyl or ethyl radical in the other ortho position; with reference to Belgian Patent No. 810,763, reference will be made to compounds no 7, 13 and 18; other less interesting homologs of these compounds are also described, for example the compounds 6, 9 and 16 and 17, which have methoxyethyl or methoxypropyl radicals on the nitrogen atom, a methoxy or etho-xy radical in one ortho position and a methyl radical in the other ortho position.

US Patent No. 3,442,945 contains certain herbicidal data relating to the above-mentioned compounds having a chemical configuration most closely related to the compounds of the present invention, and certain data are presented in the other patents for other purposes. other homologous compounds and analogues, less intimately linked 35 ′ from the point of view of chemical structure, for example compounds n ° 6 and 9 in Belgian patent n ° 810,763. More particularly, these most interesting references, while writing 3.

herbicidal activity on a large number of weeds does not provide results for compounds which are shown to additionally and / or simultaneously control hard-to-destroy perennial weeds, consisting of quack grass and the yellow sedge of walnut trees, and a wide range of annual weeds, including broad-leaved, annual weeds that are difficult to destroy, such as spiny AIDS, hemp sesbania, so-called jimson grass, etc. and grassy type annual weeds such as young grass seedlings

Johnson, brittle cane, Alexander grass (brachiaria), i, panicums (Texas, Fall and wild prosomillet), red rice and spicy grass (Raoul grass), while also controlling other noxious, perennial and perennial weeds, for example beautiful grass, quarter lamb, 1'-anserine, fox tails, large wild grass and backyard grass.

A highly useful and desirable property of herbicides is the ability to maintain control or destruction of weeds for an extended period of time; the longer this period, the better it is during each harvest season. With many prior art herbicides, control or weed control is adequate only for 2 or 3 weeks, or in some cases higher, may be up to 4-6 weeks, before the chemical loses its effective phytotoxic properties. As a result, a disadvantage of most prior art herbicides is their relatively short lifespan in the soil. Another disadvantage of some prior art herbicides, somewhat related to longevity in the soil under normal climatic conditions, is the lack of persistence of weed control under a heavy rain fall which disables nom-35 * weedy herbicides.

Another disadvantage of many prior art herbicides is the limitation of their use.

in specified soil types, that is, while some herbicides are effective in soils with low amounts of organic matter, they are ineffective in other soils with high organic matter content or vice vice versa. It is therefore advantageous that a herbicide is useful in all types of soil, ranging from light organic soil to heavy clay and manure (hard-k).

Yet another disadvantage of many herbal cides of the prior art is the limitation to a particular effective mode of application, that is to say by the mode of application of pre-emergence on the surface or by incorporation. in the ground. It is highly desirable to be able to apply the herbicidal ion according to any mode of application, whether by surface application or by incorporation into the soil.

Finally, a disadvantage in some herbicides is the need to adopt and maintain special handling procedures due to their toxic nature. Therefore, another wish is that a herbicide be safe to handle.

It is therefore an object of the present invention to provide a decomposed herbicide group which overcomes the above-mentioned drawbacks of the prior art and which provides a multiplicity of advantages hitherto not obtained in a single group of herbicides.

It is another object of the present invention to provide herbicides which control an-C weeds. 30 beetles and perennials, difficult to destroy, such as charlatan grass, yellow sedge of walnut trees, young Johnson grass plants, spiny AIDS, sesbania hemp, brittle cane, Alexander grass , panicums, red rice and stinging grass, as well as, and in addition, a wide range of other noxious weeds, for example beautiful grass, quarter lamb, anserine, l grass called jimson, fox tails, backyard grass and grass.

be wild, and also provide increased suppression of resistant weeds such as rag grass (tattered grass), velvet leaf, garden volubilis and field niel, while maintaining security plants to be harvested in a large number of crops including soybeans), cotton, peanuts, rapeseed and / or white beans.

It is another object of the present invention to provide herbicidal efficacy in the soil for periods of up to 18 weeks.

It is yet another object of the present invention to provide herbicides which resist leaching and dilution due to high humidity conditions, for example in the form of heavy rain.

Still another object of the present invention is the provision of herbicides which are effective in a wide range of soils, for example, from light to medium organic soil to heavy clay and manure (garbage).

Another advantage of the herbicides of the present invention is the flexibility available from the point of view of application, that is to say by application of pre-emergence on the surface and by incorporation into the soil.

Finally, it is an advantage of the herbicides of the present invention that they are safe and do not require special handling procedures.

The objects indicated above and other objects of the present invention will appear from the detailed description below.

The present invention relates to herbicide active compounds, herbicidal compositions containing these compounds as active ingredients and herbicidal methods of using these compounds in particular crops.

We have now found that a selective group of "35 .2-haloacetanilides, characterized by specific hydrocarbyloxymethyl radicals on the anilide nitrogen atom, specific alkoxy radicals in an ortho position and 6.

hydrogen or a methyl or ethyl radical in the other ortho position, possess remarkable and unexpectedly superior herbicidal properties compared to herbicides of the prior art comprising compounds homologous to the most advantageous prior art.

A main feature of the herbicidal compositions of the present invention is their ability to control a wide range of weeds # including weeds controllable by common herbicides and # 10 in addition, several weeds which # individually and / or collectively # have escaped heretofore controlled or destroyed by a single class of known herbicides # while maintaining safety for the plants to be harvested> with respect to one or more crops comprising # in particular, soybeans # of cotton # peanuts # rapeseed and brittle beans # and other crops. While prior art herbicides are useful for controlling or destroying a large number of weeds including occasional resistant weeds, the unique herbicides of the present invention have been found to be able to control or suppress greatly several resistant annual and perennial weeds # such as perennial weeds consisting of quack grass and yellow sedge of walnut trees, annual broadleaf weeds such as spiny aids, sesbania hemp, so-called grass jimson, beautiful grass, quarter lamb, anserine, and annual herbs such as brittle cane, Alexander grass, young Johnson herb plants, Texas panicum, wild prosomillet 30 ge, red rice, stinging grass and other noxious weeds such as fall panicum, fox tails, backyard grass and wild grass. Improvement in weed foot reduction has also been obtained for resistant weeds such as rag grass (shredded grass) velvet leaf, garden volubilis and field niel.

The compounds of the present invention are characterized 7.

0 laughed at by the formula; C1CH-C CH.OR Δ \ / 1 ^ where R is the ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, cyclopropylmethyl, allyl or propargyl group; is methyl, ethyl, n-propyl or isopropyl, and R2 is hydrogen, methyl or ethyl; 15 provided that; when R £ is hydrogen, R ^ is the ethyl group, and R is the allyl group; when is the ethyl group, R ^ is the methyl group and R is the isopropyl group; 2n when R ^ is the methyl group, R is the ethyl, isopropyl, isobutyl, sec-butyl or cyclopropylme-thyle group; when is the ethyl group, R is the sec-butyl, allyl or propargyl group; ? When R ^ is the n-propyl group, R is the ethyl group, and when R ^ is the isopropyl group, R is the ethyl or n-propyl group.

The preferred species of compound of the present invention is 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide.

Additional species of the present invention are: ie 2'-methoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2'-methoxy-6'-methyl-N- (1-sec- butoxy-methyl) -2-chloroacetanilide, 35 8.

2'-ethoxy-6'-methyl-N- (allyloxymethyl) -2-chloroactanilide, 2'-ethoxy-6'-methyl-N- (propargyloxymethyl) -2-chloroacetanilide, 5. 2'-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide, 2'-methoxy-6'-ethyl-N- (isopropoxymethyl) -2-chloroacetanilide,.

2'-ethoxy-61-methyl-N- (1-methylpropoxymethyl) -2-10 chloroacetanilide, 21-n-propoxy-6 * -methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2'-isopropoxy -61-methyl-N- (ethoxymethyl) -2-chloroacetanilide; and 2'-isopropoxy-6'-methyl-N- (n-propoxymethyl) -2-chl-oroacetanilide.

The usefulness of the compounds of the present invention as active ingredients in herbicidal compositions formulated with these compounds and their method of use will be described below.

The compounds of the present invention can be made in a number of ways. For example, these compounds can be prepared by the azomeethine method described in US Pat. Nos. 3,442,945 and No. 3,547,620 indicated above. According to the azomethine process, the appropriate primary aniline is reacted with formaldehyde to obtain the corresponding methyleneaniline (substituted phenylazomethine), which is then reacted with a haloacetylating agent such as chloro-30 chloride acetyl or chloroacetic acid anhydride, which in turn is reacted with the appropriate alcohol to obtain the corresponding N-alkoxymethyl-2-chloroacetanilide as a final product.

Another procedure described in more detail below involves transetherification of the appropriate N-methylene-ether-2-haloacetanilide with the desired alcohol to obtain the N-hydrocarbylmethyl-2-haloacetanilide 9.

corresponding transetherification.

Yet another process for producing compounds according to the present invention involves N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent under basic conditions. The N-alkylation process is described in more detail in Examples 11-14 here.

EXAMPLE 1

This example describes the preparation of a ready-made species, 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chlo-roacetanilide.

2'-methoxy-6 * -methyl-N- (methoxymethyl) -2-chloroacetanilide (0.025 mole) in 100-150 ml of isopropanol containing about 0.02 mole of methanesulfonic acid was heated at reflux in an extraction device called Soxhlet, the cartridge of which contained Molecular Sieves called 3A activated (25 g) to absorb the released methanol. The course of the reaction was followed by gas-liquid chromatography. When the reaction was complete, the excess alcohol was removed in vacuo and the residue taken up in ether or chloroform. The solution was washed with 5% sodium carbonate solution, dried (MgSO 4) and evaporated. The product was purified by distillation in a device called Kugelrohr. Yield, 55%; pale amber solid, m.p. 40-41eC.

Analysis calculated for C14H2QC1N03 (%): C, 58.84; H, 7.05; N, 4.90; Cl, 12, 41.

Found: C, 58.55; H, 7.08; N, 4.89; Cl, 12.45.

The product was identified as being that described in the first phase of this example.

EXAMPLES 2-9

By following substantially the same procedures, the same quantities of reactants and the same general conditions as those described in Example 1, but by substituting the appropriate alcohol to carry out the transetherification in order to obtain the final product, other N-hydro-carbyloxymethyl-2-haloacetanilides, according to the formula indicated 10.

above, have been prepared; these compounds are identified in Table I.

