NL8101323A - 2-HALOGENIC ACETANILIDES WITH HERBICIDE ACTION, HERBICIDE PREPARATIONS CONTAINING THESE COMPOUNDS AND METHOD FOR CONTROLLING WEEDS. - Google Patents

Description

- 1 - β- * ϊ + '-ia ^ 2-haloacetanilides with herbicidal action, herbicidal preparations containing these compounds and method of weed control.

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

The state of I relevant to this invention

The art encompasses numerous descriptions of 2-haloacetanilides which may be unsubstituted or substituted with a wide variety of substituents on the anilide nitrogen atom or on the anilide ring, including alkyl, alkoxy, alkoxyalkyl groups, halogen, etc.

As relevant to the compounds of the invention, which are characterized in that they have an alkoxy methyl group or alkenyloxymethyl group on the anilide nitrogen, an alkoxy group in one ortho position and a specific alkyl group in the other ortho position. the closest prior art, as far as known to the applicant, is formed by U.S. Pat. Nos. 3,442,945 and 3,547,620.

The most relevant disclosures in the aforementioned patents are the compounds 2, -tert-butyl-2-chloro-N-methoxynethyl-ö'-methoxyacetanilides and their bromine analog (Examples 20, 18 and 34 of U.S. Pat. No. 3,547,620 and Examples 18 and 36 of U.S. Patent 3,442,945).

US Pat. Nos. 4,070,389 and 4,152,137 disclose general formulas comprising compounds of the type disclosed in said U.S. Pat. Nos. 3,442,945 and 3,547,620. However, the only specific compound with an alkyl group in one ortho position and an alkoxy group in the other ortho position described has an alkoxyethyl group on the anilide nitrogen atom; compounds of this type are discussed in more detail below.

Other less relevant prior art is Belgian patent 810,763 and 8101323 V? - 2 -

German patent application 2,402,983. The compounds of these literature sites include compounds of the type described in U.S. Pat. Nos. 4,070,389 and 4,152,137 and are characterized by an alkoxyalkyl group having 2 or more 5 carbon atoms between the anilide nitrogen atom and the oxygen atom of the alkoxy group. The most relevant specific disclosures in said Belgian Patent Specification 810,763 and in said German Patent Application 2,402,983 appear to be compounds with an ethoxyethyl group on the anilide nitrogen atom, a methoxy or ethoxy group in the one ortho position and a methyl -, ethyl or isopropyl group in the other ortho position; With regard to Belgian patent 810,763, see compounds no. 7, 13, 18 to 20 and 26; other less relevant homologues of these compounds are also described, for example, compounds 6, 9, 16 and 17, which have substituted methoxyethyl or methoxypropyl groups on the nitrogen atom and a methoxy or ethoxy group in the one ortho position and a methyl group in the other ortho position.

The above-mentioned U.S. Patent 20 3,442,945 contains some herbicidal data regarding those above-mentioned compounds having a chemical configuration that is nauxist related to the compounds of the invention and some data are provided for other homologous and analogous compounds that are less closely related in terms of chemical structure, for example said compounds no. 6 and 9 in said Belgian patent 810,763. More specifically, these most relevant references, while describing herbicidal activity against a variety of weeds, do not provide data for any of the compounds shown to additionally and / or simultaneously the stubborn narrow-leaved weeds, black grass, Filtrated oats and fluffy dravik, and other weeds such as yellow needle nature, annuals rye, coot, and digitaria, although the aforementioned Belgian Patent 810,763 provides data showing good control of wild oats and undefined species of various other beet weeds. As in e 1 01 3 2 3

i I

However, compounds of the present invention unexpectedly have superior properties as selective herbicides in sugar beets as compared to the homologous compounds of the prior art.

A further disadvantage of many known herbicides is their limited applicability to special soil types, ie although some herbicides are effective in soils with only small amounts of organic matter, they are ineffective in other soils with a high organic matter content. or vice versa. It is therefore exemplary that a herbicide can be used in all soil types, ranging from light organic to heavy clay and peat.

Yet another drawback of some prior art herbicides is the lack of weed management persistence in heavy rains resulting in leaching of the herbicide.

Finally, a drawback of some herbicides is the need to use special handling procedures due to their toxic nature. A further desideratum 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 which overcome the aforementioned drawbacks of the prior art and provide a multitude of advantages for a single group of herbicides.

An object of the invention is to provide herbicides containing various weeds, especially annual grasses, including intractable narrow-leaved weeds, such as black grass, wild oats and fluffy swamp, and other annual grasses, such as yellow needle, coot, digitaria and annual rye, selective control, especially in sugar beets.

Yet another object of the invention is to provide herbicides which are effective over a wide range of soils, for example, from light medium organic to heavy clay and peat.

Another object of the invention is to provide 8101323i. - 4 - purchase herbicides that can withstand leaching in heavy rain.

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

The above and other ends of the invention will become more apparent from the defined description below.

The present invention relates to compounds with herbicidal activity, herbicidal compositions containing these compounds as active ingredients and methods of using these compositions as herbicides in certain cultivated crops. It has now been found that a selective group of 2-haloacetanilides, characterized by specific combinations of alkoxymethyl or alkanyloxymethyl groups on the anilide nitrogen atom, specific alkoxy groups in the one ortho position and a C 1-6 alkyl, e.g. methyl, ethyl or isopropyl group in the other ortho position, unexpectedly have superior and excellent selective herbicidal properties as sugar beet herbicides compared to prior art herbicides, including most relevant prior art homologous compounds.

A primary aspect of the herbicidal compositions of the invention is their ability to control narrow-leaved weeds in sugar beets, especially the stubborn species, such as wild oats and black grass, as well as less resistant species, such as yellow needle, coot, digitaria and others. weeds.

The compounds of the invention are characterized by formula 1 of the formula sheet, wherein R is ethyl, n-propyl, isopropyl, isobutyl, allyl or butenyl; R 1 is methyl, n-propyl, isopropyl, n-butyl, isobutyl or isoamyl and R 1 is methyl, ethyl or isopropyl; under the conditions that when R 1 is isopropyl, R is ethyl and R 1 is n-butyl; ·· 35 when ethyl is, R is ethyl, n-propyl or allyl and Rj is n-butyl or isobutyl; when R is n-propyl, R 1 is n-butyl or isobutyl; 011 01323 * 1 - 5 - when R is isopropyl R 1 is isobutyl; when R is isobutyl, R is n-propyl, isopropyl, isobutyl or isoamyl and when R is butenyl, R 1 is methyl.

Particularly useful and interesting compounds are those wherein in the above formula R is an alkyl group, preferably ethyl, n-propyl, or allyl, R is C 1 -J or C 1 -alkyl, especially n-butyl or isobutyl and methyl or ethyl.

Specific compounds of the present invention are: X- (isobutoxymethyl) -2r-isopropoxy-6r-methyl-2-chloroacetanilide; N- (isobutoxymethyl) -2'-isoamyloxy-6, -methyl-2-chloroacetanilide; N- (n-propoxynethyl) -2T-isobutoxy-6 '-methyl-2-chloroacetanilide; X- (ethoxymethyl) -2'-n-butoxy-6, -isopropyl-2-chloroacetanilide; N- (isobutoxymethyl) -2'-isobutoxy-6, -methyl-2-chloroacetanilide; X-iisopropoxymethyl-Z'-isobutoxy-6'-methyl-2-chloroacetanilide; X- (isobutoxyir.ethyl) -2-n-propoxy-6 '-methyl-2-chloroacetanilide; X- (2-buten-3-yloxymethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide; 20 X- (n-propoxymethyl) -2'-n-butoxy-6-ethyl-2-chloroacetanilide; X- (allyloxymethyl) -2'-n-hutoxy-6'-ethyl-2-chloroacetanilide; X- (ethaxymethyl) -2-isobutoxy-6'-ethyl-2-chloroacetanilide; and X- (allylox * methyl) -2 r-isobutoxy-6, -ethyl-2-chloroacetanilide.

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

The compounds of the invention can be prepared in various ways. For example, these compounds can be prepared by the azomethine pathway described in the above-mentioned U.S. Pat. Nos. 3,442,945 and 3,547,620. According to the azomethine method, the appropriate primary aniline is reacted with formaldehyde to give the corresponding methylene aniline (substituted phenylazo-methine) which is then reacted with a haioethyl acetylating agent such as chloroacetyl chloride or chloroacetyl anhydride containing 8101323 VI - 6 - in turn is reacted with the appropriate alcohol to yield the corresponding N-alkoxymethyl-2-chloroacetanilide as the final product.

