NL8101326A - HERBICIDE 2-HALOGENENE ACETANILIDES, AND METHOD FOR PREPARING HERBICIDE PREPARATIONS HEREBY. - Google Patents

Description

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Herbicide 2-haloacetanilides, as well as a method of preparing herbicidal preparations therewith.

The invention relates to 2-haloacetanilides and their use in agriculture, for example as herbicides.

Numerous 2-haloacetyl anilides have been disclosed hitherto, which are unsubstituted or substituted with a wide variety of substituents on the anilide nitrogen atom and / or on the anilidation, including alkyl, alkoxy, alkoxyalkyl, haloalkyl, halogen, etc. .

The closest prior art, for the compounds of the invention, which are characterized by a hydrocarbyloxymethyl residue on the anilide nitrogen, a trifluoromethyl residue in one ortho site and a methyl residue or, in special cases, an ethyl residue or hydrogen in the other ortho site, according to the Applicant, the Belgian patent is 810,763.

In general, N-alkoxyethyl or alkyl substituted alkoxyethyl 2-chloroacetanilides are discussed herein, which may or may not be substituted on the anilidation on the ortho and meta sites having one or more residues selected from a number of radicals including halogen, alkyl, alkoxy or trifluoromethyl.

More specifically, the list of compounds in Table B includes species substituted with a trifluoromethyl moiety at one ortho site and no substituent at the other ortho site (compounds no. 37-8) and compounds with a trifluoromethyl substitution at one meta site with one ortho site unsubstituted and the other ortho site substituted with a methoxy radical (compounds no. 22-25) or a chlorine atom (compounds no. 33-36).

However, no special examples are given of 2-haloacetanilides substituted with a trifluoromethyl residue in one ortho position and a methyl or ethyl residue in the other ortho-position as in the compounds of the invention. In addition, 8101326-2 - the compounds in this patent are characterized by an alkoxyalkyl group substituted on the anilide nitrogen atom, the alkylene nucleus having no less than two carbon atoms between the nitrogen atom and the oxygen atom of the alkoxy nucleus. In contrast, the compounds of the invention are further characterized in part by the substitution of the anilide nitrogen atom with an alkoxymethyl radical. The significance of the aforementioned distinction between the compounds of the Belgian patent and those of the invention will become clear from the comparative herbicidal data, which will be given below, and which clearly shows the superiority of the compounds of the invention in terms of activity , selectivity, weed control spectrum and crop protection.

Other prior art less relevant than the aforementioned Belgian patent include U.S. Pat. Nos. 3,966,811 and H,152,137, German Pat. No. 2,102,93, British Pat. No. 2,013,188, and South African Pat. Although these references generally disclose 2-haloacetanilides, which may have, inter alia, trifluoromethyl substitution on the anilidation, the only disclosures of such types of compounds in each of these references are found in said U.S. Patent 3,966,811 and South African Patent. 25 7V0767. Both of the latter patents even contain species of orthotrifluoromethyl substituted compounds generally or more particularly such compounds which are further substituted at the other ortho site with a methyl or ethyl moiety; the only trifluoromethyl substituted species disclosed in these patents are: meta trifluoromethyl substituted compounds. In addition, both of the latter patents, as well as the said Belgian patent, require that no less than two carbon atoms are present between the anilide nitrogen and the oxygen in the alkoxy-35 core, a requirement described in each of the foregoing 8101326% - 3 - references, except said U.S. Patent No. k,152,137, which does not disclose trifluoromethyl substituted compounds at all.

Of the aforementioned most relevant prior art, only said Belgian Patent Specification 810,763 and South African Patent Specification 7/0767 disclose any herbicidal data regarding N-alkoxyalkyl-2-haloacetanilides with trifluoromethyl substitution to the anilidation.

As said, it is vague, undefined and incomplete.

For example, the Belgian patent discloses limited herbicidal data for only one trifluoromethyl substituted compound, namely compound no. 37 (vessel is the same compound as in example II) ie 2-trifluoromethyl N- (2'-methoxyethyl) 2-chloroacetanilide. In Table 3 of said Belgian Patent Specification, compound No. 37 is shown to contain certain unidentified species of "Cuperus",

Setaria, Digitaria and Echinochloa destroys or severely damages, with little damage to the Avena fatua weeds and an undefined Lolium species in certain crops. The lack of specific identity of five of the six weeds tested has prevented a meaningful appreciation of the herbicidal effectiveness of said compound 37.

Likewise, said South African patent discloses limited herbicidal data only one trifluoro-methyl-substituted compound, namely compound No. 78, i.e. 2,6-dimethyl 3-trifluoromethyl N- (2'-methoxyethyl) N-2-chloroacetanilide. The only herbicide data disclosed for Compound No. 78 is in Example V, where Compound No. 78 is said to exhibit very strong growth inhibition for four types of grass weeds. However, no laboratory or field data is disclosed in said patent regarding the effect of compound No. 78 on any crop or that this compound will exhibit selective control on any weeds in any crop, so that any significant appreciation of this connection based on such limited 8101326 *? - k - data is made impossible. Furthermore, although the above most relevant references, although indicating herbicidal activity on a number of weeds, do not disclose any of any trifluoroethyl substituted N-alkoxyalkyl compounds, or additionally and / or simultaneously in one or more crops the perennial which is difficult to destroy weeds such as cultivated grass, yellow and purple nut sedges and a broad spectrum of annual weeds, including such hard-to-decide annual grass seeds, such as seedling aleppo millet, brittle reed, short stem 10 (Brachiaria plantaginea), handgrass (Texas and wild pseudo-millet) red rice and itch grass (Raoulgras) would control or suppress, while other harmful perennial and annuals, such as fall grass, knotweed, loosestrife, melgan foot, foxtails (for example giant and 15 yellow), blood millet, hawp, dayflower, mallow, burdock, posteslein »sesbania hemp, lancing, etc. would be controlled or suppressed.

A very useful and desirable property of herbicide is its ability to maintain weed control over an extended period of time, the longer the better, during each crop season. In many herbicides known hitherto, the weeds are only adequately controlled for about 2 or 3 weeks or, in more superior cases, sometimes up to 6 weeks before the chemical loses its effective phytotoxic properties. A disadvantage of most herbicides known so far is therefore a relatively short soil life.

Another drawback of some heretofore known herbicides, which is somewhat related to soil life under normal weather conditions, is the lack of blowing weed control under heavy rainfall, which inactivates many herbicides.

A further disadvantage of many herbicides known hitherto is the limitation in their use to specified soil types, ie while some herbicides are effective in soil types with low amounts of organic matter, they are ineffective in other soil types have a high organic material content or vice versa. It would therefore be advantageous if a herbicide would be useful in all soil types ranging from light organic to heavy clay and peat.

Yet another drawback of many heretofore known herbicides is the limitation to a particular effective application method i.e. as a pre-germination surface application or as a soil incorporation, before and / or after planting. It is highly desirable to be able to apply a herbicide in any manner of application, either by application to the surface or incorporation into the soil.

Finally, a drawback of some herbicides is the need to maintain certain procedures because of their toxic nature. A further consideration is therefore that a herbicide must be safe to handle.

It is therefore an object of the invention to provide a group of herbicidal compounds, overcoming the above-mentioned drawbacks of the hitherto known and providing a multitude of advantages which have hitherto not been obtained in a single group of herbicides.

It is an object of the invention to provide herbicides which control and / or suppress perennial perennial and annual weeds as described above, while maintaining crop protection in a number of crops, in particular corn and soybeans, and others including cotton , ninda, turnip, kidney beans, wheat and / or barley.

It is a further object of the invention to provide soil herbicide effectiveness for periods of up to 12 weeks.

Yet another object of the invention is to provide herbicides which resist leaching and dilution due to very humid conditions, such as heavy rainfall.

Yet another object of the invention is provided by herbicides effective over a width range of 8101326

* V

£ * - 6 - soils, for example from light to medium organic to heavy clay and peat.

Another advantage of the herbicides according to the invention is the pliability in the manner of application, ie on the soil before germination or by incorporation into the soil.

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

The above and other objects of the invention will become apparent from the following detailed description.