TABLE I

1 Example- Compound [Formula ëm- PE1 Analysis - ~ 5 J pie pirique ° C Ëla- Calcu- Trou- n ° (mm ment lëe vé ___ H £) _____ 2 2 '-methoxÿ-6' -mé CnH C1N0, 17Ö C 57.46 57.19 thyl-N- (ethoxyma- ((0.1) H 6.67 6.70 thyl) -2-chloro- N 5.16 5.11 acetanilide Cl 13.05 13.09 10 3 2'-methoxy-6'-me- C H9 ~ C1N07 C 60.10 59.90 thyl-N- (1-methyl- 13 6 H 7.40 7.36 „propoxymethyl) -2- N 4.67 4.62 chloroacetanilide Cl 11.83 11.97 4 2'-ethoxy-6'-me- ClnH-ClNO. 110 C 60.50 60.30 thyl-N- (allyloxy- ιυ ΔΌ * (0.07! H 6.77 6.80 methyl) -2-chloro- N 4.70 4.64 15 acetanilide Cl 11.91 11.69 5 2'-ethoxy-6'-meC, _HinClN0. 140 C 60.91 60.98 thyl-N- (propargy- (0,1) H 6,13 6,14 loxymethyl) -2- N 4.74 4.74 chloroacetanilide Cl 11.99 11.94 6 2'-efhoxy-6-me- C1 # .H9 CINO ^ 135 C 61.24 60.98 20 thyl-N- (1-methyl- ± b J (0.09! H 7.71 7.69 propoxymethyl) -2- N 4.46 4.42 chloroacetanili- Cl 11.30 11.22 of 7 2 '-methoxy-6' -m- CH „C1N0 , 140 C 60.10 59.88 tfiyl-Nr (isobuto * 1 1 6 (0.1) H 7.40 7.41 xymethyl) -2-chlo- N 4.67 4.62 25 roacetanilide Cl 11.83 11.82 8 2'-methoxy-6'-met .. ςΗ_ C1N0., 145 C 60.50 60.26 thyl-N- (cyclopro- J (0,1) H 6,77 6,77 pylmethoxymethyl ) - N 4.70 4.66 2-chloroacetani- Cl 11.91 11.80 lide 9 2'-methoxy-61- C. H C1NO, oil C 60.10 59.81 ethyl-N- (isopro- ± :> JH 7.40 7.46 poxymethyl) -2- N 4.67 4.61 chloroacetanili- Cl 11.83 11.71, __ of _____- _ EXAMPLE 10 This example describes the preparation of the starting materials consisting of N - (methoxymeth yl) tertiary anilides, used to prepare the final products in Examples 1-9.

π.

The starting materials consisting of N-methyleneether-substituted 2-chloroaceous-tanilide used in Examples 1 ^ 9 were prepared by alkylating the appropriate secondary 2-haloacetanili-by the N-alkylation process referred to above. This process will be illustrated in this example with respect to the preparation of the starting material in Example 1.

2'-methoxy-6'-methyl-2-chloroacetanilide (0.025 mole), methyl bromomethyl ether (0.05 mole) and benzyltriethylammonium bromide (2 g) were dissolved in chloride methylene (70 ml). A sodium hydroxide solution (40 ml of a 50% solution) was then added in parts with stirring and cooling, keeping the temperature between 20 and 25 ° C. When the stirring was complete, the mixture was stirred for an additional 1.5 hours. Water (100 ml) was then added with cooling and the layers separated. The methylene chloride layer was washed twice with 30 ml of saturated sodium chloride solution, dried (MgSO 4) and evaporated. The residual product was crystallized or distilled under vacuum to obtain a yellow liquid, e.g. 140 ° C. under 1.2 mm Hg.

Analysis calculated for ci2H16ClN03 (%)! c> 55.92; H, 6.26; N, 5.44;

Found: c, 56.15; H, 6.33; 25 N, 5.36.

The product has been identified as 2'-methoxy-6'-methyl-N- (methoxymethyl) -2-chloroacetanilide.

Similarly, the starting N-methyleneether-substituted 2-chloroacetanilides shown in Examples 2-9 were prepared by alkylation of the corresponding secondary anilide with bromomethyl ether, respectively; it is also possible to use analogous ethers of chloromethyl and iodomethyl and methyl.

The starting material consisting of secondary anilide-35 re, used in this example to prepare the tertiary N-me-thoxymethyl compound, was prepared by chloroacetylation of the corresponding primary amine as follows; 12.

2-methoxy-6-methylaniline (0.03 mole) in. methylene chloride (30 ml) was stirred vigorously with a 10% sodium hydroxide solution (0.05 mole), while a solution of ehloroacetyl chloride (0.033 mole) in methylene chloride (20 ml) was added while maintaining the temperature between 15 and 25 ° C with external cooling.

The reaction mixture was stirred for a further 30 minutes after the addition was complete, the layers separated and the layer of methylene chloride washed with water, dried and evaporated in vacuo. The product was crystallized from a suitable solvent to obtain white needles, m.p. 130-131 ° C.

Analysis calculated for ci0Hi2C1N02 (%): C, 56.21; H, 5.66; N, 6.56; Cl, 16.59 Found: C, 56.16; H, 5.66; N, 6.57; Cl, 16.55.

The product has been identified as 2'-methoxy-6'-methyl-2-chloroacetanilide.

The secondary anilides used as starting materials in Examples 2-9 were prepared in a similar manner.

The primary amines used to prepare the above mentioned secondary anilides can be prepared by known means, for example by catalytic reduction of the corresponding substituted nitrobenzene in ethanol, using a platinum oxide catalyst.

As mentioned above, the products of the present invention can also be prepared directly from the secondary anilide using the N-alkylation process, without first preparing the intermediate Jtf-hydrocarbyloxymethyligue (as described in Example 10), which is then transetherified to provide the final product as described in Example 1. Examples 11-14 illustrate the preparation of the species of the present invention by this N-alkylation process.

EXAMPLE 11

2'-n-propoxy-6'-methyl-2-chloroacetanilide 13.

(4.35 g), ethyl chloromethyl ether (3.4 g), benzyltriethylammonium chloride (1.5 g) were mixed in 250 ml of methylene chloride and cooled. To the mixture was added 50 ml of 50% NaOH at 15 ° C and stirred for 2 hours, then 100 ml of water was added. The layers were separated, washed with water and then dried over MgSO4 and evaporated. The product was purified by distillation in the so-called Kugelrohr device to obtain 4.8 g (89% yield) of clear liquid, e.g. 130 ° C under 0.07 XO mm Hg.

Analysis calculated for C ^ H ^ ClNO-j (%): C, 60.10; H, 7.40;

Cl, 11.83.

Find ; C, 59.95; H, 7.39;

Cl, 11.79.

The product has been identified as 2'-n-propoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide.

EXAMPLE 12

2'-isopropoxy-6'-methyl-2-chloroacetanilide (5.55 g), chloromethyl ether (4.4 g), benzyltriethylammonium chloride (2.5 g), in 250 ml of methylene chloride, were mixed and cooled to 0 ° C. To the mixture, 50 ml of 50% NaOH was added all at once, while keeping the temperature below 15 ° C. The mixture was stirred for 2 hours, cooled, then 100 ml of water was added. The layers were separated, washed with water, dried over MgSO 4 and evaporated to obtain 4.7 g (yield 69%) of the product which is a yellow oil.

Analysis calculated for cx5H22ClN03 (%): C, 60.10; H, 7.40; 30 N, 4.67; Cl, 11.83;

Find ; C, 60.10; H, 7.40; N, 4.64; Cl, 11.73.

The product has been identified as 2'-isopropoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide.

35 EXAMPLE 13

By following substantially the same procedure as that described in Examples 11 and 12, but using 14.

chloromethyl ether of propyl as alkylating agent, 5.0 g (88% yield) of a yellow oil were obtained. Analysis calculated for C16H24C1N03 (%): C, 61.24; H, 7.71; N, 4.46; Cl, 11.30.

5 Found: C, 61.18; H,. 7.76; N, 4.43; Cl, 11.31.

The product has been identified as 2'-isopropoxy-6-methyl-N- (n-propoxymethyl) -2-ohloroacetanilide.

EXAMPLE 14 Following the same procedure as that described in Examples 11-13, but substituting the appropriate sec-anilide and halomethyl and allyl ether, a yellow oil was obtained, eg 134eC / 0 , 08 mm Hg (device known as Kugel-rohr).

Analysis calculated for C] _4Hi8C1N03 (%): C, 59.26; H, 6.39; N, 6.94; Cl, 12.49.

Found: C, 59.20; H, 6.41; N, 6.95; Cl, 12.52.

The product has been identified as 2'-ethoxy-N- (allyl-20 oxymethyl) -2-chloroacetanilide.

The herbicides of the present invention have been found to possess unexpectedly superior properties as pre-emergence herbicides, particularly for selective control or selective destruction of hard-to-destroy annual and perennial weeds. , including perennial weeds such as quack grass and yellow walnut sedge; broadleaf annual weeds, such as spiny aids, sesbania hemp, jimson grass, belle-grass, quarter lamb, ansërine and annual herbs such as seedlings Johnson grasses, brittle cane, Alexander grass (Brachiaria plantaginea), Texas panicum, red rice, wild prosomillet, stinging grass, fox tails (e.g. re-35 tail. green nard and giant fox tail), backyard grass and large wild grass. Improved reduction in weed feet compared to 15 acetanilides.

The prior art has also been obtained on other resistant species, such as rag grass (tattered grass), velvet leaf, garden volubilis and field niel.

Selective control and increased control of the aforementioned weeds with the herbicides of the present invention have been found in a large number of crops, including soybeans, cotton, peanuts, rapeseed and brittle beans (White beans).

] _0 Selectivity has been presented in some tests on sugar beets, field corn, wheat, soft corn, barley and sorghum; however, these plants for harvesting are ordinarily less tolerant of the herbicides of the present invention than the plants for harvesting earlier. Those skilled in the art will understand that not all of the above-mentioned weeds are selectively controlled by all of the compounds of the present invention under all conditions of climate, soil type, humidity and / or 2o modes of herbicide application.

• -

To illustrate unexpectedly superior properties of the compounds of the present invention, on an absolute and a relative basis, comparative tests were conducted in greenhouses and fields with: 25 (1) prior art compounds most closely related, from the chemical structure point of view, to the compounds of the present invention, (2) other homologs included in the field of the prior art which have superior herbicidal properties and (3) herbicidal compounds of the trade with a chemical structure generally related to that of the compounds of the present invention.

