LU83234A1 - N-ALKYL-2-HALOACETANILIDE COMPOUNDS AND HERBICIDE COMPOSITIONS CONTAINING THEM - Google Patents

Description

Λ ο ι / - / λ; \ 'Λα 1.

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

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

As a prior art relating to the compounds of the present invention, which are characterized in that they have a methyl or ethyl radical on the anilide nitrogen, an alkoxy radical in an ortho position and a methyl radical in the other ortho position, the closest prior art known to the applicant is shown in US Patents 3,268,584, 3,442,945, 3,773,492 and 4,152,137. U.S. Patent Nos. 3,773,492 and 4,152,137 describe generic formulas for herbicidal compounds which broadly include the compounds of the present invention. However, the only compound of N-alkyl-substituted 2-haloacetanilide specifically described by US Patent No. 3,773,492 or US Patent No. 4,152,137 is the product known as propachlor, that is ** 2 .

ie N-isopropyl-2-chloroacetanilide, which is a well-known commercial herbicide; neither of these patents describe herbicide results relating to propachlor. U.S. Patent No. 2,863,752 (Reissue Patent No. 26,961) describes compounds of a class including propachlor (not specifically named), its counterparts and analogs. Among the compounds included in the scope of protection of US Pat. No. 2,863,752, propachlor has been found to be the most effective herbici-10 of, and therefore has been developed as than commercial herbicide. US Patent No. 2,863,752 indicates that 3 of the compounds presented can be used at rates as low as 1.12 kg / ha; however, as shown in Example 4, the experimental results presented are limited to application rates of 5.6 kg / ha and 28 kg / ha. In addition, N-ethyl-2-chloroacetanilide is a species named in US Patent No. 2,863,752. however, US Patent No. 4,137,070 indicates that this compound (Example No. 406 in US Patent No. 4,137,070) is an antidote for herbici-20 known as EPTC. In contrast to the foregoing compounds, of U.S. Patent No. 2,863,752, the compounds of the present invention are highly effective and selective herbicides against weed species which are excessively difficult to control or destroy, at well applied rates. below the rate of 1.12 kg / ha, for example up to less than 0.07 kg / ha.

The compounds described in US Pat. Nos. 3,268,584 and 3,442,945 are perhaps more advantageous from a structural point of view for the compounds of the present invention than the product known as propachlor or related compounds. "" Tees. In particular, Example 13 of the patent: American No. 3,268,584 describes the compound Nt-butyl-2'-methoxy-2-chloroaceous-tanilide and Example 67 of American patent No. 3,442,945 describes the compound 2 '-methoxy-6'-t-butyl-2-chloroacetanilide.

35 Thus, propachlor differs from the compounds of the present invention by the type of substituent radicals in two positions, that is to say the two ortho positions of the molecule, ίι 3.

Vf as well as by the particular alkyl radical attached to the nitrogen atom. Example 13 in US Patent No. 3,268,584 differs by the type of the substituent in an ortho position, by the particular alkoxy radical da / is the other ortho position 5 and by the particular alkyl radical attached to the atom d nitrogen, and Example 67 in US Patent No. 3,442,945 differs from the compounds of the present invention by the type of substituent attached to the nitrogen atom and by the particular alkyl and alkoxy radicals respectively, attached to the positions ortho ^ q of the anilide molecule.

US Patent No. 4,146,387 describes compounds of 2-haloacetanilide which may be substituted by alkyl radicals on the nitrogen atom and in two ortho positions. The compounds of United States Patent No. 4,146,387 are described as known herbicides of the type indicated, for example in the United States Patent Nos. 3,442,945 and No. 2,863,752 mentioned above, including propachlor.

US Patent No. 3..0.8.584 contains, certain herbicidal results relating to the compounds mentioned above 2o having a chemical configuration most closely related to the compounds of the present invention, and certain results are presented for other compounds less closely related counterparts and analogues from a chemical structure point of view. More particularly, these most interesting references, while describing a herbicidal activity on a large number of weeds, do not give results for compounds which are shown to control in addition and / or simultaneously the diffuse annual weeds. - * cilia to be destroyed, such as Texas panicum, stinging grass (Raoul grass), wild prosomillet, Alexander 1-dre grass, red rice, brittle and young cane Johnson herb plants, while simultaneously controlling or suppressing a wide range of other annual and perennial noxious weeds, for example the 35 walnut sedge, beautiful grass, quarter lamb, ansenrine, fox tails, large wild grass and backyard grass.