The invention relates to herbicidally active compounds, herbicide compositions containing these compounds as active ingredients and herbicidal methods of use of said compositions in certain crops.

It has now been found that a selective group of 2-haloacetanilides characterized by specific combinations of specific hydrocarbyloxymethyl radicals on the anilide nitrogen-20 atom, a trifluoromethyl radical in one ortho site and a methyl or ethyl radical or a hydrogen atom in the other ortho site unexpectedly superior and excellent herbicide possess properties over heretofore known herbicides, including homologous compounds of the most relevant prior art. A primary feature of the herbicidal compositions of the invention is their ability to control a wide spectrum of weeds, including those controlled with conventional herbicides and, in addition, a number of weeds which, individually and / or together, have hitherto escaped control by a single class of known herbicides, while maintaining crop protection in respect of one or more of a number of crops including in the blonder corn and soybeans, but also others such as cotton, peanut, turnip, barley, wheat and kidney beans. Although the herbicides known so far are useful in controlling a number of 8101326 * if - 7 - weeds, including occasionally certain resistant weeds, the unique herbicides of the invention have been shown to be capable of a number of resistant perennial and annual weeds to control or strongly suppress, such as the perennial 5 cultivated grass, yellow and purple nut sedges, annual broadleaves such as prickly nose, sesbania hemp, knotweed, loosestrife, melgan foot and annuals such as seedling alpog millet, brittle reed, shortstalk, Texas hand grass, wild pseudo millet, red rice, itch grass and other poisonous weeds, such as drop grass, foxtail, coot, blood millet, etc. A reduction in the weed position has also been obtained with resistant weeds, such as Ambrosia, mallow, burdock, purslane, etc.

The compounds of the invention are characterized by the formula 1, wherein R = alkyl or alkoxyalkyl or alkenyl or alkinyl with up to 5 carbon atoms and R = hydrogen, methyl or ethyl, provided that when hydrogen is R is isopropyl and when R ^ is ethyl, R is ethyl, n-propyl or isopropyl.

Preferred compounds of the invention are those wherein R 1 in formula 1 is methyl or ethyl and R is alkyl.

Separately preferred compounds of the invention are the following: N- (ethoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide R- (n-propoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloro-25-acetanilide .

R- (isopropoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide.

N- (isobutoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide.

R- (ethoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacet anilide.

R- (n-propoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide.

R- (isopropoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloro-35 acetanilide.

8101326

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- 8 -

Other compounds of the invention will be discussed below.

The utility of the compounds of the invention as the active ingredient in herbicidal compositions formulated therewith, and the mode of use thereof will be discussed below.

The compounds of the invention can be prepared by N-alkylating the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent under basic conditions, such as, for example, in Example I.

Modification of said N-alkylation process involves the in situ preparation of halomethylalkyl ethers used as starting materials for said N-alkylation process and is described in Example II to prepare other compounds of the invention.

Example I

This example describes the preparation of N- (ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide.

0.02 g (0.016 mol) of 2 -'-trifluoromethyl 2 (½-methyl 2-chloroacetanilide), 3.02 g (0.032 mol) of chloromethyl ethyl ether and 2.0 g of benzyl triethyl ammonium bromide (phase transfer catalyst) are mixed in 75 ml of methylene chloride in a 500 ml round flask equipped with a mechanical stirrer and thermometer 15 ml of 50% sodium hydroxide are suddenly added with vigorous stirring, causing the temperature to rise to 26 [deg.] C. After about 5 minutes, gas chromatography indicates that the reaction is complete.

After 15 min, ice and water are added, the layers are separated and the organic layer is washed with 2.5% sodium chloride, dried, filtered and distilled off. The dark colored residue is distilled on a ball tube ("Kugelrohr") and 3.5 g of a yellow oil fraction boiling at 110-115 ° C at 0.1 mm of mercury is collected This fraction is taken up in cyclohexane and purified by HPLC using 20% ethyl acetate in cyclohexane. Further distillation of peak fraction by Kugelrohr 35 yields 3.2 g (65%) colorless oil, boiling point 100-110 ° C at 8101326 - 9 - -, 1 mm of mercury. On standing, a white solid crystallizes with melting point 1 * 1-1 * 3 ° C.

Analysis for C ^ H ^ CIP ^ NO ^ {%) Element Theory Found C 50.1 * 1 50.02 5 H U, 88 U, 81 N U, 52 1 *, 38

Example II

This example illustrates the use of an improved alternative process, according to which the compounds 10 of the invention can be prepared. A feature of the process of this example is the in situ formation of the alkylating agent, whereby a more efficient, economical and simple operation is obtained.

A slurry of 7.3 g (0.096 mole) of ethylene-15 glycol monomethyl ether and 1.1 * 1 * g (0.08 mole) of paraformaldehyde in 100 ml of methylene chloride solvent in an ice-water bath is cooled and 5.9 g (0. 01 * 8 mol) of acetyl bromide. After stirring for about 1 * 5 min, 1.03 g (0.016 mol) of 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide and 2.0 g of benzyltriethylammonium-20 chloride are added. 50 ml 50 Ji's NaOH are added suddenly. Gas chromatography indicates that the reaction is complete after about 5 minutes. Ice and water are added to the mixture to effect phase separation, and then the organic phase is separated, dried, filtered and stripped. The residue is then vacuum-distilled in a short pad kettle to give 0.2 g (77%) of clear colorless oil, b.p. 150-160 ° C at 0.05 mm mercury.

Analysis for C ^ H ^ CIP ^ NO ^ (%) Element Theory Found C 1 * 9.1 * 9 1 * 9.33 H 5.0l * 5.01 * 30 N 1 *, 12 1 *, 08

The product is identified as N- (2-methoxyethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide.

When the N-alkylation process is allowed to develop at too high or too low temperatures, various impurities may arise, for example secondary anilide, corresponding to 8101326 $ i -> - 10 -

coming imidate, α-alkoxramide or diketopiperazines. Such impurities can be removed by washing the organic layer with a dilute aqueous salt or acid solution, for example 2-3% NaCl or 5% HCl. Example III-XIII

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- 13 -

The secondary anilide starting materials used in the above examples to prepare the compounds of the invention are conveniently prepared by conventional chloroacetylation of the appropriate primary amine as in the following Example XIV.

Example XIV

This example illustrates the preparation of the secondary anilide starting material to prepare the compound of formula 13.

6.0 g (0.0317¼ mol) of 2-trifluoromethyl 6-ethylaniline are dissolved in 75 ml of toluene and 3.77 g (0.033 mol) of chloroacetyl chloride are carefully added to it. The resulting slurry is brought to the reflux temperature and held for one hour. The mixture is then diluted with an equal volume of hexane and the mixture is allowed to stand. The product crystallizes out and the resulting solid is filtered off and air dried to give 5 * 8 g (69%); the filtrate is distilled off and 2.7 g of white solid with mp are obtained. 121-12U ° C (sealed tube).

20 Analysis for Ο ^ Η ^ ΟΙΡ ^ ΝΟ (%) Element Theory found C U9.73 1 * 9.36 H 1 *, 17 1 *, 09 N 5.27 5.33

The product is identified as 2-trifluoromethyl 6'-25 ethyl 2-chloroacetanilide.

Primary amines of the type used to prepare secondary anilides by haloacetylation as described above are known in the literature, see, for example, U.S. Pat. No. 3,966,811,30 and British Pat. No. 2,013,183 mentioned above.

As mentioned above, the compounds of the invention have been found to be effective as herbicides, especially as pre-germination herbicides, although post-germination activity is also shown. The pre-germination tests included both greenhouse and field tests. In the greenhouse tests, the herbicide is applied both to the surface after planting the 81 01 326 - 1¾ seeds or vegetative propagation parts or to be incorporated in an amount of soil which is applied as a coating over the test seeds in pre-sown test pots. In the field trials, the herbicide may be applied to incorporate the plant 5 into the soil ("PPI"), i.e. the herbicide is applied to the surface of the soil, then incorporated therein by mixing means followed by planting the crop seeds, or the herbicide can be applied to the surface ("SA") after the crop seed has been planted.