All of the compounds in the comparative tests below are generically defined as phenyl-N-aïcoxÿàlkyl · -2-haloacét ^ nilides. As used in the result tables here, the compounds of the prior art compared are identified as follows: A. 2'-methoxy-6'-t-butyl-N- (methoxymethyl) -2-chlo- 16 .

roacetanilide (example 18, US patents · 3,442,945 and 3,547,620).

B. 2'-methoxy-6'-t-butyl-N- (methoxymethyl) -2-bromo-acetanilide (example 34 of American patent n ° 5 3,547,620 and example 36 of American patent n ° 3,442,945 ).

C. 21.6'-diethyl-N- (methoxymethyl) -2-chloroaceta-nilide (example 5 of American patent n ° 3,547,620 and American patent n ° 3,442,945; this compound has the common name "alachlor "and is the active ingredient in the commercial herbicide known under the registered trademark LASSO, registered trademark of the company known as Monsanto Company).

D. 2'-methyl-6'-ethyl-N- (ethoxymethyl) -2-chloroacetanilide (Example 53 in US Patent No. 3,547,620; common name "acetochlor").

E. 2 ', 6'-dimethyl-N- (isopropoxymethyl) -2-chloroaceous-tanilide (example 31 of American patent n ° 3,547,620 and example 33 of American patent n ° 20 3,442,945).

F. 2'-methoxy-6'-methyl-N- (methoxyethyl) -2-chloroaceous-tanilide (compound no 6 of Belgian patent n ° 810,763).

G. 2'-methoxy-6'-methyl-N- (ethoxyethyl) -2-chloroaceous-tanilide (compound no. 7 of Belgian patent no. 810,763).

H. 2'-methoxy-6'-methyl-N- (1-methoxyprop-2-yl) -2-chloroacetanilide (compound no. 9 in Belgian patent no. 810,763); and 3q I. 2'-methyl-6'-ethyl-N- (1-methoxyprop-2-yl) -2-chloroacetanilide (US Patent No. 3,937,730; common name "metolachlor"; this compound is the ingredient active in the commercial herbicide known • under the registered trademark "Dual" which is a registered trademark of the company called Ciba-Geigy Corpora tion).

In pre-emergence herbicide tests, the 17.

The present invention has been compared to prior art AI compounds against the control of various annual and perennial weeds, emphasizing hard-to-destroy species which are predominant infestations in important crops such as than soybeans, cotton, peanuts, rapeseed and white beans. The experimental results are presented below.

In the discussion of the results below, reference is made to the rates of herbicide application indicated symbolically by "GR ^ g" and "GRgg"; these rates are given in kilograms per hectare (kg / ha). GR ^ g defines the maximum rate of herbicide required to obtain 15% (or less) of crop damage, and GRg5 defines the minimum rate exi-15 gë to obtain 85% inhibition of weeds. The GR ^ çj and GRgg rates are used as measures of potential commercial performance, it being understood of course that suitable commercial herbicides can cause more or less damage to plants within reasonable limits.

Another guide to the effectiveness of a chemical as a selective herbicide is the "selectivity factor" ("FS") for a herbicide in given crops and weeds. The selectivity factor is a measure of the degree of safety for the crops and is expressed by the ratio GR ^ / GRg,., That is to say the rate GR ^ for the harvest divided by the rate GRg5 for the bad grass, the two rates being in kg / ha. In the tables below, when used, the selectivity factors are shown in parentheses after the weed; the symbol "NS" indicates "non-selective"; marginal or undetermined selectivity is indicated by a dash (-) after the weed and a space left blank indicates that the plant species was not present in a particular test, which was not 35 Obtained the results for certain reasons or that these results were less important than other results present, for example some shorter-term observations are 18.

removed in favor of longer term results or. longer term results are suppressed because the shorter term results were final for a particular herbicidal activity.

5 Since crop tolerance and weed control are interrelated, a brief discussion of this relationship in terms of selectivity factors is significant. In general, it is desirable that the tolerance values for the crops be high, since higher concentrations of herbicide are frequently desired for one reason or another. Conversely, it is desirable that weed control rates be low, that is, that the products have high unit activity for economic and possibly ecological reasons. However, low rates of herbicide application may not be adequate for controlling certain weeds and a higher rate may be required. Therefore, the best herbicides are those that control the greatest number of weeds with the least amount of herbicide and which. provide the highest level of crop security, i.e. tolerance for crops. Therefore, "selectivity factors" (defined above) are used to quantify the relationship between crop security and weed control. With reference to the selectivity factors shown in the tables, the higher the numerical value, the greater the selectivity of the herbicide for weed control in a given crop.

The pre-emergence tests referred to here include tests in the fields and tests in the greenhouses. In tests in greenhouses, the herbicide is applied either as a surface application, after having planted seeds or vegetative propagules, or by incorporation in a certain amount of soil to be applied as a covering layer on the experimental seeds in pre-sown experimental containers.

these. In field tests, the herbicide is incorporated before the plant ("PPI") into the soil, that is, the herbicide is applied to the soil surface and then incorporated into it by means of mixing, followed by planting of the 5 plant seeds to be harvested.

The experimental surface application process used in the greenhouse is carried out as follows: receptacles, for example aluminum boxes typically 24.13 cm x 13.34 cm x 6.99 cm, or plastic pots, of 10 9.53 cm x 9.53 cm x 7.62 cm, having drainage holes in the bottom, are filled at level with a soil of mud soil (silty soil) called RAy and then compacted until a level of 1.27 cm from the top of the pots. The pots are then seeded with a species of plant to be tested, then covered with a 1.27 cm layer of the experimental soil. The herbicide is then applied to the soil surface with a belt sprayer at the rate of 187 liters per hectare, under a pressure of 2.11 2 kg / cm; other spraying means, for example a positive spraying device known as DeVilbiss, are also used on occasion. Each pot receives 0.64 cm of water as top irrigation and the pots are then placed on greenhouse benches for further irrigation from below, as necessary. As an alternative procedure, overhead irrigation can be omitted. Observations of herbicidal effects are made approximately three weeks after treatment.

The following herbicide incorporation treatments used in greenhouse tests are as follows:

A good quality top soil is placed in. aluminum cans and is compacted to a depth of 9.5mm to 12.7mm from the top of the box. Above the ground are placed a number of 35 * seeds or vegetative propagules of various plant species. The soil required to fill the boxes at level after sowing or adding vegetative propagules is small.

dried in a box. The soil and a known amount of the active ingredient applied in a solvent or as a wettable powder suspension are completely mixed # and used to coat the prepared dishes. After treatment, the boxes are given an initial aqueous irrigation at the top equivalent to a 0.64 cm rainfall, then the boxes are moistened by irrigation from below, as necessary to give adequate humidity for the germination and growth. As a procedure as an alternative XO, top irrigation can be omitted.

Observations are made approximately three weeks after> seeding and treatment.

In a first series of tests, the results of pre-emergent herbicidal activity are presented in table II, comparing the relative efficacy of the compounds of the present invention, with compounds of interest in the prior art against yellow sedge of walnut trees and quack grass in soybeans, cotton and corn.

TABLE II

20, _; _

Rate for GRQC. Rate for GR.

(kg / ha) _ (kg / ha) lb_

Corn- Carex Soybean Cotton Corn laid charla- __nut trees tan_____ A> 2.24 “3.13 (-)> 2.24 R 0.17 (NS) 25 1.56 0.28 (NS) 0.28 (NS) B 0.70 0.56 (NS)> 2.24 (> 2.0) 0.035 (NS) 2.80 1.12 (NS) 0.07 (NS) C 0.44 1.68 ( 4) 0.84 (2) 0.56 1.12 (2) 0.84 (1.5) D 0.22 0.39 (1.5) 0.27 (1) 0.22 (1) 30 0.18 0.39 (2) 0.22 (1) E 0.16 0.21 (1) 0.48 (3) 0.096 (NS) P 0.32 0.21 (NS) 0.21 (NS ) <0.22 (NS) 0.26 0.21 (NS) <0.22 (NS) G 0.24 <0.07 (NS) 0.39 31.5) <0.07 (NS) 0 , 20 <0.07 (NS) <0.07 (NS) 35 'H 1.45 2.191 (1.5) 2.91 (2) <1.45 (NS) 0.36 2.15 (6) 2.70 (7.5) 1.25 (3.5) I 1.68 <1.68 (NS) <1.68 (NS) <1.68 (NS) 0.09 1.34 (1, 5) 1.34 (1.5) <0.88 (NS)

Ex. 1 0.104 0.28 (3) 0.28 (3) '<0.07 (NS) 0.20 0.28 (1.5) <0.07 (NS) 21.

TABLE II (Continued)

Ex. 2 0.16 0.17 (1) 0.17 (1) <0.17 (NS) 0.07 0.13 (2) 0.07 (1) <0.07 (NS) 5 Ex. 3 0.26 0.77 (3) 0.77 (3) <0.26 (NS) 0.13 0.80 (6) <0.13 (NS)

Ex. 4 0.33 1.00 (3.0) 1.00 (3.0) <0.32 (NS) 0.22 1.00 (4.5) <0.22 (NS)

Ex. 5 0.28 3.36 (12.0) 2.80 (30.0) <0.28 (NS) 0.28 3.36 (12.0) <0.28 (NS) 10 Ex. 6 0.26 2.01 (8.0) 2.57 (10.0) <0.26 (NS) 0.28 2.24 (8.0) <0.28 (NS)

Ex. 7 0.22 0.89 (4.0) 1.45 (6.5) 0.14 (NS) 0.56 0.89 (1.6) 0.14 (NS)

Ex. 8 0.37 0.56 (1.5) 0.71 (1.9X0.13 (NS) 0.17 0.56 (3.3) <0.13 (NS) 15 Ex. 9 0, 56 5.6 (10.0) 1.68 (3.0) <0.28 (NS) 0.47 5.6 (11.9) <0.28 (NS)

Ex. 12 0.12 0.28 (2.5) 0.27 (2.0) <0.12 (NS) 0.11 0.28 (2.5) <0.11 (NS)

Ex. 13 0.22 0.45 (2.0) 2.70 (12.0X0.22 (NS) 0.28 0.56 (2.0) <0.28 (NS) 20 Ex. 14 0, 36> 5.6 015.6) 1.40 (3, * 9) 5.6 (15.6) 0.50> 5.6 (> 11.1) 5.6 (11.1)

Referring to the results in Table XI, it will be seen that in general the compounds of the present invention, as a class, are significantly more active, i.e., they have a higher unit of activity, against the yellow sedge of the walnut trees and the quack grass and that they present a greater safety for the plants to be harvested, in soya beans and cotton, compared to the reference compounds.