Another x <7 method for producing compounds of the invention involves an N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent under basic conditions.

Example I below illustrates the use of said N-alkylation to prepare a compound of the invention. A modified N-alkylation process is described in Example II, to prepare another compound of the invention. The modified N-alkylation process as described in Example II involves the in-situ preparation of halomethylalkyl or alkenyl ethers used as starting materials in the N-alkylation process. Example I

2'-isobutoxy-6'-methyl-2-chloroacetanilide,

5.6 g (0.022 mol), chloromethyl-n-propyl ether, 4.75 g (0.44 mol) and 2.0 g benzyl triethyl ammonium chloride were mixed in 250 ml methylene chloride and cooled. To the mixture at 15 ° C

50 ml of a 50% NaOH solution was suddenly added and the mixture was stirred for 2 hours. 100 ml of cold water was then added. The layers were separated, washed with xrater, then dried over MgSO4 and evaporated by Kugelrohr to obtain 6.5 g (90% yield) of clear oil, bp 130 ° C at 0.04 mm Hg.

Anal Calculated for Cj ^ H ^ gClNO ^ (%): C 62.28, H 7.99, Cl 10.81

Found: C 62.27, H 8.01, Cl 10.81.

The product was identified as N- (n-propoxymethyl) -2'-30 isobutoxy-6'-methyl-2-chloroacetanilide.

Example II

This example describes a modification of the N-alkylation method described in Example I. In this embodiment of the xr method, the alkylating agent is formed in situ, which accomplishes a more efficient, economical and simple operation.

81 013 2 3 4 4 - 7 -

6.1 g (0.05 mol) of acetyl bromide are added to a cooled mixture of 4.5 g (0.1 mol) of ethanol, 1.5 g (0.05 mol) of anhydrous paraformaldehyde and 100 ml of methylene chloride; the mixture is stirred until all paraformaldehyde has dissolved. 5.3 g (0.038 mol) of 2I-n-butoxy-6'-isopropyl-2-chloroacetanilide, 2.0 g of benzyltriethylamonium chloride and 40 ml of mathylene chloride are then added to the mixture. The mixture was cooled to 15 ° C and 50 ml of 50% NaOH solution was added all at once. The mixture was stirred for 2 hours. The layers were separated, washed with water, dried over EgSO4 and evaporated by Kugelrohr to give 4.6 g (77% yield) of yellow liquid, bp 325 ° C at 0.07 mm Hg.

Anal. Calculated for C nH „nClN0., (%): C 63.24, H 8.26, Cl 10.37 J O O, Ο j

Found: C 63.23, E 8.29, Cl 30.37.

The product was identified as N- (ethox> TiHethyl) -2, -n-butax-6, -isopropyl-2-chloroacetanide.

Examples III to XII

Following substantially the same procedure and conditions as described in Examples I or XI, but using the appropriate secondary anilide and alkylating agent as starting materials and amounts thereof, the corresponding H- (alkoxymethyl or alkoxyoxymethyl) -2-halogen- acetanilides prepared; these compounds are listed in Table A, along with certain physical properties.

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The secondary anilide starting materials used in the above examples are prepared according to known methods, for example, by haloacetylation of the corresponding primary amine with such haloacetylating agents as a haloacetyl halide or anhydride. Typically, the appropriate amount of the appropriate primary amine is dissolved in a solvent, such as methylene chloride, which contains a base, e.g., 10% NaOH, and stirred vigorously with mixing with a solution of the haloacetyl halide, e.g., chloroacetyl chloride, under external cooling, for example at 15 to 25 ° C. The layers were separated and the organic solvent layer washed with water, dried and evaporated in vacuo.

The primary amines used to prepare the secondary anilides can also be prepared by known means, for example, by catalytic reduction of the corresponding appropriately substituted nitrobenzene, for example 2-alkoxy-6-alkyl-nitrobenzene, in a solvent such as an alcohol , for example, ethanol, using platinum oxide catalyst.

As noted above, the compounds of the invention have been shown to be effective as herbicides, especially pre-emergence herbicides, although post-emergence activity has also been demonstrated. The pre-emergence trials referred to herein include both greenhouse and open field trials. In the greenhouse tests, the herbicide is applied either to the surface after planting or sowing or by incorporation in an amount of soil to be coated over the test seeds in pre-sown test bins. In the open field trials, the herbicide can be applied by incorporation into the soil before planting or sowing, i.e. the herbicide is applied to the surface of the soil and then incorporated therein by mixing followed by sowing the cultivated seeds or the herbicide can be applied to the surface after sowing the cultivated crop seeds.

8101323 - II - * 9

The test method with surface application used in the greenhouse is carried out as follows: Holders, for example aluminum bins, typically 24, 3 os 13.34 cm x 6.99 cm, or 9.53 cm x 9.53 plastic pots cm x 7.62 cm, 5 in water drainage holes in the bottom, are filled to the brim with Ray mud soil and then pressed to a level of 1.27 cm from the top of the pots. The pots are then sown with plant species to be tested, covered with a 1.27 cm thick layer of the test soils. The herbicide is then Inangebraeht on the surface of the soil, for example with a banana sprinkler in the amount of 187 liters per hectare, 2.11 kg per cm. Each pot receives 0.64 cm of water as flooring from above and the pots are then placed on greenhouse bars for subsequent flooring from below as needed. As an alternative procedure, the flooring from above can be omitted.

Observations of herbicidal effects are made approximately 3 weeks after treatment.

The herbicide treatment by incorporation into the soil used in the greenhouse tests is as follows: 20 A good quality potting soil is placed in aluminum pans and pressed to a depth of 9.5 to 12.7 min from the top of the pan. A predetermined number of seeds or vegetative propagations of various plant species are placed on top of the soil. The soil requires to fill the pans to the brim after sowing or adding vegetative propagations is weighed in a pan. The soil and a known amount of the active ingredient applied in a solvent or as a moisturizing dispersion suspension are thoroughly mixed and used to cover the prepared pans. After treatment, the pans receive an initial watering from above, equivalent to 0.64 cm of rainfall, then watered by flooring from below as needed to provide the correct amount of moisture for germination and growth. As an alternative procedure, the irrigation can be omitted from above. Observations take place about 2 to 3 weeks after sowing and treatment.

8n /] a v r \ w 1 U i 0 ά Cj ΐ Ί - 12 -

Tables Β and C show the results of tests conducted to determine the herbicidal activity of the compounds of the present invention before emergence; in these experiments, the herbicides were applied by incorporation into the soil and only irrigated from below; a dash (-) means that the indicated plant has not been tested x <rerd. The herbicide rating x was obtained using a fixed scale based on the percentage damage of each plant species.

The rating figures are defined as follows: 10% Control Rating 0-24 0 25-49 1 50-74 2 75-100 3 15 The plant species used in one set of samples, the data for which were given in Table B, xrorden identified with a letter in accordance with the legend below: 20 A - Canada Thistle G - Yellow Cypergrass B - Burdock. H - Cultivated grass C - Chamber maple I - Johnsong grass D - Ipomoea J - Fluffy swamp E - Loosestrife K - Cepid 25 F - Water pepper 81013 2 3 - 13 -

Table B Before emergence

Plant species

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The compounds were further tested using the above procedure on the following plant species: L - Soybean R - Sesbania Hemp 5 M - Sugar Beet E - Loosestrife N - Wheat F - Water Pepper 0 - Rice C - Chamber Maple P - Millet J - Downy Swamp B - Burdock S - Finger Grass Spp.

10 Q - Wild buckwheat K - Hanepoot D - Ipomoea T - Digitaria

The results are shown in Table C.

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The herbicides of the invention have been found to have unexpectedly superior properties as selective emergence herbicides for use in sugar beets, most particularly in the selective control of hardy-necked narrow-leaved weeds, including black grass, wild oats, and fluffy swamp and others. weeds, such as yellow needle nature, annual rye, coot, and high digitaria. Selective control and suppression of the above and other weeds with the herbicides of the invention has also been found in a variety of other crops, including soybeans, cotton, groundnuts, green beans, rapeseed, cucumbers and tomatoes. However, the very excellent herbicidal properties of the compounds of the invention are most manifest in their selective control of annual grasses in sugar beet.