** * ί- 4.

A highly useful and desirable property of herbicides is the ability to maintain weed control for an extended period of time, the longer this period, the better this is during each harvest season. With many prior art herbicides, weed control is only adequate for 2 or 3 weeks, or in some superior cases, may be up to 4-6 weeks, before the chemical loses its phytotoxic property. effective. As a result, a disadvantage of most prior art herbicides is their relatively short lifespan in the soil.

Another disadvantage that some herbicides of the prior art, somewhat related to longevity in the soil under normal climatic conditions, is their sensitivity to leaching into the soil, i.e. the lack of persistence of control weeds under heavy rain which deactivate many herbicides.

Another disadvantage of many prior art herbicides is the limitation of their use in specified types of soil, i.e. while some herbicides are effective in soils having small amounts of organic matter, they are ineffective in other soils with a high content of organic matter or vice versa. It is therefore advantageous that a herbicide is useful in all types of soil ranging from light organic soil to heavy clay and manure (garbage).

<. Yet another disadvantage of many prior art herbicides is the limitation to a particular, effective mode of application, i.e., as a pre-emergence application on the surface or as a as a method of application by incorporation into the soil before the plant. It is highly desirable to be able to apply a herbicide according to any mode of application, whether by surface application or by incorporation before the plant.

Finally, a disadvantage in certain herbicides

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is the need to adopt and maintain special handling procedures due to the toxic nature of these herbicides. Therefore, another wish is that a herbicide be safe to handle.

It is therefore an object of the present invention to provide a group of herbicidal compounds which overcome the above-mentioned drawbacks of the prior art and which provide multiple advantages in a single group of herbicides.

It is an object of the present invention to provide herbicides which selectively control or destroy - hard-to-destroy annual weeds, such as Texas panicum, Raoul grass, wild prosomillet, Alexander grass , red rice, brittle cane and play-15 born Johnson grass plants, while simultaneously controlling or suppressing a wide range of less resistant annual and perennial weeds, as mentioned above, all maintaining safety for the plants to be harvested in a large number of plants to be harvested, including.

20 soybeans, cotton, peanuts, rapeseed, white beans, alfalfa and / or vegetable crops.

It is another object of the present invention to provide herbicidal efficacy in the soil for extended periods of time of up to at least 12 weeks.

Another object of the present invention is to provide herbicides which resist leaching and dilution as a result of high humidity conditions, for example ~ in the form of heavy rain.

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

Another advantage of the herbicides of the present invention is the flexibility available in the mode of application, that is, by application of pre-emergence on the surface and by incorporation into the soil before the plant.

4 Ή 6.

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

The objects indicated above and still others of the present invention will become more apparent from the detailed description below.

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

The Applicant has now found that a selective group of 2-haloacetanil.ides, characterized by the specific combinations of alkyl radicals on the nitrogen atom of anilide and in an ortho position and of specific alkoxy radicals in l the other ortho position, has remarkable and unexpectedly superior herbicidal properties compared to the herbicides of the prior art, comprising the most intimately related compounds of the most interesting technique.

A main feature of the herbicidal compositions of the present invention is their ability to control or destroy a wide range of weeds, including weeds controllable by common herbicides, and, in addition, several weeds which, individually and / or collectively, have so far escaped control by a single class of known herbicides, while maintaining safety for the plants to be harvested in relation to several plants to be harvested including, in particular, soybeans, cotton, peanuts, rapeseed, white beans (brittle beans *), alfalfa, and other plants as well. While prior art herbicides are useful for controlling a large number of weeds / occasionally including some resistant weeds, the unique herbicides of the present invention have been found to be able to greatly control or suppress several resistant weeds, especially weeds% »η i 4 annual herbs such as Texas panicum, stinging grass, wild prosomillet (panicum miliaceum), Alexander grass, red rice, brittle cane and young Johnson grass plants, while controlling and / or suppressing other less resistant annual and perennial weeds.

The compounds of the present invention are characterized by the formula: 10 0

C1CH2C. R

R „. ~ ----- χ -, ------- 0l '<.