The surface application ("SA") test method used in the greenhouse is carried out as follows: Bins eg aluminum bins of 2U, 13 x 13.3 ^ x 6.99 cm or plastic bins of 9.53 x 9 »53 x 7 »62 cm with drip holes in the bottom are filled to the ridge with Ray silt loam soil and then compacted 15 to a level of 1.27 cm from the top of the bins.

The trays are then seeded with the plants to be tested, covered with a 1.25 cm thick layer of the test soils. The herbicide is then applied to the surface of the soil, for example with a belt sprayer in an amount of 187 l per ha under a pressure of 0.2 MPa. Each tray receives 0.6H cm of water as the top irrigation and the trays are then placed on greenhouse banks for subsequent bottom irrigation as needed. As an alternative method, the irrigation from above can be omitted. The herbicidal effects are considered approximately 3 weeks after the. i 25 treatment.

The herbicidal treatment by incorporation into the soil (Si) used in the tests in the greenhouses is as follows:

A good type of topsoil is placed in aluminum pans and compressed to a depth of 0.95-1.25 cm 3j6 from the top of the pan. On top of the soil one brings a number of seeds or vegetative reproductive parts of different plant species. The soil needed to fill the pans completely after sowing or adding the vegetative plant parts is weighed in a pan. The soil and a known amount of the active ingredient, which is applied in an 8101326-15 solvent or as a wettable powder suspension, are thoroughly mixed and used to cover the prepared pans. When treated, the pans are given an initial irrigation of water from above, equivalent to 0.6bcm of rainfall, and then wetted by irrigation as needed to obtain a suitable moisture content for germination in growth. On the other hand, irrigation from above can be omitted. Observations are made approximately 2-3 weeks after sowing and treatment.

Tables B and C show the results of tests conducted to determine the pre-germination herbicidal activity of the compounds of the invention. In these tests, the herbicide is applied by incorporation into the soil and by adding water only from below. The herbicide rating is obtained using a fixed scale based on the percentage damage of each plant species.

The rating scale is as follows:% Combat Rating 0-2k 0 25-b9 1 50-7b 2 75-100 3, indefinite 5

The plant species used in one set of experiments, the data of which are shown in Table B, are identified by letters according to the following table: A Canada Thistle E Loosestrife I Aleppo Millet £ IQis F Knotweed J Gentle Swab C Mallow G Yellow Nut Sedge H hanepoot D Dayflower H ^ eras 8101326 - 16 -

Table B pre-germinating compound pltteoort of example kg / ha ABCDEFGHIJK- I 11.2 53333 3 33333 5.6 52233333333 II 11.2 21132233333 5.6 32132302233 III 11.2 31233333233 5.6 20233233133 IV 11.2 53233333333 5.6 52123333333 3333 532 532333333 VI 11.2 52133333333 5.6 5 2 0 1 3 3 3 3 3 3 3 VII 11.2 3 1 2 2 3 0 2 3 1 3 3 5.6 10 113 0 13 13 3 VIII 11.2 32023333333 5.6 3 1 0 3 3 3 3 3 2 3 3 IX 11.2 32233333333 5.6 32123333133 X 11.2 3 2 1 3 3 3 3 3 3 3 3 5.6 3 1 1 2 3 3 3 3 0 3 3 XI 11.2 31133333033 5.6 3 1 1 2 3 3 1 3 1 3 3 XII 11.2 32023333033 5.6 31021233333 XIII 11.2 32233333333 5.6 32233333233

The compounds are further tested by applying the above-mentioned procedure to the following plant species: L soybean Q wild buckwheat J soft carrot M sugar beet D day flour S hand grass es wheat N hemp K hand leg 0 rice E loosestrife P millet P millipede B burdock C mallow

The results are shown in Table C: 81013 2 6 - 17 -

Table C

Pre-germinating connection of front

image _kg / ha L Μ N 0 P B Q D R E F C J S K T

I 5.6 1233303333323333 1.12 01 1 2 301223203333 0.28 0102101033302333 0.056 000000001 1 100223 0.0112 0000000001100122 II 5.6 1323312333303335 1.12 032320131 2203335 0.28 0201 1001 1 1003335 0.056 0100000000001 135 0.0112 000000 0113310313003333 OOO220OOO3OOI 1.12 0.28 0.056 0001 333 000 002 300 333 0.0112 0.0056 00000000030001 0000000001000333 2333323333313333 01 IV 5.6 1.12 0.28 1323313233313333 0122101013302333 0111221021100223 0.056 0.0112 0100000001000333 1233313333313333 V 5.6 1.12 0.28 0223302023303333 0213322323303333 0101212013102333 0 0.056 , 0112 010001 1003101233 VI 5.6 12.1 1333323333313333 0103313313303333 0202222133303333 0.28 0.056 0.0112 0201212223102333 0322302223003333 0201022223101 133 VII 5.6 1.12 0.28 0100101002000233 0000001200000223 0101000003200023 0.056 1.12 VIII 5.6 2333323333313333 1233302013303333 0011100001101333 0 0.056 0.28 0121202021 102333 , 0112 1000010010001023 8101326 - 18 -

Table C (continued)

Pre-germinating

connection of example_kg / ha LMNOPBQ DREFCJSKT

IX 5.6 2233323332313333 1.12 12331 13122203333 0.28 1223201121103333 0.056 000000000210233 3 0.0112 0000000000000033 X 5,6 3333323333303333 1.12 1233303322303313 0.28 0222201023203333 0.056 010100001 0000333 0.0001 .28 0 21210001 1 103335 0.056 OIOOOOOO5OOOI235 0.0112 0100000000000135 XII 5.6 1223312202103333 1.12 1212302212203333 0.28 010100100100123 2 0.056 Ο5ΟΟΟΟ5ΟΟΟΟΟΟΟ2Ο XIII 5.6 2333323333323333 1.12 123330223230

The herbicides according to the invention have unexpectedly been found to have superior properties as pre-germinating herbicides, particularly in the selective control of difficult to destroy perennial and annual weeds, including such perennials as cultivated grass, yellow and purple nut sedges, annual broadleaf weeds such as lamprey, sesbania hemp, knotweed, loosestrife, melgan foot and annual grasses such as brittle reed, short stem, aleppo millet, Texas hand grass, wild pseudo millet, red rice, itch grass (Raoul grass, Rottboellia exaltata), foxtails eg green, yellow and giant cultivated grass. Weed stance reduction has also been obtained from other resistant species such as Ambrosia, mallow, day flower, burdock, purslane, etc.

8101 326 - 19 -

Selective control and increased suppression of the above weeds with the herbicides of the invention have been found in a number of crops including corn and soybeans of particular interest, but others such as cotton, peanut, turnip, brown bean, wheat and millet as well. However, the latter two crops are usually less tolerant of the inventive herbicides than the other mentioned crops. Such reduced tolerance can be improved by using Safeguards, ie herbicidal antidotes.

The discussion in the tables which follow now refers to herbicidal application amounts symbolized by "GR ^" and "GRq ^". These amounts are expressed in kg / ha. GR ^ defines the maximum amount of herbicide required 15 to 15% or less crop damage and GRg ^ defines the minimum amount required to achieve 85% weed inhibition The GR ^ and GRg ^ amounts are used as a measure of potential commercial behavior, it being understood that suitable commercial herbicides will be more or 20 less severe plant damage within reasonable limits.

A further guideline for the effectiveness of a chemical as a selective herbicide is the "selectivity factor" (SF ”) for a herbicide in certain crops and weeds. The selectivity factor is a measure of the relative degree of crop safety and weed damage and is expressed in the GR ^ / GRg ^ ratio, i.e. the GR ^ quantity for the crop divided by the GRg ^ quantity for the weeds, both in kg / ha, The following tables show the 30 selectivity factors (behind the GRg, amount for each weed. The symbol "NS" means non-selective. Marginal or indeterminate selectivity is indicated by a dash.