To illustrate the unexpectedly superior properties of the compounds of the invention on both an absolute and relative basis, comparative tests are conducted in the greenhouse with: (1) prior art homologous compounds most closely related in chemical structure. with the compounds of the invention and (2) are other compounds which, although not homologs, are within the scope of the said prior art and one of which has superior properties as a sugar beet herbicide and two of which are commercial herbicides. All compounds in the comparative tests shown below are generically defined as substituted phenyl-N-hydrocarbyloxyalkyl-2-haloacetanilides. As used in the tables of data in the present application, the compared compounds of the prior art are identified as follows: 30 A. N- (methoxymethyl) -2, -methoxy-6, -tert-butyl-2-chloro- acetal anilide. (Example 18, U.S. Patents 3,442,945 and 3,547,620).

B. N- (methoxymethyl) -2'-methoxy-6'-tert-butyl-2-bromoacetanilide. (Example 34 of U.S. Patent 3,547,620 and Example 36 of U.S. Patent 3,442,945).

8101 323-19 - C. X- (isobutoxymathyl) -2 ', 6'-dimethyl-2-chloroethanetiide; trivial name "delachlor" (Example 31 of U.S. Patent 3,442,945 and Example 24 of U.S. Patent 3,547,620).

5 D. X- (allylexymethyl) -2 *, 6'-dimethyl-2-chloroethylanilide.

(Example 47 of U.S. Pat. No. 3,547,620).

E. X- (ethoxyethyl) -2 ', 6'-diethyl-2-chloroacetanilide. (Example 5 of U.S. Pat. Nos. 3,547,62S and 2,442,945); trivial name "alachlor", active ingredient in * C the commercial herbicide LASSO '^ v9 tr.erkr.asr. from Monsanto

Company.

F. X- (methox / methyl) -2, -methoxy-6'-methyl-E-chloroacetanilide. (Compound No. 6 of the Belgian patent specification 8,763; also disclosed in German patent application 2,402,983).

15 G. X- (ethoxyethyl) -2'-methoxy-1,6-methyl-2-chloroacetanilide.

(Compound nc. 7 in Belgian patent 810.763).

K. X- (1-methoxy-prop-2-yl) -2'-methoxy-6'-methyl-chloroeareacanilide. (Compound no. 9 of the Belgian patent S10.763).

20 I. X- (methoxyethyl) -2 r-ethoxy-6'-inethyl-2-chloroacetanilide.

(Compound no. 16 of the Belgian patent 810,763).

J. X- (ethoxyethyl) -2'-ethoxy-6T-methyl-2-chloroacetanilide. (Compound Xo. 18 of the Belgian patent 810,763).

K. X- (methoxyethyl) -2'-methoxy-6, -isopropyl-2-chloroacetanilide.

25 (Compound No. 26 of the Belgian patent 810,763).

L. X- (isopropoxyethyl) -2T-methoxy-6'-methyl-2-chloroacetanilide. Μ. X- (1-ir.ethoxyprcp-2-yl) -2 '-ethyl-6'-thy-1-2-chloroacetanil ide.

(U.S. Patent No. 3,937,730 and German Patent Application 2,402,988); trivial name "metolachlcr'1, active bastanc-30 part in the commercial herbicide" Dual brand name of

Ciba Geigv Corporation.

Although the above compound C is structurally less similar to the said homologous herbicides in the aforementioned U.S. Pat. Nos. 3,442,945 and 3,547,620.35 in that an alkoxy substituent is missing in an ortho position, it has been included in the present experiments because they have superior 81013 Has exhibited properties as a sugar beet herbicide compared to other compounds in the aforementioned U.S. Pat. Nos. 3,442,945 and 3,547,620. Likewise, compounds E and M have been included in the present experiments because they fall within the framework of the indicated relevant prior art and have acquired commercial status. Compounds F to L are included in the present experiments because they show some similarity in structure to certain compounds of the invention.

In emergence herbicidal trials, compounds of the invention were compared to prior art compounds A to M in the control of various weeds, with an emphasis on annuals of narrow-leaved species predominant in sugar beets.

15 The test results are shown below x <.

In the discussion of data below, herbicidal application amounts are symbolized as "GRj, -" and "GRg ^"; these quantities are given in kg / ha. GRj, - defines the maximum amount of herbicidal that is required to bring about 15% or less damage to the tex-crop crop, and GRoc defines the minimum amount required to achieve 85% weed inhibition.

The quantities GRj ^ and GRgj. are used as a measure of potential commercial applicability, of course, it goes without saying that suitable commercial herbicides may exhibit greater or lesser 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 given crops and weeds. The selectivity factor is a measure of the relative degree of crop safety and weed damage and is expressed in terms of the ratio GR1c / GRoc, ie the GRjg for the crop divided by the GRg ^ for the weeds, both 35 quantities in kg per hectare. In the tables below, selectivity factors, if used, are indicated in brackets S1 01 3 2 3 - 21 - after the weeds; the symbol "NS" indicates "non-selective"; a dash after the weeds indicates marginal or indeterminate selectivity, for example, because the actual GR, _ and / c £ GRC_ are higher or lower than the maximum or minimum J o co 5 amounts used in the indicated tests.

Since the tolerance of the case and the control of the weeds are interrelated, a brief discussion of this relationship in terms of selectivity factors is useful. In general, it is desirable that crop safety factors, which include herbicide tolerance, are high since higher concentrations of herbicide are often desired for some reason. Conversely, it is desirable that the weed control amounts are small, that is, that the herbicide is one. has high unit activity, for economic and possibly also ecological reasons. However, small amounts of a herbicide may not be adequate to control certain weeds and a larger amount may be required. Therefore, the best herbicides are those that control the greatest number of weeds with the smallest amount of 2Q herbicide and provide the greatest degree of crop safety, i.e. crop tolerance. Therefore, use is made of selectivity factors (described above) to quantify the relationship between crop safety and herb control. With regard to the selectivity factors 25 shown in the table, it appears that the higher the numerical value, the higher the selectivity of the herbicide for weed control in a given crop.

In the tables below, the data for compounds tested in multiple embodiments are p, 'j gc-cmacecc and o ... ccne-y' ue delivery reference nec c '~ co net range from 0.14 to 2.24 kg / ha. Incidentally, various tables contain single-embodiment data for application rates down to 0.07 kg per hectare or up to 4.48 kg / ha.

In a first series of experiments, herbicidal activity data for emergence is presented in Table D, O Λ md X 0 'X v 1 U i 0 (L s) - 22 - showing the relative effectiveness of representative compounds of the invention is compared to that of relevant compounds of the prior art as selective herbicides against specific weeds commonly found in sugar beet. The weeds used in the present experiments are abbreviated in the tables as follows: wild oats (WH), coot (HP), high digitaria (HD), black grass (ZG) and yellow needle (GNA).

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From the data in Table D it appears that with regard to crop safety (as indicated by the quantity GR for sugar beet) the compounds according to the invention showed a far superiority compared to the compounds according to the prior art. More specifically, relative to the most closely related compounds of the prior art in structure, i.e. the compounds A and B with the N-alkoxymethyl-2, -alkoxy-6, -alkyl-2-haloacetanilide- configuration, the compounds of the invention in the experiment were 5.8 to more than 8.0 times safer on beet than Compound B and about 2.8 to more than 4.0 times safer than Compound A. More notably, the compounds of the invention were 22 to more than 32 times safer on sugar beets than homologous compounds of prior art F, G and L, each of which yielded more than 15% sugar beet damage at the very low amount of less than 0, 07 kg / ha.

Although not homologous of the compounds of the invention, Compound C is known to have superior sugar beet herbicide properties compared to other compounds described in U.S. Pat. Nos. 3,442,945 and 3,547,620 above, which also include Compounds A and B. Likewise, although compound M is not homologous of the compounds of the invention, it falls within the scope of said German Patent Application 2,402,983, which also describes compounds F and G and generically comprises compound L; compound M is the active ingredient in a commercial herbicide as indicated above.

As for the GR1 data in Table D for compounds C and M, it will be noted that these compounds exhibited a higher safety factor than the other prior art compounds. However, compound C was only about one-third to half as safe as the compounds of the invention and compound M was only about half to two-thirds as safe as the compounds of the invention.

In conjunction with the indicated high degree of crop safety, the compounds of the invention exhibited unit activities (i.e., phytotoxicity per unit of herbicide) against the weeds tested (as indicated by ce GRg_) that do not or do not compare with the compounds 5 according to the prior art, the technique. The combination of high crop safety factor and high unit activity against weeds resulted in far higher selectivity factors for the compounds of the invention than for the compounds of the prior art, with the only exception of the 10 compound of Example IV against black grass.