15 2 O | 1 x x ^ R ..

where R is methyl or ethyl; is an a.lkyl radical a Cj_t, preferably alkyl radicals in R2 is methyl, ethyl or t. -but y le, preferably the methyl group, and R ^ is hydrogen or the methyl group in the meta position, preferably hydrogen; Provided that: when R is the ethyl group leaves the n-butyl group, R2 is the methyl group and R is hydrogen; when R ^ is methyl, R and R ^ are also methyl and R ^ is isopropyl or n-butyl; i when hydrogen and R and R2 are both methyl, R ^ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyle, 2-methylpentyle or 1,3-dimé-35 thylbutyle; when R2 is the ethyl group, R is the methyl group and R ^ is the isopropyl group and * r 8.

when osL la -jk, .i; x. t.-butyl, K and. Rj be all 'J <Mix I group Ul «' · Ijiy J e.

good preferred species of the present invention are as follows: N-methyl-21-isopentyloxy-6 * -methyl-2-chloroacetanilide N-methyl-21-n-propoxy-61-methyl-2-chl. oroaceta-nilide N-methyl] -2'-n-butoxy-6'-ruethyl-2-chloroacetani ~ 10 lide N-methyl-2 1 -seje-butoxy-è 1 -methyl -2-chloroacetanilide N-ethyl-21-n-butoxy-61-methyl-2-chloroacetanill-15 N-methyl 1.-2 1 -isopropoxy-6 1-methyl-2-chloroacetanilide N-niethyl-2 '- isobut oxy-6 '-methyl -2-chloroacetani-1 ide N-methy 1 -2 * -1 sopropoxy-b' -éi.hy 1 -2-chl oroaeétani - 20 The usefulness of the compounds of the present invention , as active ingredients in components. t.ions herbicides for-. 25 mulated with these compounds, and the process for their use will be described below.

The compounds of the present invention can be made in many ways. For example, these compounds can be prepared by a method involving the N-alkylation of the anion of the appropriate secondary 2-haloacetaniiide with an alkylating agent under basic conditions. The N-alkylation process is described in Examples 1 cd 2 here.

EXAMPLE 1

This example describes the period of a pre-fered species, N-methyl -2 '-n-but-oxy-6' -methy 1 -2-chl oroacëtanil ide. In this example, dimethyl sulfate esL used as the alkylating agent to prepare N-alky1-2-chloroacetanili-9.

from from the corresponding dry-amide anion.

2'-n-butoxy-6'-methyl-2-chloroacetanilide, in an amount of 4.9 g (0.02 mole), dimethyl sulfate in the amount of 2.6 g (0.02 mole ) and 2.0 g of triethylbenzylammonium bromide were mixed in 250 ml of CH 4 Cl 4 with cooling. 50 ml of 50% NaOH was then added all at once at 15 ° C and the mixture was stirred for two hours. Water (100 ml) was added and the resulting layers separated. The organic layer was washed with water, dried over MgSO 4 and evaporated by the device called Kugelrohr.

A clear liquid with a boiling point of 135 ° C. under 0.07 mm Hg was obtained with a yield of 78% (4.2 g); it was recrystallized leaving it to stand to provide a colorless solid with a melting point of 41-42.5 ° C.

Analysis calculated for c14H2qc; ln02 (%): C '62.33; H, 7.47;

Cl, 13.14.

Found: C, 62.34; H, 7.49;

Cl, 13.16.

The product has been identified as N-methyl-2'-n-buto-20 xy-6'-methyl-2-chloroacetanilide.

EXAMPLE 2

In a cooled mixture (15 ° C) of 2'-n-butoxy-6'-methyl-2-chloroacetanilide in the amount of 5.6 g (0.022 mole), diethyl sulfate in the amount of 4.0 g (0.024 mole) and 2.2 g of triethylbenzylammoniuni bromide in 250 ml of methylene chloride, 50 ml of 50% NaOH were added all at once and the mixture was stirred for 5.0 minutes. Water (150 ml) was added, and the resulting layers separated; the organic layer was washed with water, dried over 30 MgSO 4, then evaporated by the device called Kugelrohr to give 4.1 g (yield 66%) of a clear liquid with a boiling point of 114 ° C under 0.05 mm Hq.

Analysis calculated for C1SH22C1N02 (%): C, 63.48; H, 7.81;

Cl, 12.49.

35 Found: C, 63.50; H, 7.85;

Cl, 12.48.

The product has been identified as N-ethy1-2'-n-butoxy-% "10.

61-methyl-2-chloroacetanilide.

EXAMPLES 3-19

By following substantially the same procedures and using substantially the same amounts of reactive products and the same general conditions as those described in Examples 1 and 2, but by substituting the appropriate dry anilide to obtain the final product N- corresponding alkylated, other N-methyl-2-haloacetanilides according to the formula given above were prepared; these compounds are identified in Table I.