More particularly, with respect to the control of the yellow sedge of the walnut trees, it will be noted that each compound of the present invention tested was remarkably more active against the yellow sedge of the walnut trees than the compounds A and B ′, which are structurally the most intimately related among the reference compounds, and the compound H, which, while being less intimately related than A and B, may be considered more intimately related, under certain 22.

aspects, to the compounds of the present invention as the components C, D, E and I. Even more particularly) it will be noted that the compound of example 1, having a GRgg of 0.10 kg / ha was approximately two times more active than the most active of the reference compounds, compound E (GRg, from 0.16), while having a safety factor for crops (plants to be harvested) three times greater than the compound E in soybeans and equivalent safety in cotton. It will also be noted that the compounds of the present invention of Examples 2 and 12 also had equivalent unit activity and greater unit activity, respectively, than compound E with respect to the yellow sedge of the walnut trees.

In addition, although the reference compounds F and G have a fairly high unitary activity, neither of these compounds was selective for the yellow sedge sedge in soybeans , more than compound F was selective in cotton. Although the compound G selectively controls the sedge of the walnut trees in the cotton, the degree of safety was · "Tfii & fxeur ~ a ~ that existing for all the compounds of the pre-20 sente invention, except example 2, and clearly lower than that existing for examples 5,6 and 13. The selectivity factors of the compounds of examples ^ and 14 with respect to the sedge of walnut trees in soybeans were particularly remarkable.

25 With regard to the control of latan char, the compound of Example 2 was almost three times more active than the most active reference chemical, Compound D, while maintaining equivalent safety "for crops (plants to harvest) in soybeans. The starch of the present invention of Example 3 also had a greater unitary activity with respect to the charlatan herb and three times more security for the soybeans than ·> mosé D. Again, it will be noted that each compound of u -.t '/ ention tested against the charlatan grass had an ac -':> "unit ivlté remarkably superior compared to compounds A and B which are the reference compounds tested the: read intimately Although the unitary activity of the 23.

posed H against the charlatan grass is slightly higher than that for the compounds of Examples 9 and 14, the selectivity factors for the latter compounds against the charlatan grass in the soybeans was about double 5 that of the compound H, the next most closely related compound among the reference compounds. In addition, the reference compounds A, B, F and G were non-selective against quack grass in soybeans.

On the other hand, observations to note in the results of Table II are that, among all of the compounds tested / the compounds of Examples 5, 6, 9 and 14 had the most remarkably high safety factors in soybeans compared to yellow sedge of walnut trees and charlatan grass. The compounds of Examples 5, 6 and 13 had, by far, the highest safety factors in cotton compared to the yellow sedge of walnut trees. It should also be noted that the considerable safety factors for harvesting the compounds of Examples 5, 6, 9 and 13 and 14 are accompanied by very low levels GR ^,., Indicating a high unit activity against the yellow sedge of walnut trees and charlatan grass. In these tests, most of the compounds of the present invention were non-selective in corn, as were all but three of the reference compounds. However, the compound of Example 14 exhibited remarkably higher selectivity compared to quack grass and the yellow sedge of walnut trees in corn.

In other comparative tests, the pre-emergence herbicidal activities of the reference compounds B and D and of the compound of Example 1 were tested against various annual broadleaf weeds at a rate of application. of. 3.36 kg / ha. Observations were made 6-7 weeks after treatment (SAT) and the percentage of weed control was recorded; the results from these tests are presented in Table III.

24.

TABLE III

Annual broadleaf weed control, pre-emergence, 6-7 SAT

Percentage of ~ control at 3.36 kg / ha 5 Bad Grass Compound____

Example 1____C__D_

Thorny AIDS 93 35 73

Hemp. sesbania 100 0 69 10

Anserine 83 62 88

Beautiful grass 88 64 76

Quarter of lamb 75 61 81

Grass chif-15 fon (shredded grass) 72 53 43

Grass said j imson__9_8__68_ 9J_

From the results in Table III, it appears that the compound of Example 1 had a remarkably higher activity compared to the compound C

against all tested broadleaf weeds. Similarly, the compound of Example 1 exhibited markedly higher activity than compound D against thorny AIDS, sesbania hemp, beautiful grass and ragweed, while exhibiting equivalent activity against the grass. so-called jimson and slightly less unitary activity against anserine and quarter-lamb.

In other comparative tests, field tests were conducted to determine the relative pre-emergence herbicidal activities and the selectivities for the harvests of the compound of Example 1 compared to the reference compounds C, D, E and I against backyard grass, thorny AIDS and sesbania hemp in soybeans. These tests were carried out in separate field lots of clay soil (Sharkey) containing 2.0% organic matter and treated with various concentrations of each herb.

bicide applied in the form of an emulsifiable concentrate, with an application volume of 280.5 1 / ha. Observations were made 4 weeks and 7 weeks after treatment.

Based on three tests, carried out in duplicate, the experimental results show that, for the observation of 7 weeks, the only compound which selectively controlled sesbania hemp was the compound of Example 1; this control (GRgg) was obtained with only 1.96 kg / ha, while the GRg5 for each of the compounds C, E and I was 5.6 kg / ha and 5.0 kg / ha for the compound D. The in soybeans was 3.9 kg / ha, resulting in a safety factor 2.0 times greater for the compound of Example 1. Thus, it was required about 3 times more reference compounds to obtain the GRoe than what is required for the .composite of Example 1, but

Oj 15 without selectivity in soybeans.

The. compounds C and D were non-selective against thorny AIDS in soybeans for 7 SATs. Compound 1 required 4.2 kg / ha and Compound E required 2.8 kg / ha to obtain GRgj. and the selectivity factors of 1.1 times 2o and 1.5 times respectively. In contrast, the compound of Example 1 obtained a GRoe with only 0.8 kg / ha and a selectivity factor of 4.7 times in soybeans.

Compounds c, D and E were non-selective against backyard grass in soybeans for 7 SATs. Compound 1 and the compound of Example 1 had substantially equivalent safety factors, i.e. 1.5 times versus 1.4 times, respectively.

Thus, the tests in the fields indicated above show that, if it were not for the comparable control of the backyard her-30 be compared to the compound I, the compound of example 1 was clearly superior to the Reference compounds C, D, E and I for the selective control of three annual weeds in soybeans after 7 weeks after treatment.

i 35, In other tests to determine relative herbicidal activities and selectivities for even longer periods of time, the same herbicides as * 26.

those used in the previous tests were again tested in the fields, this time in .lots of land separated from loamy clay soil to loam clay potting soil containing 3.0-3.5% organic matter.

In parallel tests, emulsifiable concentrates of the respective herbicides were applied to the surface and incorporated before the plant for pre-emergence control, again at the rate of 280.5 l / ha containing the appropriate concentration of herbicide in as an active ingredient. In these 10 tests, the herbicides were compared with regard to their activity against the perennial weed constituted by quack grass and the annual broadleaf weeds constituted by rag grass, anserine and beautiful grass. in soybeans. These tests were exposed to a significant rain fall, the value of which is 4.45 cm on the 5th day after treatment ("JAT") and 2.29 cm, 1.52 cm, 1.27 cm and 1 , 27 cm of rain the following days. The experimental results are presented in Table IV.

TABLE IV

20 Pre-emergence activity

Incorporated before the plant ~~~ GRq5 Ucg7hâ5 GR15 (kg / ha)

Compound SAT Grass of! Grass Anséri-j Belle Sojas charla- cloth no grass ____tan______ 25 Ex. 1 3 2.24 1.68 6 2.24 5.88 2.24 2.52 2.52 9.5 2.52> 6.72 3.36 > 3.36 C 3> 6.72> 4.48 6> 6.72> 6.72> 6.72> 6.72> 4.48 9.5> 6.72> 6.72> 6.72> 4 , 48 30 D 3 5.60 3.92 6> 6.72> 6.72> 6.72 5.60 4.20 9.5 6.72> 6.72> 6.72 4.48 E 3> 6, 72 2.24 6> 6.72> 6.72 4.20 4.88 '2.80 9.5> 6.72> 6.72 4.48 4.20 I' 3> 6.72 1/68 35 ' 6> 6.72> 6.72> 6.72> 6.72 3.92 9.5> 6.72> 6.72 5.88 5.04 27.

TABLE IV (Continued)

Applied on the surface

Ex.l .. 3 2.52 1.68 6 2.52 4.48 4.48 3.36 3.36 9.5 4.48 5.05 3.36 4.76 4.20 5 C 3 5.90 3.92 6> 6.72> 6.72 4.48> 6.72 2.24 9.5> 6.72> 6.72 5.05 5.88> 4.48 D 3> 6.72 0.33 6> 6.72> 6.72 6.72 6.96 3.92 9.5> 6.72> 6.72 5.05 6.72 4.76 10 E 3 5.60 2.52 6> 6.72 > 6.72 5.60 4.48 1.96 9.5> 6.72> 6.72 5.05 5.60 4.76 I 3> 6.72 4.48 6> 6.72> 6.72> 6.72> 6.72 4.48 9.5> 6.72> 6.72> 6.72> 6.72 4.48 15 Referring to the results in Table IV, it will be noted that in the tests for incorporation before the plant, none of the reference compounds selectively controlled any of the experimental weeds in soybeans at rates up to 6.7 kg / ha, the maximum test rate, after six weeks and 9.5-week observations. As indicated above, the selectivity is indicated by a selectivity factor, or GR - ^ / GRgg ratio, of 1.0 or more; the higher the value, the greater the selectivity. In contrast, the compound of Example 1 exhibited selective control of quack grass, an-serine and beautiful grass after 6.0 weeks and control of quack grass. quack and beautiful grass after 9.5 weeks. It is shown that the herbicidal activity of the compound of Example 1 is of the order of 3 (or more) times greater than that of the reference compounds against quack grass and anserine (except compound D) and approximately 2 (or more) times greater than the reference compounds (except compound D for 6 and 9.5 weeks and compound E for 9.5 weeks). None of the herbicides selectively controlled rag grass (shredded grass) in this test, but the compound of Example 1 was more active against this weed than the reference compounds after 6 weeks.

28.

In the experimental results based on the surface application of the herbicides, again, none of the reference chemicals selectively controlled any of the weeds in the test in the 5 soybeans, at rates of 6.7 kg / ha or less after 6 weeks or 9.5 weeks of observations, except compound D in anserine for observations after 9.5 weeks. In these tests, selective weed control was observed for the compound of Example 1 in 10 11 quack grass and beautiful grass after 6 weeks and in anserine after 9.5 weeks; the safety factor here was slightly higher than the safety factor for compound D, i.e. 1.3 versus 1.1 times. Again, the compound of Example 1 exhibited a much higher herbicidal activity than that of the reference compounds in these tests.