Since crop tolerance and weed control are related, a brief discussion of this relationship in terms of selectivity factors 8101326-20 is significant. In general, it is desirable that crop safety factors, i.e., herbicide tolerance values, be high, since higher concentrations of herbicide are often desired for some reason. Conversely, it is desirable for herbicide levels to be small, that is, the herbicide has a high activity per unit for economic and potential environmental reasons. However, small application amounts of a herbicide may not be suitable to control certain weeds and a larger amount may be required. The top 10 herbicides are therefore those that control the greatest number of weeds with the least amount of herbicide and provide the greatest degree of crop protection, i.e. crop tolerance. Therefore, selectivity factors (as defined above) are used to quantify the relationship between crop protection and weed control. With regard to the selectivity factors listed in the tables, it is noted that the higher the numerical value, the greater the selectivity of the herbicide for weed control in a given crop.

To illustrate the unexpectedly superior properties of the compounds of the invention both on an absolute basis and on a relative basis, greenhouse tests are conducted with known compounds most closely related in chemical structure to the compounds of the invention. the invention. These known compounds are identified as follows (using the same nomenclature as for the compounds of the invention): A. N- (methoxyethyl) 2'-trifluoromethyl 2-chloroacetanilide.

B. N- (ethoxyethyl) 2'-trifluoromethyl-2-chloroacetanilide.

Tables D and E show pre-germinating herbicidal activity data comparing the relative efficacy of the compounds of the invention and said known compounds as selective herbicides 81013 2 6 - 21 - against the resistant and difficult to control perennial weed graft and yellow nut sedge with soybean resp. maize. These weeds are usually associated with such main crops as corn and soybean. The test data in Tables D and 5E were obtained under identical conditions and represent the average of two replicate tests (except for the compound of Example XIII present in one comparison test). The test procedure is the same as described for Tables B and C, but modified using an initial overhead irrigation equivalent to 0.64 cm of rainfall.

The watering after this is done by sub-irrigation. NS means non-selective within the test limits.

Table D

gr15 gr85 15 (kg / ha) (kg / ha) _ compound soybean cultivated grass yellow nut sedge A '> 2.24> 2.39 (NS) 1.13 (1.98) B 1.95 0.61 (3, 21) 0.44 (4.45)

Ex. I 2.67 0.17 (15.6) 0.17 (15.6) 20 Vb. III 1.68 0.27 (6.22) 0.19 (8.84)

Ex. IV 1.12 0.13 (8.62) 0.17 (6.59)

Ex. V 1.46 0.26 (5.62) 0.26 (5.62)

Ex. XIII 2.13 0.20 (10.65) 0.17 (12.53)

From this table it appears that each compound according to the invention exhibits much higher selectivity factors (values in brackets) against both cultivated grass and yellow nut sedge in soybeans than the known compounds. More specifically, it is noted that the unit activities (relative plant toxicity per unit of herbicide) of the compounds of the invention are markedly higher over cultivated grass and yellow nut sedge than those of the known compounds, while maintaining crop protection. Particular attention should be paid to the extraordinarily high selectivity factors of the compounds of Examples I and XIII.

Further comparison data showing the relative efficacy of the compounds of the invention over the known compounds versus culture grass and yellow nut sedge in maize are shown in the following Table E:

Table E

5 GR15 GRg5 (kg / ha) _ (kg / ha) _ compound maize cultivated grass yellow nut sedge A> 2.2U> 2.39 (NS) 1.13 (1.98) B 0.81 0.61 (1, 33) 0, UU (1.8U) 10 Ex. I 0.76 0.17 (FC VR) 0.17 (U, U7)

Ex. III 1.9H 0.27 (7.19) 0.19 (10.2)

Ex. IV 0.75 0.13 (5.85) 0.17 (U, * »7)

Ex. V 1.83 0.26 (7.0¼) 0.26 (7, <A)

Ex. XIII 2.2U 0.20 (11.2) 0.17 (13.18) From this table, it can be seen that each compound of the invention exhibits much higher selectivity factors to both maize grass and yellow nut sedge in maize than the known connections. Again, it can be noted that the unit activities of the compounds of the invention are markedly higher over cultivated grass and yellow nut sedge than those of the known compounds, while maintaining crop protection. Particular attention deserves the high selectivity factors of the compounds of Examples III, V and XIII, especially when compared to those of the known compounds.

From the comparative data shown in Tables D and E, it will be apparent that the compounds of the invention exhibit excellent higher and unexpectedly superior herbicidal efficacy against the herbicide resistant perennial weeds cultivated grass and yellow nut sedge in two main crops ie soybean and corn , then compounds A and B, the most closely related compounds, which are known.

In addition, pre-germinating herbicidal data from other experiments determined that compounds of the invention also selectively control cultivated grass, yellow nut sedge and / or 81013 2 6 - 23 - other weeds in one or more of the washed cotton, groundnut, brown bean, wheat, barley and / or turnip. For example, Table F shows data showing the herbicidal selectivity of the compounds of Examples I and III against rape, brown bean, barley, and wheat culture grass. Unless otherwise noted, greenhouse tests in Table F and in other tables that follow involve herbicidal treatments by incorporation into the soil and an initial top irrigation followed by bottom irrigation, as previously described.

10 Table F

®15 ^ 85 _ (kg / ha) _ (kg / ha)

Compound turnip green beans millet wheat cultivated grass

Ex. I 0.86 - 0.12 (7.2) 15 - 0.90 - - 0.12 (7.5) 0.2k - 0.12 (2.0) - - - 0.21 0.12 ( 1.8)

Ex. III 1.9 - - - 0.28 (6.8) 2.2k - - 0.28 (8.0) 20 - - 0.8U - 0.28 (3.0) - - - 0.28 0 , 28 (1.0)

The compounds of Example I are also tested in the field to determine their pre-germination selectivity to foxtail species, coot and white pseudo millet in a number of crops. The data (representing three replicate trials) is shown in Table V for both surface application (SA) and soil incorporation (PPI, i.e., before planting) of the herbicide. The seeds are planted in a fine seed bed of mud loam of medium moisture. The seeds are planted to a depth of 5.08 cm.

The first rainfall (0.51 cm) occurred the day following the treatment, the second 0.6k cm the second day after the treatment, while the cumulative rainfall 22 days after the treatment was 57 cm. The observations were made 6 weeks after the treatment.

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The data in Table G show that, in general, the compound of Formula 1 behaves better as a selective herbicide when applied to the surface than when incorporated into the soil. More specifically, in the surface application tests, the herbicide selectively controlled the three weeds in the test at application rates above 0.58 kg per ha, while maintaining crop protection (that is to say up to about 15% maximum damage) in field corn and soybean up to maximum U, U8 kg per ha and protection for sweet corn, groundnut and turnip at more than 2.2¾ kg per ha and for cotton, millet and brown bean at just under 2.2¾ kg per ha. In the FPI trials, the compound of Formula 1 selectively controlled foxtail and coot at less than 1.12 kg / ha, while maintaining crop safety with field corn, groundnut and turnip at rates up to 2.2 kg / ha and slightly below 2.2¾ kg / ha for soybean.

Other field trial data for the compound of Formula 1 show pre-germination selective control of other weeds in soybean, corn, cotton and / or groundnut such as purple nut sedge, giant food tail, yellow foxtail, loosestrife, day flower, burdock, mallow, knotweed, purslane, blood millet, goose grass, Texas hand grass, Florida postal system and / or bristly prickly nose. It will be apparent to those skilled in the art that not all of said weeds are selectively controlled in all said crops including conditions of climate, soil, moisture and / or herbicidal application methods. Selectivity data for control of the above weeds in the washed soybean, corn, cotton and groundnut for a number of field trials in different locations under different soil, moisture, etc. conditions are shown together in the following tables H, J, K and L. Herein means "WHAT" weeks after treatment of the plants with the herbicide applied either by surface application (SA) or by incorporation into the soil before planting (PP1). The application amount of data for each crop / weed combination is shown in terms of GR and GR amounts (previously defined), the 85% 8101326-26 GR / GRg ratio providing the selectivity factor SP. NS means non-selective and a flat dash indicates marginal or indeterminate selectivity, for example because the actual GR ^ and GRg ^ quantities are higher or lower than the maximum or minimum quantities used in the indicated test. In Tables H, J, K and L, a blank indicates that the plant species was not in a given pilot plan or that the data was not obtained or was less important than other data mentioned, e.g. some 3 WHAT observations have been omitted in favor of 6 WHAT data or 6 WHAT data omitted because the 3 WHAT data were final.