TABLE I

__j Compound ^ Formula ein- ~ r "PE Analysis_ pie I pirique ° C 'Ëlé-Calcu-Trou-, n ° j (mm mentlée vé i5 j _._! Hg) | 3; N-methyl-2'-isopento- C, cH ^ XINÔ ,, 120 C 63,48 163,38- j xy-6'-methyl-2-chlo- (0,05) H! 7,81. 7,80j j roacetanilide; Cl112, 49} 12 , 44d 4 {N-methyl-21-n-propo- CJ .ClNO "130 C, 61.05 60.88 |, xy-61-methyl-2-chlo- (0.15) · H 7.09 ' 7/12! J roacetanilide i Cl '13.86 13.70}

20: · I

5 N-methyl-21-sec-bu- C1 il C1N09 C [62.33: 62.161 toxy-6'-methyl-2- 1 u Z | H j 7.47: 7.50; chloroacetanilide Clj13,14,13,10 6 N-methyl-2 '-isopro- C. ^ H ^ CINO »127 C | 61.05i61.05 poxy-6'-methyl-2- 13 10 ^ (0,03) 'HJ 7.09 d 7.09 d chloroacetanilide' Cl! 13.86 '13.83 *, i', 25 7 N-methyl-21-isopro- 0η4H ~ nClN09 105 (C j62.33 62.40 poxy-6 '-ethyl-2- 14 * (0.01) f H 7.4 7 7.52 chloroacetanilide i Clj13.14 13.03 8 N-methyl-2'-isobuto- 0, .H, C1N0 „115 j C 62.33 62.32 xy-6 '-methyl- 2-chlo- (0,03) j H 7,47 7,49 ^ roacetanilide Cl 13,14 13,12 r> ç) 9 N-methyl-2 '-methoxy- C, .H0 C1N00 99- C 62, 33 6 2.25, 6'-t-butyl-2-chloro-100 H 7.47 7.51 acetanilide (pf) Cl 13.14 13.14 10 N-methyl-2'-ethoxy- c. "H. , .C1N00 57 ~ 5 £ C 59,63 59,63 6'-methyl-2-chloro- (pf) H 6,67 6,71 acetanilide 01 14,67 14,67 11 N-methyl-2 '- ( l-m- c,, -Ηο / 101Ν0 „120 C 64.53 64.42 35 thylpentoxy) -6'-m- Z (0.08) H 8.12 8.15

j thyl-2-chloroacéta- Cl 11.90 11.8S

j nilide il j TAbLHAU____1 (SuJ tu) 1 1.

12 N-meLhyl-2'-n-penLoxy-: C H ClNü „! 125 C 62.48 63.36 61-methyl-2 ~ chloroaceous-Î 22 i (0.12) 1 H 7.81 7.81 'tanilide. ! Ci 12.49 12.50 j 13 N-methyl- ^ n-jxopôxyntéthyL-i-c H C1N0 120- C 62.33 61, 59, 0 6 '-inethyl-2-chloroaceous- | 4 20 2 160 H 7.47 7.51 tanilide j (0.05- N 5.19 i .. 0.1) 14 N-methyl-21-isopropoxy ClitH ^ .ClN0o 121 C 62.33 62.65 5 ', 6'-dimethyl -2-chloro- 14 *> 2 (0.01) H 7.47 6 * 84 acetanilide Cl 13.14 13.17 15 N-methyl-2'-n-butoxy- C II ClNü 108 C 63.48 63.54 10 3 ', 6 ^ imiétiji-2-chloroacé- Lj 22 1 (0,07) H 7,81 7,80 tanilide Cl 12,49 12,48 16 N-methyl-2' -butoxy- C, -Il .CiNf '). 46- C 63.48 63.56 5 ', 6 ^ iméÜil-2-chloroacô- ^ 2 “47 H 7.81 7.82 tanilide (pf) Cl 12.49 12.52 17 N-methyl-2'- (2-methyl-C, H. ClNn 116 c: 64.53 64.59 pentoxy) -6 '-methyl-2- 1 -4 (0.03) H 8.12 8.11 chloroacetanilide Cl 11.90 1.1.96 18 N-methyl-2 (2-methyl L- c, rH FIVE.-, 120 C 63.48 63.53 butoxy) -6 '-methyl-2- 2 ~ (0.06) H 7, 81. 7.85 chloroacetanilide Cl 12.49 12.45 19 N-methyl-2 '- (1,3-di- C. H ClNü 128 C 64.53 64.49 methylbutoxy-6'-me- 1 ”2i (0 , 15) H 8.12 8.14 20 thyl-2-chloroaceta-Cl 11.90 11.89 ____nilide________ ____ _____, ___