Of particular interest in Table II when comparing the selectivity factors of the prior art compounds with that of the compound of Example I against the respective weeds in sugar beet is that the compound of Example I was more selective than the compounds of the state of the art with factors from about 2.4 to more than 4.7 against wild oats, from about 2.1 to down than 34.6 against coot and yellow sewing and from about 1.8 to near than 34.6 against digitaria and black grass.

Further experiments with selected compounds of the invention have demonstrated control of coot, digitaria, black grass and yellow needle at application rates of no more than or even less than 0.07 kg / ha.

Thus, the compound of Example I has shown control of each of the above weeds at 0.07 kg / ha or less; the compound of Example IV has shown control of coot, digitaria and yellow needle at less than 0.07 kg / ha and the compound of Example III has control of coot and guitars at 0.07 kg / ha or less.

2b In other comparative tests, the harbical activities and the selectivity factors for emergence of the compounds C, E, H and M were determined in the prior art and compared with those of the compounds of Examples I to VIII; the data from these tests is presented in Table E.

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Table E shows that each compound of the invention had a significantly higher safety factor in sugar regions than all of the compounds of the prior art. Particular attention is drawn to the safety factors of the compounds of Examples I, III and VI to VIII, which range from 2.7 to over 36 stitches greater than those of the compounds of the invention. In addition, except that they had higher safety factors, the compounds of the invention showed uniform and excellent superior state of the art except in isolated cases. For example, the selectivity factor of compound C was marginally greater than that of example VII against wild oats, slightly greater than that of the compound of example IV, and equivalent to that of example VI against black grass. It will be noted that the compounds E. H and H of the prior art showed no selectivity to wild oats and black grass and the selectivity of the compounds E and H to the other weeds was questionable or marginal at most; in any case, the low safety factors of these compounds make them unsuitable as sugar beet herbicides.

Since the herbicidal emergence data, shown in Tables D and E, were obtained according to identical routine procedures, a comparison can also be made of the herbicidal efficacy of compounds of the invention in Table D against that for the prior art compounds. the technique in Table E, which are not listed in Table D, and vice versa. Here again it is clear that each of the compounds according to the invention is far superior

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state of the art in terms of crop safety, without exception, and selective weed control, or evidenced by selectivity factors; again with exceptions in isolated cases. For example, the selectivity factor of a prior art SpSClf ICcic VC: j ΧΏD ΧΏ 35 against a particular weed may be greater than that of a specific compound according to the invention; but in either case, the low sugar beet safety factor renders the prior art compound unsuitable as a sugar beet herbicide. For example, the selectivity factor (2.0) of compound B (Table D) against wild oats 5 in sugar beet is greater than that for the compounds of Examples VII and VIII (1.0 and 1.3, respectively, as shown in Table E). However, the safety factors for the two compounds according to the invention are eight times as great as those for compound B in sugar beets and the selectivity factors of the said compounds according to the invention are at least four times greater than that of compound B against coot, digitaria and yellow needle and equivalent. to that of compound B against black grass.

In another comparative herbicidal efficacy test, the compound of Example I and the compounds I and J were tested against wild oats, coot, high digitaria, black grass and yellow needle. The results of that test (representing the average of two replicate runs) are shown in Table F; observations were made approximately 18 days after treatment; the selectivity factors are shown in brackets below the X-value for GRg ^ for each of the weeds.

Table F

GRj5 GRg5 (kg / ha) 25 Conver- (kg / ha)

ding_Sugarbeets_WH HP HP_ZG GNA

Ex. I <1.12 0.35 <0.14 <0.14 <0.14 <0.14 (> 3.2) (> 8.0) (> 8.0) (> 8.0) (> 8.0) I <0.28 ^ 0.99 <0.34 <0.14 0.21 <0.14 30 (NS) (^ 2.0) (^ 2.0) (M, 3) ( ^ 2.0) J <0.21 0.28 <0.14 <0.14 0.21 <0.14 (NS) (M, 5) (M, 5) (NS) (M, 5)

The excellent superiority of the compound of Example I over compounds I and J is evident from the viewpoint of crop safety factor and selectivity against each of the weeds in the test; compound J was non-selective against wild oats and black grass and compound I.

8101323 - 29 - was nonselective against skinned oats and hardly selective against black grass in sugar beet.

In one test, the compound of Example I and the compounds I and J were further tested against fluffy dravik (DB), red goosefoot (EGV) and annual rye (ER) in sugar beet at amounts of administration within the range of 0.07 to 2, 12 kg / ha; observations were made 18 days after treatment; the results of this test are shown in Table C; selectivity factors are indicated in brackets after el? -:! 1 of da weeds.

Table G

GR] 5 (kg / ha) GRg (kg / ha)

Verb in Sugar beet DD RG7 ER

thing___________ 15 Yb. I> 1.12 0.07> 1.12 <0.09 (> 26.0) (-) (> 12.0) I 0.07 <0.14 0.07 0.28 (NS) (1 .0) (NS) J <0.07 <0.09 <0.07 <0.07 20 (NS) (-) (-)

The test data showed that prior art compounds I and J were harmful to sugar beets in amounts as low as not more than 0.07 kg / ha or less and that compound I was non-selective against cottony swamp and annual rye while compound J was nonselective against fluffy dravik and of marginal or indeterminate selectivity in amounts below 0.07 kg / ha. In contrast, the compound of Example I was safe on sugar beets in an amount of 1.12 kg / ha (the maximum amount in this 3 'test) while fluffy swamp and annual rye were selectively feather 15 and 12, albeit that the control of goose fat was marginal or indefinite above 1.12 kg / ha.

A further test was performed in the kiss 35 to compare compounds of the invention of Examples II and Y with the compounds n and D, i.e. the most closely related compounds of the prior art / ** i J z \ i * rr -jiwiv - 30 - of the technique. Example II and compound K are characterized in that they have an isopropyl group in one ortho position, an alkoxy group in the other ortho position and an alkoxyalkyl group on the anilide nitrogen atom. Compound D and the compound of Example V are characterized in that they have alkenyloxy-methyl groups attached to the nitrogen atom and have a methyl group in the one ortho position. The herbicides were applied to the plants in amounts within the range of 0.07 to 1.12 kg / ha; observations were made 19 days after treatment; the results are shown in table H.

Table H

GR] 5 GRg5 (kg / ha)

Verb in (kg / ha)

ding_Sugar beet WH_HP_ HP _ZG_GNA

15 Ex. II> 1.12 0.14 <0.07 <0.07 0.24 <0.07 (> 8.0) (> 16.0) (> 16.0) (> 4.7) (> 16 .0) K 0.19 0.07 <0.07 <0.07 0.49 <0.07 (2.7) (2.7) (2.7) (NS) (2.7)

Ex. V 1.12 0.14 <0.07 <0.07 0.78 0.09 20 (8.0) (> 36.0) (> 16.0) (1.4) (13.1) D 0.19 0.19 <0.07 <0.07 0.56 <0.07 (1.0) {> 2.1) {> 2.1) (NS) {> 2.1) from the data Table H clearly shows the excellent superiority of the compounds of the invention compared to the compounds D and K. In particular, the compounds of Examples II and V are safe on sugar beet in amounts of 1.12 kg / ha and more. while compounds D and K had GRj values of only 0.19 kg / ha. Furthermore, the selectivity factors of the compounds of the invention several times exceeded the selectivity factors of the compounds of the prior art against each of the weeds in the sugar beet test; the prior art compounds were non-selective against black grass in sugar beets.

Other experiments were performed to demonstrate the superior herbicidal properties of other compounds of the present invention. In a series of tests 8101323 - 31 -

in the greenhouse, the compounds of Examples IX to XII

tested against wild oats, coot, high digitaria, black grass and yellow beet in sugar beet; the results of these tests are shown in Table I.

Table I

GR ,. GR0. (kg / ha) 1 o So

Commit- (kg / ha)

thing Sugar beet KH HP HD ZG GXA

Tb. IXa 1.0 0.55 <0.14 <0.14 0.39 <0.14 10 ¢ 1.8) (7.1) (7.1) (5.2) (7.1) 7th. : r> i, 12 0.34 <0.14 -0.14 <0.14 <0.14 (> 3.3) (> 8.0) (> 8, C) (> 3.0) ( > 8.0)

Va. XIC> 1.12 0.19 <0.14 <0.14 <0.14 <0.14 (> 5.9) (> 8.0) (> 8.0) (> 3.0) (> 8.0) H Ex. XII> 3.12 0.84 <0.14 0.34 0.34 0.14 (> 3.3) (> 8.0) (> 8.0) (> S, 0) (> 8.0 ) a. Data represent the average of four replicate cests.