Table H

apply crop / weed connection - WHAT GR.-A / Rg-SF

combination method 5?

Ex. I soy / giant SA 3 needle 5> ^, H8 / <1.12 (> ^, 0) PPI 3 5> fc, WJ / <1.12 (> U, 0) 8> U, U8 / <1, 12 (> M) soy / yellow SA 6 2.52 / 2.8 (NS) needle needle PPI 6 1, ty <1.12 (> 1.3) soy / loosestrife SA 6 2.52 / 2.52 (1 .0) PPI 6 1.4 / 2.8 (NS) soy / Pennsyl PPI .8 4.48 / 2.52 (1.8) vania knotweed

The data of Table H show that the compound of Example I selectively combats giant and yellow needle pinar, loosestrife and knotweed from Pennsylvania in 6-8 watts of soybeans in both the SA and PPI modes of application.

8101 326 - 27 -

Table J

apply crop / weed connection - WHAT GR ^ / GR * ,. SP combination is them

Ex. I maize / giant SA 6 4.48 / 0.12 (U, 0) needle needle SA 6.5> 7.84 / 8.4 (NS) PPI 6 4.76 / 1.96 (2.5) PPI 6 .5> 6.72 / 4.48 (1.5) maize / day flour SA 3> 4.48 /> 4.48 (-) SA 6> 4.48 /> 4.48 (-) PPI 3 4, 76 /> 4.43 (-) PPI 6 4.76 /> 4.48 (-) corn / burdock SA 3> 4.48 /> 4.48 (-) SA 6> 4.48 /> 4.48 (-) PPI 3 4.76 /> 4.48 (-) PPI 6 4.76 /> 4.48 (-)

The data of Table J shows that the compound of Example I selectively fights giant needle in 6-6.5 WAT corn according to either the SA or PPI mode of application.

The selectivity to day flower and burdock is undetermined in the test quantities, where suppression of these weeds is evident.

Table K.

crop / weed connection applied - WHAT GR ^ / GRe, - SF

combination method

Ex. I cotton / purple SA 6 3.64 / 1.68 (2.17) nut sedge SA 9 3.36 / 2.2¾ (1.5) PPI 6 3.36 / 4.2 (NS) cotton / needle nose SA 6 3.64 / 3.03 (1.18) SA 9 3.36 / 4.76 (NS) PPI 6 3.36 / 4.76 (NS) cotton / purslane SA 9 3.36 / 1.96 (1 , 7) cotton / blood millet SA 7 1.4 / <1.12 (> 1.25) (smooth and hairy) ρρχ γ 0.84 / 1.12 (NS) cotton / adhesive PPI 7 0.84 / < 1.12 (-) herb

The data of Table K show that the compound of Example I selectively combats purple nut sedge and purslane up to a maximum of 9 watts, prick nose up to a maximum of 6 watts and blood millet up to a maximum of 8101326 τ - 28 - 7 watts, while the control of cleavers is marginal or indefinite.

Table L presents pre-germination activity data for the compound of Example I against three resistant annual weeds, ie Texas palm grass, bristly starbur and Florida purslane on groundnuts for periods up to 12 watts. The data in Table L represents the average of three replicate tests in sandy loam soil with 1.3% organic matter, 97.2% sand and 10% clay with the herbicide applied to the surface.

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The data in Table L shows that the compounds of Example I selectively control Texas hand grass in groundnuts for up to 3 weeks and provide a high degree of control even at 12 watts at about 1 +, 1 + 8 kg / ha.

5 Selective control of bristly starbur is obtained at 3.36 kg / ha for 8 weeks and full control maintained for 12 WHAT at 1 +, 1 + 8 kg / ha and selective control of Florida purslane is obtained with less than 2.2U kg / ha at 8 WAT and with 1 +, 1 + 8 kg / ha, 95% control is obtained at 10 WAT.

In other greenhouse tests, compounds of the invention have been found to selectively control a number of annual and perennial weeds in different crops. As a further illustration, the compound of Example I selectively combats purple nut sedge in both corn and soybean, the resp. crop / weed GR ^ / GRg, - ratios (expressed in kg / ha) are 0.67 / 0.25 (SF = 2.7) in maize and 1.12 / 0.25 (SF = U, 5) in soya bean. The compound of Example XI has been found to selectively control yellow nut sedge and farm grass in corn and soybeans.

20 The resp. crop / yellow nut sedge GR ^ / GRq ^ ratios are 2.21 + / 0.95 (SF «2.1+) for maize and 2.21 + / 0.5 (SF = 1 +, 5) for soybean and the resp. . GR ^ / GRqj. proportions for both corn and soybean for farm grass is 2.21 +/- 0.5 (SF = 1.5 +). In a test against yellow nut sedge in cotton, the GR ^ / GRg ^ ratio (average of 25 two replicas) is 1.95 / 0.95 (SF = 2.1). Likewise, the compound of Example XIII shows selective control of yellow nut sedge in cotton and cultivated grass in wheat, the resp. GR ^ / GRg ^ ratios 0.7 / 0.1 + 7 (SF = 1.7) are in cotton and 0.58 / 0.1 + 7 (SF = 1.2) in wheat.

In a multiple greenhouse crop test, the compounds of Examples I, XIII, XIV and XV are tested against yellow nut sedge in cotton, soy, corn and rice. Each compound was non-selective with regard to yellow nut sedge in rice. However, remarkably high selectivities for 35 yellow nut sedge in cotton, soy and corn are shown for each of the 8101326-31 compounds of the test. The respective GR and GRg amounts for these compounds are shown in Table M. The selectivity factors are shown in brackets after each crop.

Table M

GR85 GR15 (kg / ha) (kg / ha) compound yellow nut sedge cotton soybean corn 10 Ex. I 0.24 1.96 (8.2) 0.87 (3.6) 0.69 (2.9)

Ex. XIII 0.21 2.52 (12.0) 1.96 (9.3) 2.52 (12.0)

Ex. XIV 0.38 2.8 (7, ¾) 2.21+ (5.9) 1.68 (4.4)

Ex. XV 0.44 2.8 (6.4) 1.96 (4.5) 1.96 (4.5)

The compounds of Examples I and XIII-XV

15 are further tested against cultivated grass in wheat, soybeans and corn, each compound proving to be non-selective for wheat. The selectivity data for the above compounds against culture grass in soybean and corn are shown in Table H ".

20 Table I GR85 ®15 (kg / ha) (kg / ha) compound cultivated grass soy corn

Ex. I 0.07 0.81 (11.6) 0.69 (9.9) 25 Ex. XIII 0.36 1.68 (4.7) 1.68 (4.7)

Ex. XIV 0.45 1.46 (3.2) 2.52 (5.6)

Ex. XV 0.75 (1.96) (2.6) 2.24 (3.0)

In still other greenhouse tests for herbicidal effectiveness, the compounds of Examples I and III are used

30 tested against a number of annual grasses, including resistant weeds such as Texas hand grass, seedling alepo millet, brittle reed, short stalk, wild pseudo millet (panicum milicaeum), red rice and itch grass. The results of these experiments are shown in Table 0, where the selectivity factors are again shown in brackets and a flat dash indicates marginal or indeterminate selectivity.

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The data in Table O show that the compound of Example I selectively controls each annual weed of the test in soybean. The compound of Example III shows positive selective control against all weeds, except Texas hand grass, skinned pseudo millet and itch grass at the maximum test rate of 1.12 kg / ha. A larger amount would be needed to determine the selectivity of the compound against the three weeds, which are not selectively controlled in the test amount.

A clear advantage of a herbicide is its ability to function in a wide variety of soil types. Therefore, Table P provides data on the herbicidal effect of the compound of Example I on soybean grass in a wide variety of soil types of varying organic matter and clay content. The herbicidal treatments are carried out by incorporation into the soil of seeds planted at 0.95 cm deep with 0.6 cm of irrigation from above. Observations are made approximately 3 weeks after treatment. The selectivity factors are again in brackets.