The second anilides which are used as starting materials in the above N-alkyl process are prepared by known methods, for example by haloacylated ion of the corresponding aniline. For example, the starting sec-anilide used in Example 1 was separated as follows: 2-n-butoxy-6-methylanine, in an amount of 27.4 g (0.0153 mole), in 250 ml of methylene ohioride was - acted vigorously with a 10% sodium hydroxide solution (0.25 mol) while a solution of chloroacety chloride in the amount of 17.4 g (0.0154 mol) in methylene chloride was added over 30 minutes, maintaining the temperature between 15 and 25 ° C with external cooling. The reaction mixture was stirred for another 60 minutes. After the addition was complete, the separated layers and the methylene chloride layer were washed with water, dried 12.

and evaporated in vacuo to obtain 28.3 g of a white solid with a melting point of 127-128 ° C.

Analysis calculated for C ^ H ^ gClNC ^ (%): C, 61.05; H, 7.09;

Cl, 13.86.

5 Found: C, 61.04; H, 7.08;

Cl, 13.86.

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

The secondary anilides used as starting materials, 2.0 in Examples 3-19 were prepared in a similar manner.

The primary amines used to prepare the secondary anilides mentioned above can be prepared by known means, for example by catalytic reduction of the corresponding 2-alkoxy-6-alkyl-ni.trobenzene in ethanol, using a platinum oxide catalyst.

As noted above, the compounds of the present invention have been found to be effective as herbicides particularly as pre-emergence herbicides, although post-emergence activity has also been presented. The pre-emergence tests referred to here include both tests in greenhouses and tests in the fields.

In tests in greenhouses, the herbicide is applied either as a surface application after planting the seeds or vegetative propagules, or by incorporation in a certain amount of soil to be applied as a covering layer on the seeds in pre-seeded experimental containers. In field tests, the herbicide is incorporated before the plant ("PPI") into the soil, that is, the herbicide is applied to the soil surface and then incorporated into it by means of mixing, followed by planting the seeds of the plants to be harvested.

The experimental surface application process used in the greenhouse is carried out as follows: 35 Containers, for example aluminum boxes typically 24.13 cm x 1.3.34 cm x 6.99 cm or plastic pots of 9.53 cm x 9.53 cm x 7.62 cm, having "13.

drainage holes at the bottom, are filled at level with silt soil known as Ray, then compacted to a level of 1.27 cm from the top of the pots. The pots are then sown with species of plants to be tested, then covered with a 1.27 cm layer of the experimental soil. The herbicide is then applied to the soil surface with a belt sprayer, at the rate of 187 2 1 / ha under a pressure of 2.11 kg / cm. Each pot receives 0.64 cm of water as top irrigation, and the “10” pots are then placed in greenhouse benches for subsequent irrigation from below, as necessary. Alternatively, top irrigation can be omitted.

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

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

Good top soil quality is placed in aluminum boxes and compacted to a depth of 9.5mm to 12.7mm from the top of the box. Above the ground, a predetermined number of seeds or vegetative propagules of various plant species are placed. The soil required to fill the boxes at the level after sowing or adding vegetative propagules is weighed in a box. The sol and a known amount of the active ingredient applied in a solvent or in the form of a wettable powder suspension are completely mixed and used to coat the prepared dishes. After treatment, the boxes are given an initial irrigation of water from above, equivalent to 0.64 cm of rain, then humidified by irrigation from below, as is necessary to give 5 adequate humidity for germination and growth. As an alternative procedure, top irrigation can be omitted. Observations are made approximately 2-3 weeks after seeding and treatment.

35 The tables ET. and III summarize the results of tests carried out to determine the herbicidal activity of preemergence of the compounds of the present invention; in these tests,

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herbicides were applied by incorporation into the soil and humidification by bottom irrigation only; a dash (-) indicates that the indicated plant has not been tested. The herbicidal rating was obtained by means of a fixed scale, based on the percentage of damage of each plant species. Evaluations are defined as follows:

% of control Assessment 0-24 O

. 10 25-49 1 50-74 2 75-100 3

The plant species used in a series of tests, the results of which are presented in Table II, 15 are identified by a letter according to the following legend: A Canada thistle E Quarter lamb I Grass of B Fieldnuts F Beautiful grass Johnson C Velvet leaf G Yellow sedge J Fluffy brome D Volubilis of walnut gardens K Bass grass- 20 H Charla- tan grass

TABLE II

Pre-emergence activity 25 Composed of __Species of plants

example n ° kg / ha ___ ABC_D E_F G H I J K

1 11.2 33 3 333 333 331 ί 5.6 322 333 333 333 Î 2 11.2 311 233-3333; 5.6 301133-3133 3 J 11.2 3 2 333333333 30 ί 5.6 31323333233? 4 11.2 32333333333 5.6 21323333333 5 11.2 32333333333 5.6 32333333333 6 11.2 322 3333 3 333 35 5.6 322333332 3 3 7 11.2 33333333 3 33 5.6 31233333333 15.