From the results in Table IV, it appears that, starting from the criteria of unitary activity against weeds, the tolerance for soybeans with respect to herbicides, the safety factors and the modes of application. of herbicides, the compound of Example 1 exhibited significantly superior properties, as a pre-emergence herbicide, compared to the reference compounds compared.

The persistent weed control presented by the compound of Example 1 under the conditions of heavy rain noted above clearly showed that the compound was not easily leached.

In other comparative field tests, the compounds of Example 1 and the reference compounds D and E were tested for the selective control of thorny AIDS and of wild grass in cotton in modes of application of herbicide by surface application and by incorporation before the plant; the yellow sedge of the walnut trees was included in the incorporation test before the plant. The soil in these tests was loamy soil with 1.7% organic matter. The observations were made after "29.

2/6 and 9 weeks after treatment. Based on three tests carried out twice, the results from the surface application tests showed that the compound of Example 1 had more than twice as much unitary activity against thorny AIDS as compounds D and E after 6 weeks and 1.5 times their activities after 9 weeks. Compound D was non-selective against thorny AIDS in cotton after 6 and 9 weeks. The selectivity factors for compound E after 6 and 9 weeks respectively were 1.1 and 1.2, compared with 3.3 and 1.8 for the compound of Example 1. Good that the unitary activities of each compound tested are comparable against wild grass after 6 weeks, the compound of Example 1 was more active than Compound E after 9 weeks and 15 and more selective (it is ie FS> 4.0) than compound D having an F.'S. 2.8.

In the tests with incorporation before the plant, after 9 weeks, the unitary activity of the compound of Example 1 was more than twice that of the reference chemicals against the yellow sedge of walnut trees, slightly less than twice the unit activity of reference chemicals against wild grass and more than 1.33 times the unit activity of reference chemicals against thorny AIDS. In this field test, the compound of Example 1 selectively controlled the yellow sedge of the walnuts in cotton up to 6 weeks after treatment, but the reference chemicals did not show selectivity even after 2 weeks of observation. Although none of the experimental chemical rates selectively controls spiny AIDS in this P.P.I. test, the margin of selectivity was much closer to the compound for Example 1 than for the other compounds.

The compound of Example 1 and Compound E tightly controlled the wild grass after 2 weeks, but were not subsequently selective; Compound D was not selective against wild grass on any of the observation dates.

30.

Thus, the predominant conclusions which can be drawn from the tests mentioned above in the fields for cotton are that the compound of Example 1 was clearly more active than the reference compounds against the bad weeds constituted by the yellow sedge walnut trees and thorny idae, while maintaining this activity for a longer period of time, and that the compound of Example 1 had higher selectivity factors compared to these weeds. In addition, the compound of Example 1 had a higher unit activity compared to compound E and a higher selectivity compared to compound D against wild herb in cotton after 9 weeks.

Other comparative tests between the compound of Example 1 and compounds D and E were carried out to determine their relative herbicidal activities and their duration of use in the soil against the perennial weeds constituted by the yellow sedge walnut trees and charlatan grass. Compounds D and E are among the most active selective herbicides among the 2-haloacetanilides of the prior art and have been considered as class standards in tests for other herbicides against walnut sedge, grass quack and other weeds. In the tests indicated here, two tests carried out twice of each treatment were carried out by planting 25 to 25 tubers of yellow sedge from the walnut trees and 25 fragments of rhizomes of charlatan grass. The herbicides were incorporated into the soil cover layer at rates sufficient to determine the GR rate, -q, i.e. the minimum rate (in kg / ha) required to obtain control of 30 50% weeds; the rate of 11.2 kg / ha represented the maximum rate and 1.20 kg / ha the minimum rate applied in fact. Observations were made after 3, 6, 12, and 18 weeks. After each observation, the covering layer of the soil was removed, the old tuberous roots and the old fragments of rhizomes removed, replanted and then placed in the greenhouse for the next cycle. The experimental results are presented in Table V; "SAT" 31.

means "weeks after treatment".

TABLE V

Duration of use in soil GRg0 kg / ha *

Composed. Yellow sedge Chargrass- SÄT

5 ___ walnut trees___latan___

Example 1 <1.4 <1.4 3 <1.4 <1.4 6 1.4 1.4 12 8.4 11.2 18 D <1.4 <1.4 3 1.12 <1.4 6 10 5 , 9 5.6 12> 11.2> 11.2 18 E <1.4 <1.4 3 1.4 1.7 6 7.8 11.2 12> 11.2> 11.2 18 15 Referring to the results for the control of the yellow sedge of the walnut trees in table V, it is seen that after 3 weeks after the treatment, the GR5Q rate of each compound was less than 1.4 kg / ha, certain defined differences appearing after 6 weeks. After 12 to 20 weeks of birth, significant differences in the control of the walnut sedge were visible. Thus, where only 1.4 kg / ha of the compound of Example 1 was required to control 50% of the weed, 5.9 kg / ha of compound D and 7.8 kg / ha of the compound were required. compound E to obtain the same for control of the yellow sedge of the walnut trees. Also, for 18 SAT, only 8.4 kg / ha of the compound of Example 1 was required to control 50% of the walnut sedge by comparison with a certain indeterminate quantity greater than 11.2 kg / ha (maximum rate used) compounds D and E.

Similarly, the results for the quack grass in Table V show that, for 6 SATs, the compound of Example 1 and the compound D had slightly higher activity compared to the compound E. However, for 12 SAT, the remarkable supremacy of the compound of Example 1 is presented by the fact that it requires only 1.4 kg / ha to obtain the same control of the quack grass as that required by 5, 6 kg / ha of compound D and 11.2 kg / ha of 32.

compound £. The superior herbicidal activity of the compound of Example 1 also appeared for 18 SATs. >

A distinct advantage of the herbicide is its ability to work in a wide range of soil types. Accordingly, results are presented in Table VI showing the herbicidal effect of the compound of Example 1 on the yellow ca-rex of walnut trees in cotton and in soybeans in a wide range of soil types with variable content in organic matter and clay. The herbicide treatments were incorporated into the soil with seeds planted at 0.95 cm in depth, with a top irrigation of 0.64 cm. The observations were made 18 days after treatment.

TABLE VI

15 (kgjfôa) __ (kg / 'fia):

Corn- Type Matië- Clay, Carex Cotton Sojas; posed re or-% yellow! gani-. of ___ that,% ___ walnut trees___

Example - Soil li- 1.0 9.6 0.22 0.73 0.56

pie 1 moneux says 20 RaY

Soil of clay says

Sarpy 2.3 - 0.07 0.95 0.95

Soil clay clay known as 25 Georgeville 2.9 37.0 0.12 0.47 0.56

Soil of clay says

Wabash 4.3 33.0 0.22 1.12 0.95

Clay pellet li-30 moneuse dit

Drummer 6.0 37.0 0.22 0.95 0.87

Sand of

Florida 6.8 1.8 0.27 0.56 0.48

The results in Table VI show that the compound of Example 1 seems to be quite insensitive to the type of soil and to the content of organic matter, exhibiting selective control of the yellow sedge sediment in cotton and in the soybeans in soils with organic matter 33.

between 1.0 and 6.8% and clay between 1.8 and 9/6% .- The factors of selectivity were the highest in clay soil known as Sarpy.

Additional tests were conducted to determine the herbicidal performance of the compound of Example 1 in soils containing a large amount of organic matter. In three tests carried out in duplicate, in the fields # the activity of the compound of Example 1 was tested against anserine and a quarter of lamb in soybeans planted in 10 manure soil (garbage). Compounds C, D, £ and I were also tested for comparative purposes. These tests were carried out in application modes both by incorporation before the plant and by surface application in manure soil containing 23% organic matter.

15 In these tests, both in the P.P.I. and by surface application, the compound of Example 1 exhibited the highest unit activity against quarter lamb for 4 SATs and, in PPI mode, the most important selectivity factor in soybeans, that is that is, more than 2.7 versus 1.1 for each of compounds C and D; compounds E and I were non-selective for 4 SATs. All of the compounds were non-selective against quarter lamb for 7 SAT in either mode of application of the herbicide; Compound E was slightly more active than Compound of Example 1 for 7 SAT in both modes of herbicide application. Against anserine, compound D had the highest unit activity and the highest selectivity factor (1.9), for 7 SAT in the modes of application of both P.P.I. and by surface application; in the latter mode, the fac-. The selectivity of compound D was almost twice that of the compound of Example 1 and of compound E; no other compound selectively controlled anserine for 7 SAT in surface application or P.P.I. The compound of Example 1 (F.S .: 2,0) and the compounds C and E (F.S .: 35 -1,0) selectively controlled the anserine for 4 SATs in the P.P.I. mode.

Consequently, the above tests indicate that, 34.

compared to the reference compounds, in manure soil, the best selective control of quarter lamb in s.ojas is provided by the compound of Example 1 applied by the P.P.I mode; this compound had the highest unitary activity and the highest selectivity factor for 4 SATs among all the compounds in the test. In addition, the compound of Example 1 selectively controlled the anserine up to about 7 SAT in the surface application mode and up to 4 SAT in the P.P.I. mode. Compound D provided the best control of anserine for 7 SAT in both modes of application. The relative performance of the compound of Example 1 ′ and of compound D in manure soil must also be compared with the relative performance of these two compounds in soils having a lower content of organic matter, for example 3, 0-3.5%, where the compound of Example 1 has a higher unit activity and a longer longevity in the soil coupled with a selectivity in the soybeans, in the two modes of application PPI and by surface application, as presented in Table IV.

The foregoing description has emphasized the remarkable herbicidal efficacy of the compounds of the present invention in controlling perennial weeds and annual broadleaf weeds in soybeans and cotton. In addition, the following has also been indicated. above and occasionally demonstrated, for example in tests involving backyard grass and wild grass, that the compounds of the present invention also have remarkable herbicidal activity against annual narrow-leaved weeds, that is to say herbs. In fact, as will be shown below with respect to certain annual herbs the compounds of the present invention exhibit marked superiority over the most effective 2-haloacetanilides of the prior art herbicide and / or commercially available. As will be apparent from the experimental results herein, there are cases where a 2-halo-acetanilide of interest in the prior art exhibits superior herbicidal efficacy compared to the compounds 35.

of the present invention with respect to specific annual weeds under comparable conditions. However, it will also be evident from the comparative experimental results here that the compounds according to the present invention, overall, are at least comparable and frequently are superior, sometimes remarkably, to the best 2-haloacetanilides as selective herbicides to control narrow-leaved annual and perennial weeds in soybeans, cotton, arachi-10 des and other crops.