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The data of Table P shows that the compound of Example I appears to be very insensitive to soil types of different organic matter content, and to show selective control of culture grass in soy in soils with 1.0 - 60% organic matter and clay contents of 1.8 - 37 / ». The data for soy in sludge-like clay from Wabash are undetermined in this test. Also, the specified selectivity factors in sludge-like clay from sarpy and Drummer and dredge from Florida are minimum values, since the maximum test amount is 2.2h kg / ha and the herbicide is safe for soy at the same amount above 2.2k kg / ha.

Laboratory tests are conducted to determine the resistance of herbicides of the invention to soil leaching and resulting herbicidal effectiveness.

In these tests, the compounds of Examples I and IV-VI are formulated in acetone and then sprayed at different concentrations onto a weighed amount of Ray sludge loam and Drummer sludge clay loam in pots with filter holes covered by filter paper. bottom. The pots with the treated earths are subjected to dripping by placing them on a turntable rotating under two nozzles of a water vessel, which mimics 2.5 cm of rainfall per hour. The watering amounts are set by varying the time on the turntable. Water is added to the soil in the pots and percolated through the filter paper and drainage holes. The pots are then allowed to stand at room temperature for 3 days. The treated soil in the pots is then softened, crumbled and placed as a surface layer on top of other pots containing the above earths, seeded with hanepod. The pots are then placed on greenhouse banks, irrigated from below and grown for 2-3 weeks. Visual valuation of the percent growth inhibition compared to blank (untreated) pots and fresh weed leg weights are recorded. The data for the blank represents six replicas and that of the test compounds three replicates. The test results are shown in Table Q. Fresh weights of the weeds were not measured in the Drummer mud loam soil tests.

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The data in Table Q shows that the compounds of the invention are very resistant to soil leakage under varying rainfall conditions. In particular, at 2.2¼ kg / ha, each of the compounds of the invention control coot under the equivalent of 10.16 cm of rainfall in Ray mud and Drummer mud clay except the compounds of Examples I and V in Ray mud, where control was maintained below the equivalent of 5.08 cm of rainfall. Even at the low application rate of 0.1U kg / ha 10 combating compounds of Examples I, IV and V coot in Drummer muddy clay loam under the equivalent of 5.08 cm of rainfall.

Toxicity studies on the compound of Example I have shown this to be completely safe. It is slightly toxic (OLD ^ q 2300 rag / kg; MLD ^ Q over 5010 mg / kg) and is slightly irritating to the eye but not to the skin. No special treatment procedures other than normal precautions are considered necessary.

Therefore, it will be apparent from the foregoing detailed description that compounds of this invention have been found to have unexpected and extremely superior herbicidal properties both absolutely and relatively above the most structurally relevant prior art compounds. More particularly, the compounds of the invention have been found to be extremely selective herbicides, particularly for controlling hard-to-destroy perennial and annual grasses in soy and corn, but also in groundnut, cotton and other crops. More particularly, compounds of the invention exhibit extra ordinary pest control of perennial weeds such as cultivated grass and nut sedges and resistant annual grasses such as Texas hand grass, itch grass, wild pseudo millet, short stem, seedling aleppo millet, brittle reed and / or red rice , while other less resistant annual grasses and perennial are also controlled and / or suppressed.

8101326 - 39 -

The herbicide compositions of the invention, including concentrates that require dilution for use, contain at least one active ingredient and an additive in liquid or solid form. The compositions are prepared by mixing the active ingredient with an additive, including diluents, thickeners, carriers and conditioners to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient should be used with an additive such as a particulate solid, an organic liquid, water, a wetting agent, a dispersing agent, an emulsifying agent, or any suitable combination thereof.

The compositions according to the invention, in particular liquids and wettable powders, preferably contain as one conditioning agent one or more surfactants in amounts sufficient to make a given composition easily dispersible in water or in oil. The inclusion of a surfactant in the 20 compositions greatly increases their effectiveness. The term "surfactant" is here understood to mean wetting agents, dispersants, suspending agents and dispersing agents. Anionic, cationic and non-ionic agents can be used with the same ease.

Preferred humectants are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty acid alcohols, amines or acid amides, long chain fatty acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters (sulfonated phenol ethenylphenol acetol oils, polyphenylene glycol acetates, polyolethyl acetate oils, especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono higher fatty acid esters of hexitol anhydrides (e.g., sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl, 8101326-UO-naphthalene sulfonates, sodium naphthalene sulfonate, and the polymethylene bisnaphthalene sulfonate.

Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid thickener, and one or more wetting and dispersing agents. The inert solid thickeners are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such thickeners are kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the invention usually contain 0.5-60 parts (preferably 5-20 parts) of active ingredient, 0.25-25 parts (preferably 1-15 parts) of wetting agent, 0.25-25 15 parts (preferably 1.0-15 parts) dispersant and 5-95 parts (preferably 5-50 parts) inert solid thickener, all parts by weight of the total composition. If required, 0.1-2.0 parts of the solid inert thickener can be replaced with a corrosion inhibitor or anti-foaming agent 2Qf or both.

Other formulations include dust concentrates containing 0.1-6% by weight of the active ingredient to a suitable thickener. These powders can be diluted before application at concentrations within the range of 0.1-10% by weight. Aqueous suspensions or emulsions can be prepared by stirring an aqueous mixture of a water-insoluble active ingredient and an emulsifying agent to uniform and then homogenizing to a stable emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that the coating is very uniform upon dilution and spraying. Suitable concentrations of these recipes contain 0.1-60, preferably 5-50% by weight of active ingredient, the upper limit being determined by the solubility limit of active ingredient in the solvent.

8101326, 4 - In -

In another form of aqueous suspensions, a water-immiscible herbicide is encapsulated to obtain a microencapsulated phase dispersed in an aqueous phase. In one embodiment, very 5 small capsules are formed by combining an aqueous phase containing a lignin sulfonate emulsifying agent and a water-immiscible chemical with polymethylene polyphenyl isocyanate, dispersing the water-immiscible phase 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 immiscible water-miscible chemical to form microcapsules thereof. Generally, the concentration of the microencapsulated material will range from 1 * 80-700 g / l total composition, preferably U80-600 g / l.

Concentrates are usually solutions of active ingredient in water-immiscible or partially water-miscible solvents together with a surfactant. Suitable solvents for the active ingredient according to the invention include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones. However, other strong liquid concentrates can be formulated by dissolving the active ingredient in a solvent, after which it is diluted, for example, with kerosene to spray.

The concentrates generally contain about 0.1-95 parts (preferably 5-60 parts) of active ingredient, 0.25-50 parts (preferably 1-25 parts) of surfactant and, if required, about U-9U parts of solvent , all 30 parts by weight based on the total weight of emulsifiable oil.

Granules are physically stable particulate compositions containing active ingredient attached to or distributed by a base soil mass of an inert particulate particulate thickener. In order to prevent the active ingredient from being leached from the particles, a surfactant such as those mentioned above may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of active classes of particulate mineral thickeners.

The preferred thickeners are the porous absorbent preformed particles such as preformed and sieved particulate attapulgite or heat expanded particulate vermiculite and the finely divided clays such as kaolin clays, hydrated attapulgite or bentonite clays.

These thickeners are sprayed or mixed with the active ingredient to form herbicidal granules.

The granular compositions according to the invention can contain about 0.1-30 parts, preferably 3-20 wt.

15 parts of active ingredient contain per 100 parts by weight of clay and 0-5 parts by weight of surfactant per 100 parts by weight of particulate clay.