20 b. Data represent the average of two replicate tests.

c. Data represents the average of three replicate tests.

Once again, the superior herbicidal activity of compounds of the invention appears before emergence, both on an absolute basis and relative to the behavior of relevant prior art compounds, as shown in the. Tables D to H, pertaining to crop safety factors, unit activities, weed control and crop / weed-33 s e1e ct iv i te it sf ac, for compounds tested in multiple embodiments taken from trials with herbicide application rates within the range of 0 , 14 to 1.12 kg / ha. However, further tests with selected compounds of the invention have shown sugar beet safety in amounts of at least 4.48 kg / ha and selective control of various weeds in amounts of not more than 0.07 kg / ha. for example, the connection of

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- 32 - Image I demonstrate selective control of the more resistant weeds zxrart grass and fluffy swamp and less resistant weeds coot, high digitaria, yellow needle and annuals, in quantities of no more than 0.07 kg / ha and less.

Likewise, other compounds of the present invention have also controlled one or more of the above-mentioned less resistant weeds at 0.07 kg / ha.

In an open field trial with respect to relative sugar beet safety and weed control, the compound of Example I and the compounds C, E and M were tested in the art against coot and green needle with application to the surface (AO ) and pre-planting (OW) in amounts within the range of 1.12 to 4.48 kg / ha. The treatments were administered to a Ray sludge soil with 3.8% organic matter; conditions were relatively dry as only 0.03 cm of rain fell within the first 7 days of treatment; the results of the test in open ground are shown in Table J.

Table J

20% inhibition__

Verbin- How much- Sugar beet Hanepoot Green needle planting __ (kg / ha) OVP AO OVP A0 OVP_ A0

Ex. I 3.12 0 0 85 27 85 57 25 2.24 10 3 92 48 92 65 4.48 12 13 98 78 98 85 C 1.12 10 5 78 42 88 77 2.24 22 18 87 77 93 87 4.48 57 25 98 90 98 88 30 E 1.12 30 30 87 68 88 85 2.24 80 63 300 95 300 95 4.48 300 90 100 93 300 97 M 1.12 15 15 95 40 95 62 2.24 30 23 100 78 100 85 35 4.46 63 45 100 93 100 92

The data in Table J shows that of all tested compounds, only those of Example 1 safely x-ash (i.e., damage up to 15%) on sugar beet in amounts up to at least 4.48 kg / ha (maximum test amount), 81013 2 3 - 33 - showing selective control of so many canoe leg as a green needle at 1.12 kg / ha under CVP tools; none of the prior art compounds converted any weeds even at 2.24 kg / ha; Compound II selectively controlled 5 weeds under OVP conditions at the rate of 3.12 kg / ha, which is a rapid margin of crop tolerance.

5th compound of Example I was also tested in open ground to determine its selectivity for a variety of garden crops; the data (representing three replicate embodiments) is shown in Table K for both surface application (AQ) and soil incorporation, prior to planting (07P) the herbicide. The seeds were sown in a fine seedbed of mud. of moderate moisture content. The seeds were sown at a depth of 5.03 cm. The first rainfall (0.51 cm.) Occurred the day after treatment, the second rainfall (0.64 cm) 2 days after treatment; the cumulative rainfall 22 days after treatment was 4.57 cm. hairlings occurred 6 weeks after treatment.

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The data in Table K show that the compound of Example I generally behaved in the same way as many A0 as OY? Disorders at rates up to 4.48 kg / ha (except in tomato, cucumber and proso ~ 5 millet). , 48 kg / ha GAP and against needle and hawk at 0.58 kg / ha). In particular, in AO-controlled conditions compound of Example I, selectively needle and coot in all test crops at rates of slightly less than 1.12 kg / lia and prosc millet at 4.48 kg / ha. Under OYP awkwardnesses 1.12 and 2.24 kg / ha, net crop safety not less than 4.48 kg / ha for all crops, except tomatoes, cucumbers and string beans.

A clear advantage of a herbicide 15 is its ability to function in a wide variety of soil types. For example, Table L provides data showing the comparative herbicidal effect of the compound of Example I and compounds C and M on various annual grasses in sugar beet in a wide variety of soil types with varying organic matter and clay content. In these tests, pots are filled with mat hay sludge soil, pressed up to 0.25 cm from the surface of the pot, then sown with sugar beets, wild oats, coot, high digitaria, black grass and yellow needle. The seeds were covered with 0.327 cm Ray sludge loam, Florida cattle, Florida zsnd, ftabssh sludge clay loam, Drummer sludge-like clay and Sarpy sludge-like clay soil, respectively. Each of the herbicides was applied with a tape sprayer in an amount of 137 2 above for placement on kasbankan for subsequent flooring from below. Observations occurred 15 days after treatment. The results of the bed screws, representing the average of two replicate excursions, are shown in 35 '' Table L; the selectivity factors are shown in brackets after the GRor for the weeds. The soil type analysis 03 4,% y * / ^ v

O t -J i 0 ά Q

V * - 36 - was as follows:% inhibition_

Soil type Organic Clay Sludge Sand pH

• material _ '_'__ 5 Ray mud 1.2 1.2 74.8 18.8 6.5

Florida peat 22.1 NBa NBa NBa 5.2

Florida (Leon) sand 2.3 1.8 NBa NBa 6.1

Drummer silt-like clay 3.6 12.4 52.8 34.8 7.0

Wabash clay 2.7 44.4 34.8 20.8 6.2 a) not available.

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The data in Table L shows that the compound of Example I showed by far superior sugar beet safety and selectivity factors higher than that of compounds C and M against each weed (with two minor exceptions) in three of the five soil types, namely in Ray silt loam, Florida sand and Wabash clay. More specifically, the compound of Example I was the only compound that selectively controlled wild oats in Ray silt loam and Wabash clay, Coot in Florida sand and black grass in Wabash 10 clay. The results were fairly indeterminate in Florida peat (22.1% organic matter) in the test amount, but indicate that soils with a high organic matter content reduce the activity of each of the tested compounds. The compound of Example I did not fare as well in Drummer sludge clay as the compounds of the prior art, but did exhibit overall higher activity over a variety of soil types.

Laboratory tests were conducted to determine the relative resistance of herbicides of the invention and prior art compounds to soil leaching and the resulting herbicidal effectiveness. In these tests, the compound of Example I and the compounds C and M were taken up in acetone and then sprayed at different concentrations on a weighted amount of Ray sludge loam, kept in pots of filter paper that had drainage holes in the bottoms of covered the pots. The pots containing the treated soil were leached by placing them on a turntable rotating under two nozzles of a water container, calibrated at 2.5 cm. water 30 per hour and simulate rainfall. The leaching rates were adjusted by varying the time on the turntable. Water was supplied to the soil in the pots and allowed to percolate through the filter paper and the drainage holes. The pots were then left to stand at ambient room temperature for 7 days.

35 The treated soil in the pots was then removed, crumbled and applied as a surface layer on other pots containing 81013 2 3 - 39 -

Sav-s lib-lcerr soil, sown with sugar beet, skinned oats, hsnepoet, digicaria, black grass and yellow needles. The pots were then g * * r. a z. on iras — can, down. "* V" w. and nen grew for 2 weeks. Visual qualifications for no 5 percent growth were recorded; the data for the test compounds represent mean of two replicates; the test data are shown in Table II; weed abbreviations are as in the preceding tables.

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The data in Table M shows that the compound of Example X was safe on sugar beet totate at least 2.24 Icg / ha and selectively controlled all weeds in the test under simulated rainfall of 0.16 cm, excluding wild oats, which was controlled up to 7.62 cm of rain. At 2.24 kg / ha, compounds C and H were harmful to sugar beets up to a compound with 6.08 cm of rain, under which conditions none of the compounds selectively controlled wild oats, nor compound M black grass. At the lowest herbicidal application rate (0.14 kg / ha), the compound of Example I selectively controlled all weeds in the test under rainfall down to 1.27 cm, and coot, digitaria and yellow needle under 5.08 cm rainfall. In contrast, at 0.14 kg / ha none of the compounds C and M selectively controlled black grass, nor did compound C 15 control wild oats under any rainfall conditions, and both compounds lost selectivity against all test weeds in sugar beet below 5.08 cm rainfall. It has therefore been clearly shown that the compound of the invention was much more resistant to leaching in the soils under varying rainfall conditions than any of the prior art compounds, thereby providing a more reliable and longer lasting herbicidal action.