In a greenhouse pre-emergence test, the compounds of Examples 1 and 11 were compared with compounds C and I (both being commercial 2-haloacetanilides) for their relative herbicidal efficacy against annual leafy weeds narrow, that is to say herbs in soya beans. In this test, the herbicides were incorporated into the soil before planting the seeds and the observations made and recorded 17 days after treatment; the experimental results are presented in table VII 20 and represent the means of tests carried out in duplicate.

TABLE VII

Islands GR j GR rates, _ (kg / ha) oa ____ (kg / ha)

Com- Young | Cane Grass Prose-, Red rice Grass Sojas posed plants cas- of Alexandan- millet pico- 25 of her- health dre rescante be de ge

John- _son_____________

Ex .1 0.14 0.84 ΊΓΓ25 0.56 Ö795 Ö784 “.1.12”

Ex.ll 0.28 0.28 0.14 0.56 1.12 0.28> 1.12, 30 C 0.56 0.28 0.28 0.56 1.12 1.12> 1.12 I 1.12 1.12 0.56> 1.12> 1.12 1> 1.12> 1.12

Referring to the results in Table VII, the dominant characteristics to be noted are that: (!) Compound I exhibited the least unitary activity and the least selectivity among all the compounds against any weed in the test and did not show selectivity in soybeans compared to wild prosomillet, at s 36.

red rice or stinging grass; (2) compound C was as active as the most active of the compounds of examples 1 and 11. against brittle cane and wild prosomillet; (3) the compounds of Examples 1 and 11 were both superior to the compounds of the prior art in young Johnson grass plants and in stinging grass, and (4) the compound of Example 11 was more active against Alexander's herb and the compound of Example 1 was more active against red rice than the compounds of the prior art.

Thus, to summarize the comparative experimental results in Table VII, either or both of the compounds of the invention were, from the herbicidal point of view, as effective as the best reference compound of the prior art against two annual weeds with narrow leaves (brittle cane and wild prosomillet) and clearly superior against four weeds with narrow leaves (young plants of grass called Johnson, Alexander grass, red rice and stinging grass). Particularly noteworthy is the remarkable unitary activity of the compound of Example 1 against young seedlings of so-called Johnson grass (GRoc = 0.14 kg / ha), providing a selectivity factor

Outstanding ov of about 8.0 times in soybeans, compared to a selectivity factor of more than 2.0 times for compound C, the best of the compounds tested in the prior art. Similarly, the compound of Example 11 exhibited remarkable unitary activity against Alexander grass and stinging herb, providing selectivity factors of more than 8.0 times and 30 of more than 4.0 times , respectively, in soybeans, by comparison with corresponding selectivity factors of more than 4.0 times and more than 1.0 times, respectively, for compound C.

Another test was conducted in the soybeans; 35 this time, the seeds of Texas and Fall panicum were included with the other annual herbs mentioned in the previous test. In this test, the compounds of Examples 37.

pies 1 and 12 were compared for the pre-emergence herbicidal efficacy against compounds C, D and I of the prior art. The herbicides were incorporated into the soil and irrigated from below, as required. The maximum amount of herbicide used in the test was at the rate of 1.12 kg / ha and, therefore, the exact rates of GRq5 and GR ^ above 1.12 kg / ha would be somewhat undetermined The observations were made two weeks after treatment. The results from this test are shown in Table VIII.

TABLE VIII

! GRq5 rate GR ^ rate ,.

| (kg / ha) (kg / ha) r Corn- Texas "Young ~ 'can- | Her- Pro- Fall'" Rice Grass Sojas b, laid Pan. plants don't be so- Pan. red pico- d'her- cas- d'A- mil- tante be di- san- le- let te xan- sau-

John- dre vage ___son_______________

Ex. 1.12 <0.07 0.14 0.56 '0.5T <0.07 0.28 0.56> 1.12 20 Ex.l- 0.28 <0.07 0.14 0 , 14 0.56 <0.07 0.21, 0.07> 1.12 C 0.56 0.07 0.28 0.56 1.12 <0.07 0.28> 1.12> 1, 12 D 0.14 0.07 0.28 0.07 0.56 <0.07 <0.07 0.56 1.12 I> 1.12 0.28 0.50 0.50 1.12 <0 .07 0.56 0.84> 1.12 The analysis of the results in Table VIII shows that the compounds of the present invention of Examples 1 and 12 exhibited the highest unit activities and the highest selectivities among all the compounds in the test against young Johnson grass plants and brittle cane; the compound of Example 12 had the highest activity and the highest selectivity against stinging grass and the compounds of Examples 1 and 12 shared the strongest activities, against wild prosomillet, with compound D and, against ln Fall panicum, with each of the prior art compounds. However, the compounds of the present invention were more selective in soybeans than Compound D by using wild prosomillet. In addition, 38.

the compound of Example 12 was the second most compound. active against Texas panicum and red rice and the compound of Example 1 shared the second highest activity with compound D against the stinging herb. Compound D 5 was the most active of the experimental compounds against Texas panicum, Alexander grass and red rice.

Accordingly, it will be appreciated from previous comparative experimental results with respect to herbicidal activity involving annual herbs that the compounds of the present invention have a higher efficacy than the dominant compounds of interest in the prior art against certain annual grasses, e.g. backyard grass, wild grass (SI), brittle cane and stinging grass, and have equivalent or generally comparable herbicidal efficacy against others, e.g. grass wild (surface application), panicums, Alexander grass and red rice.

Other greenhouse and / or field tests have shown selective control by compounds of the present invention of additional weed species in soybeans, cotton and / or other crops . For example, the compound of Example 1 has been shown to selectively control the purple sedge of walnut trees and the giant fox tail in cotton, as well as the giant fox tail and velvet grass in soybeans. In addition, compared with the herbicides of interest comprising acetanilides of the prior art, the compound of Example 1 exhibited improved weed control against resistant weeds such as rag grass (shredded grass). ), the volubilis of the gardens and. the nielle of the fields. Additional weeds against which the compounds of the present invention have been shown to be herbicidally active include Canada thistle, bindweed, fluffy bromine, wild buckwheat, etc.

As noted above, the compounds of the present invention have been found to be effective herbicides 39.

in several plants to harvest. The above indications and experimental results have been applied mainly to weed control in soybeans and cotton, which are crops of prime interest and of prime utility here. Additional tests have demonstrated the usefulness of the compounds of the present invention in other crops for harvesting, as illustrated below.

In a greenhouse test, the pre-emergence herbicidal efficacy of the compounds of Examples 11 and 12 was tested by incorporation into the soil, against quack grass in rapeseed, brittle beans, sorghum and corn. The two experimental compounds selectively controlled the quack grass in rapeseed and brittle beans, the selectivity factor of the compound of Example 15 11 being 3.5 times in the two crops and that of the compound of Example 12 was 3.0 times in both crops. In this test, the two compounds were non-selective against quack grass in sorghum and wheat.

In separate tests in a greenhouse, compound 20 of Example 1 was also tested to determine its herbicidal efficacy against the yellow sedge of the walnut trees and the quack grass, respectively in rapeseed, peanuts, sugar batterave , sorghum, wheat and barley; the herbicide was applied by incorporation into the soil. In these tests, compound D was included as a reference compound against quack grass and compound E was included as a reference compound against the yellow sedge of walnut trees. The observations in the test against quack grass were made at 19 JAT and in the test against the yellow sedge of walnut trees at 18 JAT; the experimental results are presented in Table IX; the selectivity factors for herbicides are presented in parentheses after the GR ^ rate for the respective plants to be harvested. ‘40.

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Referring to the results in Table IX, it can be seen that the compound of Example 1 and Compound D both selectively controlled the quack herb in peanuts, rapeseed, sugar beets, wheat and wheat. but the selectivity factor for the compound of Example 1 was significantly higher than that for Compound D in peanuts, rapeseed and sugar beets, being equivalent in wheat and lower in barley, be compound of Example 1 selectively controlled the young sedge of walnut trees in each plant to be harvested in the test, except the sugar beets, while compound E did not selectively control the yellow sedge of the walnut trees in sugar beets, the sorghum or wheat.

The high unit activity of compounds D and E shown in Table IX is generally characteristic of the short-term performance in a greenhouse (i.e. 2-6 weeks) for these compounds against grass of quack and the yellow sedge of the walnut trees. However, as presented here, all the interesting experimental results, both in the greenhouse and in the field have established the uniformly superior unit activity against the quack grass and the yellow sedge of the walnut trees and the selectivity for the plants to harvest the compound of Example 1 with respect to compounds D and E, for remarkably longer periods of time. In this report, reference should again be made: (1) to Table IV which contains comparative experimental results in fields for up to 9.5 weeks for the performance of these compounds against quack grass and other weeds in soybeans (neither cceoposite D nor compound E selectively controlled the herb quack in soybeans, even for observation at 3 SAT); (2) to the above discussion of comparative experimental field results for the performance of these compounds against yellow sedge of walnut trees and other weeds in cotton for up to 9 weeks (neither the Compound D or Compound E did not selectively control the yellow sedge of walnuts in cotton, even for observation 42.

at 2 SAT) jet (3) in Table V which presents comparative results of duration of use in the soil for, the compound of Example 1 and the compounds D and E against the yellow sedge of the walnut trees and the grass quack for 3, 6, 12 and 18 · 5 weeks, where the compound of Example 1 had higher activity units than those of compounds D and £ at 3 SAT (according to several orders of magnitude for observation performed at 12 SAT and according to an indefinite quantity for the observations carried out at 18 SAT). It should also be mentioned here that the combined unitary activity, the duration of use in the soil and the selectivity for the plants to be harvested of the compound of Example 1 with respect to compounds D and E, with regard to relates to the yellow sedge of the walnut trees and the quack grass, are also applicable to the relative performance of these compounds in many other weeds, in particular of young seedlings of grass known as Johnson, hemp sesbania, thorny aids, beautiful grass, quarter of lamb, etc.

In a multi-plant to harvest / weed 2o test, the pre-emergence activity of the compound of Example 1 was further tested in the fields against certain annual weeds in several plants to be harvested. In parallel tests, the herbicides were applied on the surface and incorporated before the plant. Observations were made and recorded 33 days after treatment for the test with incorporation before the plant and 34 JAT for the tests by surface application. In the two tests, the compound of Example 1 checked the selectivity of backyard grass and green fox tail in corn, soybeans, cotton, white haridots and peanuts; the quarter of lamb was also checked in the soybeans. In addition, in the P.P.I.test, backyard grass and fox tail were also selectively controlled in sorghum and soft corn.