The compositions of the invention may also contain other additives, for example, fertilizers, other herbicides, other pesticides, protectants and the like used as additives or in combination with any of the additives described above. Chemicals useful in combination with the active ingredients of the invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, triazole, benzoic acids, nitriles, biphenyl ethers and the like such as:

Heterocyclic nitrogen / sulfur derivatives 2-chloro H-ethylamino 6-isopropylamino s-triazine 30 2-chloro U, 6-bis (isopropyl amino) s-triazine 2-chloro, 6-bis (ethylamino) s-triazine 3-isopropyl 1H-2,1,3-benzothiadiazin-U- (3H) -one 2,2-dioxide 3-amino 1,2, U-triazole 6,7-dihydrodipyrido (1,2-a: 2 ', 1' -c) -pyrazidinium salt 35 5-bromo 3-isopropyl 6-methyluracil 1,1'-dimethyl U, V-bipyridinium 8101326 - ^ 3-

Urea N '- (H-chlorophenoxy) phenyl N, N-dimethyl urea N, Ν-dimethyl N' - (3-chloro-H-methylphenyl) urea 3- (3,1-dichlorophenyl) 1,1-dimethyl urea 5 1.3 -dimethyl 3- (2-benzothiazolyl) urea 3- (p-chlorophenyl) 1,1-dimethyl urea 1-butyl 3- (3, H-dichlorophenyl) 1-methyl urea

Carbamates / thiolearbamates 2-chlorallyl diethyldithiocarbamate 10 S- (1 * -chlorobenzyl) N, N-diethylthiol carbamate isopropyl N- (3-chlorophenyl) carbamate S-2,3-dichloroallyl N, N-diisopropylthiolcarbamate ethyl N, propyl dipropylthiol carbamate 15 Acetamides / acetanilides / anilines / amides 2-chloro N, N-diallylacetamide N, Ν-dimethyl 2,2-diphenylacetamide N- (2, ^ - dimethyl 5- / "7Γ & rifluoromethyl) sulfonyl7araino7phenyl) -acetamide 20 N- isopropyl 2-chloroacetanilide 2 ', 6'-diethyl N-methoxymethyl 2-chloroacetanilide 2'-methyl 6'-ethyl N- (2-methoxyprop-2-yl) 2-chloroacetanilide α, α, α-trifluoro 2,6- dinitro Ν, Ν-dipropyl p-toluidine N- (1,1-dimethylpropynyl) 3,5-dichlorobenzamide 25 acids / esters / alcohols 2,2-dichloropropionic acid 2-methyl U-chlorophenoxyacetic acid 2, U-dichlorophenoxyacetic acid methyl 2- / "U- (2, H-dichlorophenoxy) phenoxypropionate 30 3-amino 2,5-dichlorobenzoic acid 2-methoxy 3,6-dichlorobenzoic acid 2,3, β-trichlorophenylacetic acid N-1-naphthylphthalamic acid sodium 5- / ~ 2 -chloro (trifluoromethyl) phenoxy 2-nitrobenzoate 35 lf, 6-dinitro o-sec-butylphenol 8101326 -1A- 'N- (phosphonomethyl) glycine and the C ^ g monoalkylamine and alkaline metal combinations thereof Ethers 2, U-dichlorophenyl ^ - nitrophenyl ether 2 2-chloro α, α, α-trifluoro p-tolyl 3-ethoxy U-nitrodiphenyl ether miscellaneous 2,6-dichlorobenzonitrile monosodium acid methanesaronate disodium methanesaronate 10 fertilizers useful in combination with the active ingredients include eg ammonium nitrate, urea potassium carbonate and superphosphate. Other useful additives include materials in which plant organisms root and grow, such as compost, manure, humus, sand and the like.

The herbicidal recipes of the types discussed above are exemplified below in various illustrative embodiments.

I. Emulsifiable concentrates wt. % 20 A. Compound of Example No. 1 50.0 calcium dodecylbenzene sulfonate / polyoxyethylene ethers mixture (eg, Atlox 3J + 37F) M5

Calcium dodecylbenzene sulfonate 2j (FloMo 60H) 0.15C aromatic solvent 1 * 5.00 100.00 B. Compound of Example IV 85.0

Calcium dodecyl sulfonate / alkylaryl 2o polyether alcohol mixture 1 *, 0

Cp aromatic hydrocarbon solvent 11.0 100.00 81013 2 6 - ^ 5- C. Compound of Example VI 5.0 calcium dodecylbenzene sulfonate / polyoxyethylene ethers mixture (e.g., Atlox 3 ^ 37F) 1.0 xylene 9 ^ 0 100 .00 II. Liquid Concentrates wt.% A. Compound of Example No. IV 10.0 xylene 90.0 100.00 B. Compound of Example No. V 85.0 dimethyl sulfoxide 15.0, 100.00 C. Compound of Example No. VI 50.0 N-methylpyrrolidone 50.0 100.00 D. Compound of example No. VII 5.0 ethoxylated castor oil 20.0 rhodamine B 0.5 dimethyl formamide 7.5-5 100.00 III. Emulsion A. Compound of Example No. XII ^ 0.0 polyoxyethylene / polyoxypropylene block with butanol (e.g. Tergitol XH) 0.0 water 56.0 100.00 B. Compound of example No. XIII 5.0 polyoxyethylene / polyoxypropylene block copolymer with butanol 3.5 water 91.5 100.00 8101326 - 1 + 6 - V * IV. Wettable powders 7% by weight. A. Compound of example No. I 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 no. XII 80.0 sodium dioctyl sulfosuccinate 1.25 calcium lignosulfonate 2.75 amorphous silica (synthetic) 16.00 100.00 C. Compound of Example No. XIII '10.0 sodium lignosulfonate 3.0 sodium N-methyl-oleyl taurate 1 .0 Kaolinite clay 86.0 100.00 V. Dusting powders by weight $ A. Compound of Example No. VII 2.0 Attapulgite 98.0 100.00 B. Compound of Example No. VIII 60.0 Montmorillonite 1 + 0 .0 100.00 C. Compound of Example No. IX 30.0 Bentonite 70.0 100.00 D. Compound of Example No. X 1.0 Diatomaceous Earth 99.0 100.00 VI. Granules by weight $ A. Compound of Example No. I 15.0 granulated attapulgite (0.1 + 2 / 0.81 + ram) 85.0 100.00 8101326 - 47 - Β. Compound of example No. VI 30.0 diatomaceous earth (0.42 / 0.8¼ mm) 70.0 100.00 C. Compound of example No. XII 0.5 5 bentonite (0.42 / 0.84) 99.5 100 .00 D. Compound of Example No. XIII 5.0 Pyrophyilite (0.42 / 0.84) 95.0 100.00 ^ VII. Microcansules

Rev.% A. Compound of Example No. I encapsulated in polyurea shell 49.2 Sodium lignosulfonate (eg Reax 88 B) 0.9 15 water 49.9 100.00 B. Compound of Example No. XII encapsulated in polyurea shell 10.0 potassium lignosulfonate (eg Reax C-21) 0.5 20 water 89.5 100.00 C. Compound of example no. XIII encapsulated in polyurea scale of 80.0 magnesium salt of lignosulfate (Treax, LTM) 2, 0 25 water 18.0 100.00

When operating according to the invention, effective amounts of the acetanilides of the invention are applied to the soil containing the plants, or taken up in aqueous media in any suitable manner. The application of liquid and particulate solid compositions to the ground can be carried out in conventional ways, for example powered sprayers, pop and hand sprayers and spray atomizers. The compositions can also be applied by airplanes such as a dust or a spray 81013 2 6 - U8 - 7 * due to their effectiveness at low doses. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aqueous media in the area where control of the aquatic plants is desired.

Application of an effective amount of the compound of the invention to the site of unwanted weeds is essential and critical to the practice of the invention. The correct amount of active ingredient used depends on various factors, including the plant species and phase of development, the type and condition of the soil, the amount of rainfall and the specific acetanilide used. In selective pre-germination application on the plants or on the soil, a dosage of 0.02-11.2 kg / ha is usually used, preferably 0.05-5.60 kg / ha or suitably 1.12-5 .6 kg / ha of acetanilide. Smaller or larger quantities may be required in some cases. One skilled in the art can easily determine the optimal amount from this description, including the above examples, to be applied in each particular case.

The term "soil" used herein means soil in the broadest sense of the word as defined in Webster's Hew International Dictionary Second Edition, Unabridged 1961. Thus, the term refers to any substance or medium in which vegetation can root and grow, and includes not only soil, but also compost, manure, sludge, humus, sand and the like adapted to support plant growth.