Finally, to further demonstrate the unobvious nature of the unexpectedly superior properties of the compounds of the invention, further herbicidal data for emergence for other compounds of similar structure, including homologues of the compounds of the invention, are presented in Table N. The compounds N to T in Table N are identified as follows: 30 N. N- (isopropoxymethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide O. N- (isobutoxymethyl) -2 1'-ethoxy-2-chloroacetanilide P. N- (isobutoxymethyl) -2'-methoxy-2-chloroacetanilide Q. N- (isobutoxymethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide R. N - (ethoxymethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide.

8101 323 f -Ί “* 4 J“ S. IT- (1-tnschylnrepe: -: y: nethyl) -2'-Ethoxy-5 T-metliyl-2-ch 1 o o r a c e e t an i 1 i d e.

I. II- (etrxnrnrn: thyl) ~ 2 '-isopropony-o'-netliyl-2-chloroacetanilide.

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It is pointed out that the compounds X to I, as well as the compounds of the invention of Examples I-XII, are within the generic disclosure of the above-mentioned U.S. Pat. Nos. 3,4-2,945 and 3,547,520, but are not specifically disclosed therein. called. It is therefore expected that the specific compounds within the general disclosure of the aforementioned U.S. patent would have generally available herbicidal properties, the completely unexpected and excellent properties; the species of varoindingan. according to the invention in comparison with homologous and closely related species is further elucidated by data for compounds X to T in Table X. It will again be noted that compounds X to T (as well as other prior art compounds as shown in particular in da tables D tct K) had very small safety factors in sugar beet such as ^ 7 f ^ ï. £ ν · Γ ~ Γ0 '' kvjfh Cl * 1 cr '{rR - yohfr, ov' '' h - x-jc Mtp ^ ** '' * ^ ““ ““ lo ”'1 ο- άθ species in Table X selective control for wild oats in sugar beets. It is also important to note that compound non-selective eras against which of the weeds then also in the test and likewise that the compounds X, 0, Q and R were completely non-selective and / or marginally selective against all weeds

Zll ^ tltè ~ '-i Tr2.'l. C.0-? ^ o "Ί V ^ lT ^ O.'i i j.P '· -1" connections F and? selective control of coot, digitaria, black grass and yellow needle. Again, however, it is pointed out that the unacceptably low tolerance of sugar beet for compounds S and 1, coupled with just non-selectivity to wild barer and hardly selectivity to the other weeds 3'ictictero icidan. The results of the safety factors in sugar beets and the selectivity tractors for the compounds of the invention in the above weeds are far superior to those of the compounds S and T (refer to tables T and H).

Therefore, it will be apparent from the above detailed description that compounds of the invention, - λ · „i; i i l *. The present invention has exhibited unexpected and far superior herbicidal properties, both absolutely and relative to the most structurally relevant compounds, other related homologues and analogues, including commercial 2-halo-5-acetanilides, according to the prior art. In particular, compounds of the invention have shown excellent crop safety in sugar beets and selectivity factors particularly with regard to stubborn weeds, such as wild oats, black grass and fluffy swamp and other problematic weeds, such as yellow needle, coot, digitaria, annual rye, etc., as shown in Tables B to J.

The herbicidal compositions of the invention, including concentrates that require dilution prior to administration, contain at least one active ingredient and an additive in liquid or solid form. The preparations are prepared by mixing the active ingredient with an additive, including diluents, extenders, carriers and conditioners, to provide preparations in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. For example, the active ingredient can be used with an additive, such as a finely divided 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 conditioner one or more surfactants in amounts sufficient to render a given composition easily dispersible in water or in oil. The inclusion of a surfactant in the compositions greatly increases their effectiveness. The term "surfactant" is intended to include wetting agents, dispersants, suspending agents and emulsifying agents.

Anionic, cationic and non-ionic agents can be used with equal utility.

o ') f% 4 G »Λ C7 a! 01ó2i - 47 -

Preferred fastening microparticles are alkyl benzene and alkyl naphthalene sulfonates, sulfated earth fatty alcohols, amines and acid acids, long chain acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfated fatty esters, petroleum sulfonates, sulfonic sulphylates, sulfuryl acetates Ethyl derivatives of alkylphenols (especially isctylphenol and nonylphenyl) and polyoxyethylene derivatives of the luono-higher fatty acid esters of Tieuitolanhydridan (for example, yg, t · "" ", Vo: .z, deserving dispersant,: (-" cellulose, polyvinyl alcohol, sodium lignin sulfonates, gummer alkylnaphthalene sulfonates, sodium naphthalene sulfonate and the polyethylene bisnaphthalene sulfonate.

Wettable powders are deeper-J5-digestible preparations containing one or down active ingredients, an inert solid extender and one or more wetting, and dispersing agents. Inert solid adjuvant parts are generally of mineral origin, such as the natural clays, diatomaceous earth and synthetic materials derived from silica r-cionyde and the like. Examples of such an extension agent include kaclinites, attapulgite clay and synthetic magnesium silicate. The wettable powdered compositions of the invention typically contain about 0.5 to 60 parts (preferably 5 to 10 parts) of active scanned part, about 0.25 to 25 parts (preferably 1 to 15 parts) of wetting agent, about 0.25 up to 25 parts (preferably 1.0 to 15 parts) of dispersant and 5 to about 95 parts (preferably 5 to 50 parts) of an inert solid extender, all parts being nichtsdalses,. : "" "On the total preparation, blaze · koa approx. 5 ,! p g. o ...,, "... -.a r an act .onre iitm e.cuiaeng: - rc_ ^ a. j ..-_. a: ... “trapped by a corrosion inhibitor or anti-skewer or both.

Other assemblies include dusty concentrates comprising 0.1 to 60 parts by weight of the active ingredient cp a suitable extender; these dusty materials can be diluted for application at concentrations within the range of about 0.1 to 10 gen. 5.

J101 5 2 5 - 48 -

Aqueous suspensions or emulsions can be prepared by stirring an aqueous mixture of a xl insoluble active test ingredient and an emulsifying agent to uniformity and then homogenizing to provide 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 compositions contain about 0.1 to 60 and preferably 5 to 50% by weight of the active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent.

In another form of aqueous suspensions, a herbicide immiscible with x rater is encapsulated to form a phase encapsulated in micro-capsules dispersed in an aqueous phase. In one embodiment, small capsules are formed by bringing together an aqueous phase containing a lignin sulfonate emulsifier and a water-immiscible chemical and polymethylene polyphenyl isocyanate, dispersing the water-immiscible phase in the x-phase, followed by adding a polyfunctional amine. The isocyanate and amine react to form a solid urea shell wall around particles of the water-immiscible chemical to form micro-capsules thereof. Generally, the concentration of the microcapsulated material will range from about 480 to 700 grams per liter of the total formulation, preferably from 480 to 600 grams per liter.

Concentrates are usually active ingredient solutions in water-immiscible or partly water-immiscible solvents together with a surfactant. Suitable solvents for the active ingredient of the invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, carbon hydrates and water immiscible ethers, esters or ketones. However, other high strength liquid concentrates can be formulated by dissolving the active ingredient in a solvent and then diluting C5 <3 fi Λ “7 Λ * 7 ö i Ü i 0 L 0 - aS - eg fat kerosene. sproeicGneentrati.es.

The concentrate compositions in the present application generally contain about 0.1 to 95 parts (preferably 5 to -50 parts) of active ingredient, about 0.25 to 5 parts (preferably 1 to 25 parts) of surfactant agent and, if necessary, about 4 to 94 parts solvent, all parts being cell cells, based on the total weight of the emulsifiable oil.

Granules are physically stable particles or distributed by a baismatrin of. an inert, finely-divided particulate ash lengthener. In order to help leach the active ingredient from the particulate material, a surface-active agent, as mentioned above, may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of useful classes of particulate mineral lengthening materials. Preferred asn extenders are the porous, absorbent, preformed particles, such as preformed and screened particulate attapulgiat or 2C heat-expanded, particulate vernier, and the finely divided clays, such as cai clays, hydrated attapulgiez or bentonitiseka clays. These extenders are sprayed or mixed with the active ingredient to form the herbicidal granules.

The granular compositions of the invention may contain from about 0.1 to about 30 parts by weight, preferably from about 3 to 20 parts by weight of active ingredient per 103 parts by weight of clay and from 0 to about 5 parts by weight of surface active agent. del per '52 gmr.dln '. ·. j ·. Clay.