35. Consequently, it will be appreciated from the above detailed description that the compounds of the present invention have shown unexpected herbicidal properties and 43.

remarkably superior, in absolute terms and compared to the most interesting compounds from a structural point of view, other related homologs and analogs, as well as 2-haloacetanilides of the prior art. More particularly, the compounds of the present invention have shown remarkable unitary activity, remarkable longevity in the soil and remarkable safety for the plants to be harvested compared to perennial grasses and annual weeds with narrow leaves and 10 broad leaves in soybeans, cotton, peanuts, rapeseed, brittle beans and other crops to harvest. Still more particularly, the compounds of the present invention have shown superior herbicidal activity against the perennial grasses constituted by the yellow sedge of the walnut trees and the quack grass, the annual broad-leaved grasses such as the hemp sesbania, AIDS thorny, quarter-lamb and beautiful grass, and narrow-leaved annual weeds, such as backyard grass, wild grass (PPI), cane brittle and stinging grass.

In addition, it has been shown that the compounds of the present invention are generally comparable to the best of the compounds of interest, of the prior art for the control of other annual weeds (grassy type), such as the young so-called grass plants. Johnson, wild grass (surface applica-25 tion), fox tails, Texas panicum, fall panicum, wild prosomillet, Alexander grass and red rice and annual broadleaf weeds such as anserine and the herb called jimson. Finally, the compounds of the present invention have also shown increased activity and increased suppression of resistant annual broadleaf weeds such as garden volubilis, field niel, rag grass (shredded grass) and the velvet sheet.

Toxicological studies on the compound of Example 35 -pie 1 indicated that the compound was quite safe.

It was slightly toxic by ingestion (single dose DL05Q-2.600 mg / kg), slightly toxic by dermal applications.

ques unique (DLD ^ q “5.010 mgAg), and slightly irritating to the eyes and the skin. No special handling procedure, in addition to normal precautions, is considered necessary.

The herbicidal compositions of the present invention, comprising concentrates which require dilution before application, contain at least one active ingredient and an adjuvant in liquid or solid form. The compositions are prepared by mixing the active ingredient with an adjuvant comprising diluents, diluents (extenders), carriers and conditioning agents to provide compositions in the form of finely divided particulate solids , granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or not. any suitable combination of these products.

2o The compositions of the present invention, particularly wettable liquids and powders, preferably contain, as conditioning agent, one or more surface-active agents in amounts sufficient to make a given composition easily dispersible in water or 25 in oil. The incorporation of a surfactant into the compositions greatly enhances their effectiveness. By the term "surfactant" it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included. Anionic, cationic and nonionic agents can be used with equal ease.

Preferred wetting agents are alkylbenzene and alkylnaphthalenesulfonates, sulfated fatty alcohols, amino or amide acids, long chain acid esters of sodium isethionate, sulfo succinate esters sodium, esters of sulphated or sulphonated fatty acids, petroleum sulphonates, vegetable oils sulpho-45.

born, tertiary acetylenic glycols, derivatives. polyoxyethylenic alkylphenols (particularly iso-octylphenol and nonylphenol) and polyoxyethylenic derivatives of the higher monocarboxylic fatty acid esters of hexitol anhydrides (eg sorbitan). Preferred dispersion products are methylcellulose, polyvinyl alcohol, sodium ligninesulfonates, polymeric alkylnaphthalenesulfonates, sodium naphthalenesulfonate and polymethylene bisnaphthalenesulfonate.

Wettable powders are water dispersible compositions containing one or more active ingredients, an inert solid diluent (or extender) and one or more wetting and dispersing agents. Inert solid extension products are ordinarily of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals from silica and the like. Examples of these extension products include kaolinites, so-called attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the present invention ordinarily contain about 0.5 to 60 parts (preferably 5-20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1-15 parts) of agent wetting, about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersion product and 5 to about 95 parts 1 (preferably 5-50 parts) of extension (or dilution) product inert solid, all parts being by weight relative to the total composition. When required, about 0.1 to 2.0 parts of the solid inert extender can be replaced with a corrosion inhibitor or an anti-foaming agent. or both.

Other formulations include dust concentrates containing 0.1 to 60% by weight of an active ingredient, on a suitable extension product; this dust 25 * can be diluted for application at concentrations in the range of about 0.1-10% by weight.

Aqueous suspensions or emulsions can 46.

be prepared by shaking an aqueous mixture of a water-insoluble active ingredient and an emulsifying agent until they are uniform and then homogenized to give a stable emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size so that when diluted and sprayed, the coating is very uniform. Suitable concentrations of these formulations contain about 0.1-60%, preferably 5-50%, by weight of active ingredient, the upper limit being determined by the solubility limit of the active ingredient in; solvent.

In another form of aqueous suspensions, a water-immiscible herbicide is encapsulated to form a microencapsulated phase dispersed in an aqueous phase. In an exemplary embodiment, tiny capsules are formed by bringing together an aqueous phase containing an emulsifier, consisting of lignignesulfonate, a chemical immiscible with water and a polyphenylisocyanate of polymethyl-2o lene, by dispersing the non-phase miscible with water in the aqueous phase, followed by addition of a polyfunctional amine.

The isocyanate and amine compounds react to form a solid urea shell wall around particles of the water immiscible chemical, thereby forming microcapsules. Generally, the concentration of the microencapsulated material will be between approximately 480 and 700 g / l of the total composition, preferably 480 to 600 g / l.

Concentrates are ordinarily solutions of active ingredient in water-immiscible or partially water-immiscible solvents with a surfactant. Suitable solvents for the active ingredient of the present invention include dimethylformamide, dime-thylsulfoxide, N-methylpyrrolidone, hydrocarbons and ethers, esters or ketones immiscible with water.

35 - However, high concentration liquid concentrates can be formulated by dissolving the active ingredient in a solvent and then diluting, for example with kerosene, up to 47.

only at a concentration suitable for spraying.

The concentrate compositions herein generally contain about 0.1 to 95 parts (preferably 5-60 parts) of active ingredient, about 0 # 25 to 50 parts (preferably 1-25 parts) of surfactant. active and, when required, about 4 to 94 parts of solvent, all parts by weight based on the total weight of the emulsifiable oil.

The granules are physically stable particulate compositions comprising an active ingredient adhering to or distributed through a base matrix consisting of an inert, finely divided particulate extension or dilution product. To assist the leaching of the active ingredient from the particulate product, a surfactant such as those indicated above, may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of well-functioning classes of particulate mineral extension products. Preferred extension products are pre-formed, porous, absorbent particles, such as preformed and sieved particulate attapulgite or thermally expanded particulate vermiculite and finely divided clays, such as kaolin-type clays, attapulgite hydrated or bentonite clays. These extension products are sprayed or mixed with the active ingredient to form the herbicidal granules.

The granular compositions of the present invention may contain from about 0.1 to about 30 parts, preferably about 3 to 20 parts, by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight. weight of surfactant per 100 parts by weight of particulate clay.

The compositions of the present invention may also contain other additives, for example, fertilizers, other herbicides, other pesticides, safety products (safety products) and the like used as adjuvants or in combination with one 48.

any of the adjuvants described above. Useful chemicals in combination with the ingredient? active agents of the present invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, phenol or acetic acid derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers, and the like, such as: Nitrogen / sulfur heterocyclic derivatives 2-chloro-2-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 2,2-3-isopropyl-1H-2,1,3-benzothia-diazin-4- (3H) - on 3-amino-1,2,4-triazole 6,7-dihydrodipyrido salt (1,2-a: 2 ', l'-c) -pyra-zidinium 5-bromo-3-isopropyl- 6-methyluracil 1,1'-dimethyl-4,4'-bipyridinium 20 Urjgs

N '- (4-chlorophenoxy) phenyl-N, N-dimethylurea N, N-dimethyl-N' - (3-chloro-4-methylphenyl) urea la 3- (3,4-dichlorophenyl) -1,1 -dimethylurea 1,3-dimethyl-3- (2-benzothiazolyl) urea 25 3- (p-chlorophenyl) -1,1-dimethylurea 1-buty1-3- (3,4-dichlorophenyl) -1-methylurea Carbamates / thiolcarbamates 2-chloroallyl diethyldithiocarbamate Ν, Ν-diethylthiolcarbamate S- (4-chlorobenzyl) 3Q isopropyl N- (3-chlorophenyl) carbamate le, Ν-diisopropylthiolcarbamate dichloro-allyl ethyl Ν, b-dipropylthiolcarbamate \ e S-propyl dipropylthiolcarbamate 35 Acetamides / acetanilides / anillins / amides la 2-chloro-N, N-diallylacetamide la N, N-dimethyl-2,2-diphenylacetamide N- (2,4-dimethyl-5 - [[(trifluoromethyl) sulfonyl] 49.

amino] phenyl) acetamide N-isopropyl-2-chloroacetanilide 2 ', 6'-diethyl-N-methoxymethyl-2-chloroacetanili-5 2'-methyl-6'-ethyl-N- (2-methoxyprop- 2-yl) -2- chloroacetanilide la a, a, a-trifluoro-2,6-dinitro-N, N-dipropyl-p-tolui-dine la N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide 10 Acldes / esters / alcohols 2,2-dichloropropionic acid 2-methyl-4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid. methyl 2- [4- (2,4-dichlorophenoxy) phenoxy] propionate 3-amino-2,5-dichlorobenzoic acid 2-methoxy-3,6-diehlorobenzoic acid 2,3-acid, 6-trichlorophenylacetic acid Nl-naphthylphthalamic 20 sodium 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitro-benzoate 2,4-dinitro-o-sec-butylphenol N- (phosphonomethyl ) glycine, its alkali metal salts, its monoalkyl (C 1 -C 4) amine salts and combinations thereof.

Ethers 2,4-dichlorophenyl-4-nitrophenyl ether 2-chloro-a, a, a-trifluoro-p-tolyl-3-etho-xy-4-nitrodiphenyl ether 30 Various products 2,6 -dichlorobenzonitrile methanearsonate monosodium acid methanearsonate disodium

Useful fertilizers in combination with the active ingredients include, for example, ammonium nitrate, urea, potassium carbonate and superphosphate. Other useful additive products include materials where the 50.

plant organisms take root and grow, such as compost, fertilizer, humus, sand and the like.

Herbicidal formulations of the types described above are given by way of examples in several exemplary embodiments by way of illustration below.