30 8101326

Claims (45)

1. Compounds of the formula of the formula sheet, wherein R is alkyl or alkoxyalkyl or alkenyl or alkynyl with up to 5 carbon atoms and hydrogen, methyl 5 or ethyl, provided that when hydrogen is R is isopropyl and when R is ethyl, R is ethyl , n-propyl or isopropyl. Compounds according to claim 1, characterized in that R is -alkyl. Compounds according to claim 2, characterized in that R 1 is methyl. If. Compounds according to claim 3, characterized in that the 2- (ethoxymethyl) 2 * -trifluoromethyl 6'-methyl 2-chloroacetanilide. Compounds according to claim 3, characterized in that # / N- (n-propoxymethyl) 2'-trifluoromethyl-6-methyl-2-chloroacetanilide. Compounds according to claim 3, characterized in that it is N- (isopropoxymethyl) 2'-trifluoromethyl-6'-methyl 2-chloroacetanilide. Compounds according to claim 3, characterized in that N- (isobutoxymethyl) 2'-trifluoromethyl-6-methyl 2-chloroacetanilide. 8. A compound according to claim 2, characterized in that R 1 is ethyl. A compound according to claim 8, characterized in that it is N- (ethoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide. 10. A compound according to claim 8, characterized in that the N- (n-propoxymethyl) 2'-trifluoromethyl 30 is 6'-ethyl 2-chloroacetanilide. A compound according to claim 8, characterized in that the N- (isopropoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide. The compound of claim 2, The characteristic is that R1 is hydrogen. 8101326 * * - 50 - Compound according to claim 12, characterized in that it is N- (isopropoxymethyl) 2'-trifluoromethyl 2-chloroacetanilide. 1U. Compound according to claim 1.5, characterized in that R is an alkenyl radical. Compound according to claim 11, characterized in that it is R- (allyloxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. Compound according to claim 1, 10, characterized in that R is alkynyl residue. Compound according to claim 16, characterized in that it is N- (propargyloxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. 18. A compound according to claim 1, characterized in that R is an alkoxyalkyl radical with up to 5 carbon atoms. Compound according to claim 18, characterized in that it is 1- (2-methoxyethoxymethyl) 2'-trifluoro-methyl 6'-methyl 2-chloroacetanilide. 20 20 '. Herbicide composition, characterized in that it contains an additive and a herbicidally effective amount of a compound of the formula on the formula sheet, wherein R is. alkyl or alkoxyalkyl or alkenyl or alkynyl with up to 5 carbon atoms and R 1 is hydrogen, methyl or ethyl, provided that when R 1 is hydrogen, R is isopropyl and when R 1 is ethyl, R is ethyl, n-propyl or isopropyl. Compositions according to claim 20, characterized in that in said compound R is C 1-6 alkyl. 22. A composition according to claim 21, characterized in that in said compound R 1 is methyl. The composition according to claim 22, characterized in that said compound is N- (ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. 2¾. Composition according to claim 22, 35, characterized in that said compound is N- (n-propoxymethyl) 8101326 * f - 51-2-trifluoromethyl 6'-methyl 2-chloroacetanilide. Composition according to claim 22, characterized in that said compound is N- (isopropoxy-methyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. 26. A composition according to claim 22, characterized in that said compound is N- (isobutoxymethyl) 2'-trifluoromethyl 61-methyl 2-chloroacetanilide. 27. A composition according to claim 21, characterized in that it is ethyl. The composition according to claim 27, characterized in that said compound is N- (ethoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide. 29. A composition according to claim 27, characterized in that said compound is N- (n-propoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide. A composition according to claim 27, characterized in that said compound is N-J [isopropoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide. 31. A composition according to claim 21, characterized in that it is hydrogen. The composition according to claim 31, characterized in that said compound is R- (isopropoxymethyl) 2'-trifluoromethyl 2-chloroacetanilide. 33. A composition according to claim 20, characterized in that in said compound R is an alkenyl radical with a maximum of 5 carbon atoms. 3¼. Composition according to claim 33, characterized in that said compound is N- (allyloxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide, A composition according to claim 20, characterized in that in said compound R is an alkynyl radical with up to 5 carbon atoms. A composition according to claim 35, characterized in that said compound is N- (propargyloxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. 8101326 V - »* - 52 - Compositions according to claim 20, characterized in that in said compound R is an alkoxyalkyl radical having up to 5 carbon atoms. 38. A composition according to claim 37, characterized in that said compound is N- (methoxyethoxymethyl) 21-trifluoromethyl 6'-methyl 2-chloroacetanilide. 39. A method for controlling unwanted plants in crops, characterized in that a herbicidally effective amount of a compound of the formula of the formula sheet is applied in its place, in which R is C 1 -5 alkyl. or alkoxyalkyl or alkenyl or alkynyl of up to 5 carbon atoms and hydrogen, methyl or ethyl, provided that when R 1 is hydrogen, R is isopropyl and when R 1 is ethyl, R is ethyl, n-propyl or isopropyl. 15 Ho. Method according to claim 39, characterized in that in said compound R is 1 * 1. Process according to claim HO, characterized in that in said compound R 1 is methyl. k2. Process according to claim U1, 20, characterized in that said compound is N- (ethoxymethyl 2r-trifluoromethyl 6'-methyl 2-chloroacetanilide. Process according to claim U1, characterized in that said compound is N- (n-propoxymethyl) 2'-Trifluoromethyl-1'-methyl 2-chloroacetanilide A process according to claim U1, characterized in that said compound is N- (isopropoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. claim U1, characterized in that said compound is N- (isobutoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide U6 Process according to claim Ho, characterized in that R 1 is ethyl. claim Hey, characterized in that said compound is N- (ethoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroacetanilide 8101326 4 - 53 - 8. Process according to claim U6, characterized in that said compound W- (n-propoxymethyl) 2'-trifluoromethyl 6'-ethyl 2-chloroeeetanil ide is. k9. Process according to claim bè, 5 characterized in that said compound is 1- (isopropoxymethyl] 2 -trifluororaethyl 6'-ethyl 2-chloroacetanilide. 50. A process according to claim Uo, characterized in that it is hydrogen. A method according to claim 50, characterized in that said compound is N- (isopropoxymethyl) 2 -trifluoromethyl 2-chloroacetanilide. 52, Process according to claim 39, characterized in that in said compound R is an alkenyl radical with a maximum of 5 carbon atoms. 53. A process according to claim 52, characterized in that said compound is W- (allyloxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. 5U, A process according to claim 39, characterized in that in said compound R is an alkynyl radical 20 with up to 5 carbon atoms. 55. Process according to claim 5, characterized in that said compound is W- (propargyloxymethyl) 2 * -trifluoromethyl 6'-methyl 2-chloroacetanilide. 56. A process according to claim 39, characterized in that in said compound R is an alkoxyalkyl radical with up to 5 carbon atoms. 57 A method according to claim 56, characterized in that said compound is N- (methoxyethoxy-methyl) 21-trifluoromethyl 6'-methyl 2-chloroacetanilide. A method according to claim 39, characterized in that said crop is corn, millet, soy, cotton, groundnut, brown bean, wheat or turnip. 59 Process according to claim 58, characterized in that said compound is N- (ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide. 8101 326 - 5b - s «- * r- 60. A method for controlling undesired plants in corn, characterized in that a herbicidally effective amount of N- {ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide is used in its place. 61. A method for controlling undesired plant growth in eoja, characterized in that a herbicidally effective amount of N- (ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide is used in its place. 62. A method for controlling undesired plant growth in cotton, characterized in that a herbicidally effective amount of N- (ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide is applied to its place. 63. A method of controlling undesirable plant growth in turnip, characterized in that a herbicidally effective amount of N- (ethoxymethyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide is applied in its place. 6h. Method for combating undesired plant growth in string beans, characterized in that a herbicidally effective amount of N- (ethoxy-20 methyl) 2'-trifluoromethyl 6'-methyl 2-chloroacetanilide is applied in its place. 8101326 -5 \ Γ- Improvement of errata in the specification associated with patent application No. 81.01326 NED. proposed by applicant 30 JUU 1981 Change in line 5 of page 10 "XIII" to "XV" and in lines 5 and 6 of page 13 "XIV" to "XVI". JKr / JvdB 8101326 **. o II Cl ch2c ch2or \ / NT R, - (érCFi! MONSANTO COMPANY, St. Louis, Missouri, USA America 81 01 326