TABLE II (Continued) S 8! 11.2 '32333333133 5.6 32223333333 9 11.2 30333333333 5.6 30233333 3 33 5 1.12 20233123133 10 11.2 22333333333 5.6 31.3 23223233 11 11.2 32233333333 5.6 22223233333 12 11.2 32233333333 -10 5.6 31133233233 13 2 -2223333-33 5.6 -1113323-33 14 11.2 3 1 3 3 3 2 3 3 3 3 3 5.6 0023 3 233 1 33 15 11.2 1 1 2 3 3 3 3 3 13 3 15 5.6 2 0 1 2 2 L 3 2 0 3 3 16 11.2 3 112 3 3333 3 3 5.6 20003233333 17 11.2 3 1 1 0 2 3 3 3 3 3 3 5.6 3 0 223 2 33 333 18 11.2 3 2 3 3 3 3 3 3 3 3 3 20 5.6 3223 3 333333 19 11.2 31223333233 5.6 30223333133

The compounds were further tested using the above procedure on the following species of 25 plants: L Soybean R Hemp Sesbanla M Sugar beet E Quarter lamb N Wheat F Beautiful grass 0 Rice C Velvet leaf 30 p Sorghum J Fluffy Brome 'B Nielle des champs S Panicum Spp.

Q Wild buckwheat K Backyard grass D Garden volubilis T Wild grass

The results are summarized in Table III.

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TABLE III

Pre-emergence activity i Composed of j _ ** £ & ££ * A * ...... plants_; 5 example n ° _kg / ha ___; LMNOPBQDREFCJSKTj 1 5.6 T3 3 3 3 3 3 3 3 3 3 3 3 3 3 3l 1.12; 2 3 2 3 3 1 2 2 3 3 3 1 3 3 3 3 | 0.28 021331212330333 3l | 0.06 (0111312012203333 | 0.01 000000101110013 3 0.006 100000-0011000232 i * 10 2 5.6 11 2 3 3 3 1 1 2 3 3 3 1 3 3 3 - 1.12 023330103330333- 0.28 012220003110333- 0.06 000200003000113 - 0.01 000100001000001- 3 5.6 2333323333333333 1.12 1333322023323333 0.28 1223301003303333 0.06 0111000003100333 0.01 0000301000002333 0.006 000000000110001 1 4 5.6 2333333333323333 1.12 022331323323333 03313333 01 0000000-00000123 5.6 33333233333333 1.12 23333333332323 0.28 02223113 333 333 0.06 011220003331233 0.01 0000000011100133 0.006 0100000021100012 6 5.6 333 323 333-31 023 7 5.6 1333 333 333 1.12 033330333233 5 0.28 023 220 223 333 0.06 0211 110322111333 0.06 000000000023 0.00 5.600000120001022 0.00 5.600 17.

i 9 5.6 13333323333333333 I 1.12; 1233312223113333! 0.28 0122201323212233 i 0.06 0121100020200233, C 0.01 0120000021100023 1 D j 10 5.6 2233303333233333: 1.12 0223311233223333 | , 0.28 0213302223023333 d 0.060101200032023333 0.01 0100000010010003

; I

11 5.6 13 333 133 333 313 333 10! 1.12 0123302223303333 0.28 01233-0113303333! 0.06 0012100023202233! 0.01 000000000000001 3 12 | 5.6 2233313133313333 I 1.12 0233313233313333! 0.28 0233300013203333 15 J 0.06 0023302001203333! 0.01 0000000020001033 13 d 5.6 123232333332333- 1.12 022331223331333- 0.28 02230011 2320233- 0.06 d 011100001210033-0.01 000000000010101- 20! 14 i 5.6 3333313333323333! 1.12 232,330 323,333 j 0.28 222,230 232,213 333 j 0.06 021,212 122,02233 j 0.01 011,100,111,000,023 '0.006 010 100,111,00013 25 15 5.6 233,331 333,323,333 1.12 023,331 213,203 333,228 0111,213,000,233 0.01 - 30 0.28 021330001330233- 0.06 010100003100323- 0.01 000000000000111- 17 5.6 033330113331333- 1.12 022330102220333- 0.28 021320001010333- 0.06 000100001100113- 35 0.01 00000-000000001- 18 5.6 3333333333 0333303333323333 0.28 0223302023213333 0.06 0200202002303333 _ 0.01 0 2 0 0 0 0 0 0 0 C - 0 0 0 3 _3_ 18.