SI The compositions of the invention to other additives include, for example, fertilizers, other herbicides, other pesticides, safety microcellulose and chemical agents used as additives or in combination with any of the above additives. Chemicals which can be used in combination with ca active ingredients of the present invention include, for example, triazines, ureas, carbate, acetate Cl 5 5.50 amides, acetanilides, uracils, acetic or phenol derivatives, thiol carbamates, triazoles , benzoic acids, nitriles, biphenyl ethers and the like, such as:

Heterocyclic nitrogen / sulfur derivatives 5 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 3-isopropyl-1H-2,1,3-benzothiadiazin-4- (3H) -one-2,2-dioxide 3-amino-1,2,4-triazole 10 6,7-dihydrodipyrido (l 2-a: 2 ', 1, -c) -pyrazidinium salt 5-bromo-3-isopropyl-6-methyluracil 1,1, -dimethyl-4,4'-bipyridinium salt

Ureas N1- (4-chlorophenoxy) -phenyl-N, N-dimethylurea 15N, N-dimethyl-NT- (3-chloro-4-methylphenyl) -urea 3- (3,4-dichlorophenyl) -1,1 dimethyl urea 1,3-dimethyl-3- (2-benzothiazolyl) urea 3- (p-chlorophenyl) -1,1-dimethyl urea 1-butyl-3- (3,4-dichlorophenyl) -1-methyl urea 20 Carbamates / thiol carbamates 2-chloroallyl-diethyldithiocarbamate S- (4-chlorobenzyl) -N, N-diethylthiol carbamate Isopropyl-N- (3-chlorophenyl) carbamate S-2,3-dichloroallyl-N, N-diisopropylthiol carbamate 25 Ethyl "N, N-dipropylthiol S-propyl dipropylthiol carbamate

Acetamides / Acetanilides / Anilines / Amides 2-chloro-N, N-diallylacetamide N, N-dimethyl-2,2-diphenylacetamide 30 N- (2,4-dimethyl-5 ~ / / (trifluoromethyl) sulfonyl / amino / phenyl) acetamide N-isopropyl-2-chloroacetanilide 2 ', 6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl-61-ethyl-N- (2-methoxyprop-2-yl) -2-chloroacetanilide 35 a , α, α-trifluoro-2,6-dinitro-β, N-dipropyl-p-toluidine ·· N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide 8101323 ~ 51 -

Acids / ta ters / Alcohols 2,2 ~ chloroorooic acid 2-methyl-4-chlorophenony-acetic acid 2.4-dichloro-£ enc :: yazijnzunr 5 Methyl 2- / 4- (2,4-dichlorophenemy) phenc: ty_7propianate 3- ηηίηο ~ 2,5-dichloro-etc-acid 2-methorny-3,6-dichloro enzoic acid 2,3,5-trichloroanyl acetic acid-Iv-I-naphthyphthalanine acid ITairiun-5- / 2-chloro-4- (trifluoromethyl) £ enony / -2-nitroberiZC art IT-I'fojfon-'neizhvl'i-clvcine and its C, monoalkyl acetate thereof - '-' Ib and alkali metal salts and combinations thereof T: -2-d -i - «2.4- diehlecrphenyl -4-n-trotenyl-ethen] 5 2-chloro-n, u, a “triflucr-p-tolyl-3-ethosy-4-nitrcdiphenyl ether

Various 2,6-dichlorobenzonitriyllononatriurn-z uu me t; i a an a r s o n a a t B inat ri umme th a en ars cnaat.

Fertilizers useful in combination with the active stock alan include, for example, ammonium nitrast, urea, notas and superphosphate. Other useful additives include metaren and mannin olantencrganismsn paintsahieaen and growing, such as compost, manure, humus, sand and the like.

Herbicidal preparations of the types described above are exemplified in various illustrative embodiments: forms below.

I. Enulgeeroars Concentrates Mixture of Calcimdodecylbenzene-sulfonet / poly: C-methylene-ethers (for example, Atlcx ^ 34373 and Atlox 343SF) 5.0 35 100.00 * 'J' -V «., ~ 52 -

Wt. % B. Compound of Example II 85.0

Calcium dodecyl sulfonate / alkylaryl polyether alcohol 4.0 Cg aromatic hydrocarbon solvent 11.0 100.00 C. Compound of Example XI 5.0

Mixture of calcium dodecylbenzene sulfonate / 10 polyethylene ethers (eg Atlos 3437F) 1.0

Xylene 94.0 100.00 II. Liquid Concentrates A. Compound of Example I 10.0 15 Xylene 90.0 100.00 B. Compound of Example II 85.0

Dimethyl sulfoxide 15.0 20 100.00 C. Compound of example XI 50.0 N-methylpyrrolidone 50.0 100.00 25 D. Compound of example X 5.0

Ethoxylated Castor Oil 20.0

Rhodamine B 0.5 D ime thy1f ormamide 7 4 J5 30 100.00 III. Emulsions A. Compound of Example III 40.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol (eg Tergitol ^ XH) 4.0 35 Water 56.0 100.00 8101323 - 53 -

Found X

B. Compound of Example IV 5.0

Polyotcyethylene / polycmypropylene-bloyolyner ass butanol 3.5 5 male 93.5 300.0 IV. Wettable powders A. Compound λ * an example V 25.0 batreirrlr grosui — not wet ο, r -ηηοηη strings (svnerenscr) / 1, 0 300.00 3. Compound of example VI 80.0 J5 Xatriur-dioctylsulfosuccinate 1.25

Ca1c rurali gnc s ulphonate 2.75

Amorphous silica (synthetic) 16.00 300.00 20 0. Compound of Example VII 30.0

Xatriim-Lignsulfonate 5.0

Xatrinn-V-neobyl-lb-oleyl-taurate 3.0 300.00 25 V. Substances A. Compound of Example I 2.0

Attapulgite 98.0 300.0

Font Crease Not 40.0 300.00 C, Compound of Example IX 30.0 55 2ent No 70.0 300.00 T Ό - *> A 1 * -J - * · * ^ · - 54 -

Wt. % D. Compound of Example XII 1.0

Diatomaceous earth 99.0 100.00 5 VI. Granules A. Compound of Example I 15.0

Granular attapulgite (20/40 mesh) 85.0 100.00 10 B. Compound of Example XI 30.0

Diatomaceous earth (20/40) 70.0 100.00 C. Compound of example X 0.5 15 Bentonite (20/40) 99.5 300.00 D. Compound of example III 5.0

Pyrophyllite (20/40) 95.0 20 100.00 VII. Micro-capsules A. Compound of example I Encapsulated in polyurea shell wall 49.2 (r)

Sodium lignosulfonate (eg Reax 88 ^ B) 0.9 25 Water 49.9 100.00 B. Compound of Example XII encapsulated in polyurea shell wall 10.0 / p '| 30 Potassium lignosulfonate (eg Peax C-21) 0.5

Water 89.5 100.00 C. Compound of Example X encapsulated in polyurea scale 80.0.

Magnesia salt of lignosulfate (Treax ^ LTM) 2.0

Water 18.0 100.00 s j fi i v? ^ - 55 -

When used in accordance with the present invention, effective amounts of the acaec anilides of the invention are applied to the soils containing the plants or predominantly incorporated into material media on any suitable form, The application of liquid and particulate matter. Solid materials on the bottom can progress, sprung by conventional methods, for example, Zoster inverters, machine and hand nozzles, and spray nozzles. The preparations can be applied from airplanes in dust-τ P form c-r in tp, rt - tv; rm. m virosnc with sur; essassssitass o: .j low dosages. The application of herbicidal preparations to mater plants should be done conventionally by adding the preparations to the vigorous media in the area but control of the mater plants is common.

J5 The application of an effective amount of the compounds of the invention to the growing site of more common weeds is essential and critical to the practice of the present invention. The actual amount of active ingredient used more than one will depend on various factors, but the type of plant and its radium of decomposition, the type and condition of the soil, the amount of rainfall and the specific acetanilide used. When applied selectively for emergence on the plants or on the soil, a dose generally ranges from about 0.02 to about 1], 2, preferably about 0.2, Cé to about 5.60, or to suitable mine of 1.12 up to 5.6 kg / ha of acetanilide. Lower or higher amounts may be required in some cases. An expert in this field can easily determine the information in the application.

The term "boden" or "ground" is used in its broadest sense, and includes all the conventional meanings of "soils" as defined in Lobster's him International Dictionary, Second Edition, Unabridged (1521).

The term refers to all substances or media that can shoot and grow plants, and this includes not only soil but also compost, manure, peat dust, humus, sand and the like, suitable for supporting plant growth.