I. Emulsifiable concentrates% by weight A. Compound of Example 1 50.0 Mixture of calcium dodecylbenzenesulfonate 10 / polyoxyethylene ethers (for example products known under the registered trademark Atlox 3437F and Atlox 3438F) 5.0

Monochlorobenzene 45.0 100.00 15 B. Compound of Example No. 12 85.0 Cal-dium dodecylsulfonate / alkylaryl polyether alcohol mixture 4.0

Solvent consisting of C ^ aromatic hydrocarbons 11.0 20 - 100.00 C. Compound of example 13 13 5.0 Mixture of calcium dodecylbenzenesulfonate / polyoxyethylene ethers (for example product known as Atlox 3437F) 1.0 25 Xylene 94.0 100.00 II. Liquid concentrates% by weight A. Compound of Example 1 10.0 30 Xylene 90.0 100.00 B. Compound of Example 2 85.0

Dimethyl sulfoxide 15.0 ‘100.00 35 C. Compound of example 3 50.0 N-methylpyrrolidone 50.0 100.00 51.

D. Compound of Example 4 5.0

Castor oil ethoxylated 20,0 "

Product called Rhodamine B 0.5 - Dimethylformamide 74.5 _ 100.00

D

III. Emulsions% by weight A. Compound of example ηβ 1 40.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol (for example product known under the trademark Tergitol XH) 4.0

Water 56.0 100.00 v jL5 B. Compound of Example 5 5.0 5.0 Sequenced polyoxyethylene / polyoxypropylene polymer with butanol 3.5

Water 91.5 100.00 20 IV. Wettable powders'% by weight A. Compound of example ηβ 1 25.0

Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyl-taurate 1.0

Amorphous silica (synthetic) 71.0 100.00 B. Compound of Example 6 80.0

Sodium dioctylsulfosuccinate 1.25 30 Calcium lignosulfonate 2-75

Amorphous silica (synthetic) 16.00 100.00 C. Compound of Example 7 10f0

Sodium lignosulfonate 3.0 35 Sodium N-methyl-N-oleyl-taurate 1.0

Clay called kaolinite 86.0 100.00 52.

V. Dust% by weight A. Compound of Example No. 1 2.0

Attapulgite 98.0 5 100.00 B. Composed of Example 8 60.0

Montmorillonite 40.0 100.00 C. Compound of Example No. 9 30.0 10 Bentonite 70.0 100.00 D. Compound of Example No. 11 1.0

Diatomaceous earth 99.0 100.00 ^ -5 VI. Granules% by weight A. Compound of Example 1 15.0

Granular attapulgite (passing through a sieve with a 2 ° mesh opening between 0.841 mm and 0.420 mm, i.e. 20-40 mesh) 85.0 100.00 B. Compound of example n ° 12 30.0

Diatomaceous earth (passing through a 25 mesh sieve between 0.841 mm and 0.420 mm) 70.0 100.00 C. Compound of example n ° 13 0.5

Bentonite (passing through a sieve with a mesh opening of between 0.841 mm and 0.420 mm) 99.5 100.00 D. Compound of example n ° 14 5.0

Pyrophyllite (passing through a sieve 35 with a mesh opening of between 0.841 mm and 0.420 mm) 95.0 100.00 53.

VII. Microcapsules A. Compound of example n ° 1 encapsulated in a polyurea envelope wall 49.2 Sodium lignosulfonate (for example -5 pie product known under the registered trademark Reax 88 B) 0.9

Water 49.9 100.00 B. Compound of example n ° 12 encapsulated in a polyurea envelope wall 10.0 10 Potassium lignosulfonate (for example product known under the registered trademark Reax C-21) 0.5 *

Water 89.5 100.00; L5 C. Compound of Example 13 encapsulated in a polyurea envelope wall 80.0

Lignosulfate magnesium salt (product known under the trademark Treax LTM) 2.0

Water 18.0 20 100.00

When operating in accordance with the present invention effective amounts of the acetanilides of the present invention are applied to the soil containing the plants, or are incorporated into aquatic media, in any suitable manner. The application of liquid compositions and solid particulate compositions on the ground can be produced by conventional methods, for example by mechanical dust-forming devices, telescopic and hand-held spraying devices and spraying dust-forming devices. The compositions can also be applied from aircraft in the form of a dust or spray due to their effectiveness at low doses. Application of the herbicidal compositions to aquatic plants is usually accomplished by adding the compositions to the aquatic media in the surface or area where control of the aquatic plants is desired.

54.

Application of an effective amount of the compounds of the present invention to the location of the unwanted weeds is essential and critical to the practice of the present ir. The exact amount of active ingredient in-5 to be used depends on various factors, including the plant species and its stage of development, the type and condition of the soil, the amount of rainfall and acetanili. - specific employee. In a selective preemergence application to plants or soil, a dose of 0.02 to approximately 10 11.2 kg / ha, preferably from approximately 0.04 to approximately 5.60 kg / ha, or suitably 1, 12 to 5.6 kg / ha of acetanilide is commonly used. Lower or higher rates may be required in some cases. An experienced person. in the art can readily determine from this description, including the example given above, the optimum rate to be applied in any particular case.

The term "soil" is used in its broadest sense to include all conventional "soils", as defined in the New International Dictionary of Webster, 20 2nd edition, unabridged (1961). Thus, the term refers to any substance or medium where vegetation "can take root and grow, and includes not only soil but also compost, fertilizer, manure (garbage), humus, sand and analogs, adapted to maintain plant growth.

The appreciation of some of the measurement values indicated above must take into account the fact that they come from the conversion of Anglo-Saxon units into metric units.

The present invention is not limited to the exemplary embodiments which have just been described, it is on the contrary susceptible of variants and modifications which will appear to those skilled in the art.

"

Claims (26)

55. 1. Compounds, characterized in that they have the formula: O 5 CICI ^ C ^ yCÜ2OR IJ 10 M where R is ethyl, n-propyl, isopropyl, isobutyl,. sec-butyl, cyclopropylmethyl, allyl or propargyl; R 1 is methyl, ethyl, n-propyl or isopropyl, and R 2 is hydrogen, methyl, or ethyl; provided that: when R2 is hydrogen, R1 is the ethyl group and R is the allyl group; when R2 is the ethyl group, R1 is the methyl group and R is the isopropyl group; when R ^ is methyl, R is either ethyl, isopropyl, isobutyl, sec-butyl or cyclopropylmethyl; when R ^ is the ethyl group, R is the sec-butyl, allyl or propargyl group; when R ^ is the n-propyl group, R is the ethyl group; and when R1 is the isopropyl group, R is pe ethyl or n-propyl. 2. Compound according to claim 1, characterized in that it is formed by 2'-methoxy-6'-methyl-N-fisopropoxy-methyl) -2-chloroacetanilide. 35 · 3 - Compound according to claim 1, characterized in that it is formed by 2'-methoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide. 56. 4. Compound according to claim 1, characterized in that it is formed by 2'-methoxy-6'-methyl-N- (l-methyl- ’propoxymethyl) -2-chloroacetanilide. 5. Compound according to claim 1, characterized in that it is formed by 2'-ethoxy-6'-methyl-N- (allyloxy-methyl) -2-chloroacetanilide. 6. Compound according to claim 1, characterized in that it is formed by 2'-ethoxy-6'-methyl-N- (propargy-loxymethyl) -2-chloroacetanilide. 7 - Compound according to claim 1, characterized in that it is formed by 2'-ethoxy-6'-methyl-N- (1-methyl-propoxymethyl) -2-chloroacetanilide. 8. A compound according to claim 1, characterized in that it is formed by 2'-n-propoxy-6'-methyl-N- (ethoxy-methyl) -2-chloroacetanilide. 9. Compound according to claim 1, characterized in that it is formed by 2'-isopropoxy-6'-methyl-N- (ethoxy-methyl) -2-chloroacetanilide. 10. Compound according to claim 1, characterized in 2o that it is formed by 2'-isopropoxy-6'-methyl-N- (n-propo-xymethyl) -2-chloroacetanilide. 11. Compound according to claim 1, characterized in that it is formed by 2'-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide. 12 - Compound according to claim 1, characterized in that it is formed by 2'-methoxy-6'-ethyl-N- (isopropoxy-methyl) -2-chloroacetanilide. 13. Herbicidal compositions, characterized in that they include an adjuvant and a herbicidally effective amount of a compound having the formula: O C1CH-C .CH OR Y 35. L3J 57. where R, R ^ and R2 are as defined in claim 1. 14. Composition according to claim 13, characterized in that the provisions of any one of claims 2 to 12 are applied. 15. Method for combating undesirable plants associated with plants to be harvested, characterized in that it consists in applying to the place where these plants are found a quantity, herbicide-effective, of a compound having the formula: 0 cich2cv ^ ^ ch2or where R, R ^ and R2 are as defined in claim 1. 20 16 - Method according to claim 15, characterized in that one applies the provisions of any one of claims 2 at 9, 11 and 12. 17. The method of claim 15, characterized in that the plants to be harvested are soybeans, cotton, peanuts, rapeseed, white beans, sugar beets, sorghum, wheat or barley. 18. The method of claim 17, characterized in that the undesirable plants are perennial herbs, weeds of the sedge genus and 3q annual weeds. 19. The method of claim 18, characterized in that the perennial weeds are quack grass and the yellow sedge of walnut trees. 20 - - A method according to claim 18, characterized 35 - in that the annual weeds are broadleaf weeds. 21. The method of claim 20, characterized "58. in that the broadleaf weeds are spiny AIDS, hemp sesbania, anserine, 1? beautiful grass, quarter of lamb and the so-called jimson grass. 22- Method according to claim 18, characterized 5 in that. annual weeds are grasses (grassy type). 23. The method of claim 22, characterized in that these herbs are fox tails, backyard grass, wild grass, panicums, cane brittle, Alexander grass , red rice and stinging grass. 24. Method according to any one of claims 17 to 23, characterized in that the compound is 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide. 25. Method for selectively controlling the growth of weeds in soybeans, cotton, peanuts, rapeseed, brittle beans, sugar beets, sorghum, wheat or barley, characterized in that it consists in applying a herbicide-effective amount of 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanili to the place where these weeds are present. 26. A method for removing weed stalks consisting of rag grass (shredded grass), garden volubilis, field nielle and leaf of flowers, characterized in that it consists in applying instead where these weeds are found an herbicide-effective amount of 2'-methoxy-6'-methyl-N- (isopro-poxymethyl) -2-chloroacetanilide. "