The herbicides of the present invention have been found to possess unexpectedly superior properties as pre-emergence herbicides, particularly for the selective control or selective destruction of Texas hard-to-destroy annual weeds. panicum, Johnson grass seedlings, brittle cane, Alexander grass, wild prosomil-let, red rice, and stinging grass, while also controlling or suppressing many other weeds * 10 its less resistant annual and perennial herbs.

The selective control and increased control of the above-mentioned weeds with the herbicides of the present invention have been found in a large number of plants for harvest, including soybeans, cotton, macaws, rapeseed and brittle beans (white beans).

Selectivity has been shown in some tests for various application rates in sugar beets and garden peas; however, certain crop plants, particularly herbaceous crop plants, are usually less tolerant of the herbicides of the present invention than the preceding crop plants.

To illustrate the unexpectedly superior properties of the compounds of the present invention, both on an absolute and a relative basis, comparative tests were conducted in the greenhouse with the most intimately known compounds of the prior art related in structure to the compounds of the present invention. The compounds of the prior art are identified as follows: • A. Nt-butyl-2-methoxy-2-chloroacetanilide (Example 30 13, US Patent No. 3,268,584) B. 2 '-t-butyl-6' - rnothoxy-2-chloroacetanilide (example 67, American patent n ° 3,442,945) C. N-isopropyl-2-chloroacetanilide (common name "propachlor"): American patent n ° 2,863,752 35 (Reissue patent n ° 26,961) ; propachlor is indicated by way of reference in US Pat. Nos. 3,773,492 and No. 19.

4,152,137 mentioned above and is the active ingredient in the commercial herbicide known under the trademark "Ramrod", which is a trademark of the so-called Monsanto Company.

5 In the discussion of the results below, reference is made to the rates of herbicide application symbolized by "GR, and" GR0 "; these rates are given in kilograms per 1D Oj hectare (kg / ha). GR. ^ defines the maximum rate of herbicide required to produce 15% or less damage to the plants to be harvested, and GRg ^ defines the minimum rate required to obtain 85% weed inhibition. GR. c and GRg rates ^ are used as measures of potential commercial performance, it being understood of course that suitable commercial herbicides may exhibit more or less damage to plants within reasonable limits.

Another guide to the effectiveness of a chemical as a selective herbicide is the "selectivity factor" ("FS") for a herbicide in given crop plants and in given weeds. The selectivity factor is a measure of the relative degree of safety of the plants to be harvested and of damage to weeds and is expressed as a function of the ratio GR ^ / GRg, -, that is to say the rate GR ^ g for the plant to be harvested divided by the GRq5 rate for the weed, the two rates being in kg / ha. In the tables below, the selectivity factors are presented in brackets after the GRg5 rate for each weed; the symbol "NS" indicates "non-selective". Marginal or questionable selectivity is indicated by a dash (-); a blank space means that the plant indicated was not in the test or that the plant could not germinate.

Since the tolerance for the plants to be harvested and the control or destruction of weeds are interrelated, a brief discussion of this relationship as a function of selectivity factors is significant. In general, it is desirable that the safety factors of the plants to 20.

coiter, i.e. herbicide tolerance values, are high, since higher concentrations of herbicides are frequently desired for one reason or another. Conversely, it is desirable that weed control rates be low, that is, the herbicide has high unit activity, for economic and possibly ecological reasons. However, low rates of herbicide application may not be adequate for controlling certain weeds and a higher rate may be required. Therefore, the best herbicides are those that control the greatest number of weeds with the least amount of herbicide and that provide the greatest degree of safety for the plants to be harvested, i.e. tolerance to plants to harvest.

Therefore, "selectivity factors" (defined above) are used to quantify the relationship between safety for the plants to be harvested and weed control. Referring to the selectivity factors shown in the tables, the higher the numerical value, the greater the selectivity of the herbicide for weed control in a given crop.