Although the invention has been described with respect to specific modifications, the details thereof should not be construed as limitations.

£)

Ö 8 lJ 1 0 <£,

Claims (39)

2. Compounds according to claim 3, characterized in that R is an alkyl group or an allyl group of fat 2 to L cage-s t c .. a tc ven es and. _o .. ....... i ... Compounds according to claim 2, bold characterized in that est R1 is an xsobutyl group. 2c 4. Compound according to claim 3, characterized in that its Ik- (n ~ propoxyvethyl) ~ 2 "-isobutovy-6! -Vethyi ~ 2" 5. A compound according to claim 3, characterized in that the R- (isobutyl-ethyl) -21-isobuto :: γ-6 '-methy 1-2-chlorcoraceetar.ili.de. 6. A compound according to claim 3, characterized in that it is γ- (isopropoxyethyl) -2T -obutovy-6-veckyl-2-chlororacetanilida. aceecanilide. S. Compound according to claim 3, grease the d-1 Cfnl w ct'1 1 1 1 Γ. ; d zs. A compound according to claim 2, characterized in that the h- (ethoswethyl) -2 T-n-butcvy-61-acropyl-2-. V - 58 - chloroacetanilide. A compound according to claim 2, characterized in that it is N- (isobutoxymethyl) -2'-isopropoxy-6, -methyl-2-chloroacetanilide. Compound according to claim 2, characterized in that it is N- (isobutoxymethyl) -2'-n-propoxy-6'-methyl-2-chloroacetanilide. 12. A compound according to claim 2, characterized in that it is N- (n-propoxymethyl) -21-n-butoxy-6'-ethyl-2- 10 chloroacetanilide. Compound according to claim 2, characterized in that it is N- (allyloxymethyl) -2'-n-butoxy-6'-ethyl-2-chloroacetanilide. 14. Herbicidal compositions comprising an additive and an herbicidally effective amount of a compound of formula 1, wherein R is ethyl, n-propyl, isopropyl, isobutyl, allyl or butenyl; R 1 is methyl, n-propyl, isopropyl, n-butyl, isobutyl or isoamyl and R 1 is methyl, ethyl or isopropyl; under the conditions that when R ^ is isopropyl, R is ethyl and n-butyl, when R. ethyl, R is ethyl, n-propyl or allyl and R 1 is n-butyl or isobutyl; x ^ when R is n-propyl, R 1 is n-butyl or isobutyl, when R is isopropyl is isobutyl; when R is isobutyl, R 1 is n-propyl, isopropyl, isobutyl or isoamyl, and when R is butenyl, R 1 is methyl. Preparations according to claim 14, characterized in that in said compound R is an alkyl or allyl group with 2 to 4 carbon atoms and R} is an alkyl group with 3 or 4 carbon atoms. 16. Compositions according to claim 15, characterized in that R is an isobutyl group. Preparation according to claim 16, characterized in that the compound is N- (n-propoxymethyl) -2'-isobutocy-6 methyl-2-chloroacetanilide. 18. A composition according to claim 16, characterized in that the compound is N- (isobutoxymethyl) -2 "isobutoxy-6" methyl-2-chloroacetanilide. 81013 2 3 - 59 - 39. A composition according to claim 15, just the connoisseurs, that the vert ending R- (isoproponynathyl) -2'-x sobutot-rv-:? -vecbyl-d-chloroacetaniid. 20. A composition according to claim 5, which is characterized in that the compound P ~ (ethcyncechyl} -2f-isobucony ~ 6 iCit®). 21. Pr spar ast according to claim ΐδ, bold net connoisseur ':, that the compound R- (allyloxyvefcl: yl) -2 * -isobuco: · ;; .— *:' - hans: tri :, that da compound 11 - (echonyinethy 1) -21 -n-bu cc :: y-67-isopropyl-2-caloracatyl silicide. 23. A composition according to claim 15, characterized in that the compound N- (isobutonyvechyi) -d’-isoproporry-e The composition of claim 15, which is the ethyl-2-chloroacetanilide. A composition according to claim 15, fat it 25. The composition of claim 35 is just ethyl-d-chicory acetaniide. 27. Marking method for controlling spiked planter; which is suitable for culture rats, it is important to note that the growth site of the plants provides a herbicidally effective amount of a compound of formula 3, isopropyl and R 'is ethyl, etiryl or isopropyl. ar ca which of P0 is isopropyl, R is ethyl and R 1 is n-buryl; or is isobutyl; Varner R is n-propyl, R1 is n-butyl or isobutyl; when P is isopropyl, R. is isobutyl; vanneor? isobutyl, R is n-propyl, isopropyl, isobutyl or isoavyl and. , r V, ·, "j., J 3 - 60 - when R is butenyl, is methyl. 28. A method according to claim 27, characterized in that said cultivated crops are sugar beets, soybeans, cotton, groundnuts, green beans, rapeseed, cucumber or tomato. A method according to claim 28, characterized in that the cultivated geiras are sugar beets. 30. Process according to claim 29, characterized in that in said compound R is an alkyl or allyl group having 2 to 4 carbon atoms and R is an alkyl group having 3 or 4 carbon atoms. 31. Process according to claim 30, characterized in that R 1 is an isobutyl group. 32. Process according to claim 31, characterized in that the compound is N- (n-propoxymethyl) -2'-isobutoxy-6-methyl-2-chloroacetanilide. 33. A process according to claim 31, characterized in that the compound is N- (isobutoxymethyl) -2'-isobutoxy-6'-methyl-2-chloroacetanilide. 34. Process according to claim 31, characterized in that the compound is N- (isopropoxymethyl) -2f-isobutoxy-6, methyl-2-chloroacetanilide. 35. Process according to claim 31, characterized in that the compound is K- (ethoxymethyl) -2, -isobutoxy-6'-ethyl-2-chloroacetanilide. 36. Process according to claim 31, characterized in that the compound is N-Callyloxymethyl-isobutoxy-ethyl-2-chloroacetanilide. 37. A process according to claim 30, characterized in that the compound is K- (ethoxymethyl) -2'-n-butoxy-6'-isc-propyl-2-chloroacetanilide. 38. A method according to claim 30, characterized in that the compound is N- (isobutoxymethyl) -2'-isopropoxy-6'-methyl-2-chloroacetanilide. 39. A process according to claim 30, characterized in that the compound is N- (isobuto.xymethyl) -2, -n-propoxy-6'-g f n i 7 o x - 61 - rcathyl-d-chlororaoreacanilide. 40. Process according to claim 30. When wet, the compound is the compound 11-f-proponyrethyl-1-n-butoyl-S-ethyl-2-ethyl acetyl triil. 41. Process according to claim 20, having the characteristic feature, the compound is graft W- (allyloxysethyl-2 '-n-bntony-6' -ethyl-2-chloroacetanilida). 42. Method for combating undesired plantar, slide sarr.er. go wet sugar beet, just the connoisseurs, 12 that and oy 2 _ an alder. ". · '. .. i '; . . " 2eeevaelhaid II- (n-preponyriethy 1) -2f-isobutoey-6 T-nathy 1-2-chloroeeetc.nili ion. Method for controlling unwanted plants which contain gas beet sugar beet, just the learner, which yield a quantity of b- (etho; ynetbyl) -2'-isobutoxy-S'-ethyl-2 as herbicide on its growth site. -carbon nneetenilide. 44. A method according to any one of claims 27 to 42 or 43, the remaining characteristic is that said undesired plants are annuals of broadleaf weeds. 45. Methods and products in the main task as described in the description and / or the examples. -6 2.- Improvement of errata in the description associated with the patent application.neutel.01323 Ned. suggested by applicant .. 3ÖJ0LMSW dcL___________ Change in line 10 of page 12 "% Control" to "% Damage". In line 20 of page 12 change "Canada thistle" and "Yellow cypergrass" to "field thistle" 5 and "Yellow sedge" respectively. In line 21 shorten "Rweekgras" to "cultivation". In line 22 change "Chamber Maple" to "Abutilon" and after "Johnson Grass" add "(Aleppo Millet)". Change in line 23 "Fuzzy" to "soft", and in line 24 of page 12 change "Loosestrife" to "Goosefoot". 10 JKr / JvdB O 4 ƒ) A Ί O 7 y a U i Ü l 0 * '* o I! CiCHpC CHsOR ΓΤ 1¾ OR1 MONSANTO COMPANY, St. Louis, Missouri, USA St. S 'i Ö 1 3 2 3