In a first comparative test, data of pre-emergent herbicidal activity in greenhouses are presented in Table IV, comparing the relative efficacy of the compound of Example 1, which is a representative compound of the present invention, with interesting compounds of the prior art, namely compounds A, B and C, as selective herbicides against particular weeds commonly associated with soybeans. The experimental results in table IV for all the compounds were obtained 1 under identical experimental conditions, that is to say by incorporation into the soil with an initial irrigation from above; the results represent the means of two tests carried out in duplicate for each compound; two different samples of the compound of Example 1 were used and the results in the table represent the average from the two experimental samples. The bad her- 21.

bes used in the test here have the following abbreviations in the tables: Texas panicum (TP), young johnson grass seedlings (SJG), brittle cane (SC), Alexander grass (AG), wild prosomillet (WPM) , fall panicum (FP), red rice (RR) and stinging grass (GI).

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Referring to the results in Table IV, it will be seen that, with respect to weed control, none of the prior art compounds exhibited positive and selective control of weeds against. 5 te what weed in soybeans at the maximum rate of application, that is to say 1.12 kg / ha, but, with the only exception of compound C against fall panicum- and even in this case, the selectivity factor was one time less than that for the compound of Example 1. In marked contrast, Compound 10 of Example 1 selectively controlled each weed in the test at extremely low rates of application, while now security for soybeans up to 0.71 kg / ha. Of particular note is the fact that the compound of Example 1 controlled young Johnson grass plants, brittle cane, Alexander grass, fall panicum and stinging grass, at the rate of 0.07 kg / ha (the minimum rate used) or less, and also controlled the remaining weeds, i.e. Texas panicum, wild prosomillet, and red rice at rates only equal to 0 respectively , 10, 0.14 and 0.18 kg / ha.

Additional tests were conducted in the greenhouse in order to compare the relative herbicidal efficacy of the compounds of the prior art AC with the compounds of Examples 1, 3-5 and 8-17 by way of illustration of the compounds of the present invention. The tests were carried out by incorporation into the soil of the herbicide at application rates in the range of 0.07 to 1.12 kg / ha and initial irrigation from above, followed by humidification by subsequent irrigation. from below, as necessary. The 30 observations were made 19 days after treatment. The results from the additional tests are presented in Table V; the names of the weeds are indicated in abbreviation as in Table IV and the selectivity factors are presented in brackets after the GR0 rates

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Referring to the results in Table V, it will be noted that, within the limits of the experimental rates of herbicides, Compound A did not: selectively control any of the experimental weeds in soybeans; Compound B only controlled selectively marginally fall panicum (which is not a particularly resistant weed) and Compound C selectively controlled only fall panicum and, marginally, Texas panicum, Alexander grass and red rice. With the only -10 the exception of compound C against fall panicum (GRg, equal to 0.28 kg / ha), and of compound B against Alexander grass and fall panicum (GRg, - = 1, 00 kg / ha), none of the prior art compounds controlled any of the weeds in the test below 1.12 kg / ha.

In strong contrast, if not isolated cases against certain weeds, all of the compounds of the present invention exhibited remarkable positive selective control of each weed in soybeans. Only in a few cases was selective control marginal, for example that of the compounds of examples 8 and 17 against red rice, of example 9 against wild prosomillet and red rice, of example 14 against wild prosomillet and Example 15 against brittle cane. Again, as opposed to the prior art compounds and again with the noted exceptions, all of the compounds of the present invention controlled all weeds at extremely low rates of application, ranging from a value of not more than 0.56 kg / ha and lowering to less than 0.07 kg / ha, which is a remarkable performance in absolute terms due to the highly resistant nature 30 experimental weeds (except fall panicum) and particularly in relation to the inability of most of the most valuable compounds of the prior art to control any of the experimental weeds, except as noted above.

Preferred compounds of the present invention have been further tested in the field to determine their selective pre-emergence herbicidal activity and their longevity 26.

in the soil against the annual weeds formed by Texas panicum, the hairy little burdock and the grass known as Florida pusley in peanuts (Florunner). Observations were made after 4.8 and 12 weeks of birth after treatment (SAT) by surface application of herbicides; the soil type was a sandy cerreau called Dothan with 1.3% organic matter; the results are presented in table VI.

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The results in Table VI show that the compound of Example 2 selectively controlled all three weeds in peanuts at rates in the range of 2.24 to 4.48 kg / ha for a time up to 12 SAT.

The selective control of one or more of the experimental weeds was also presented by the compounds of Examples 1 and 3 at lower rates, for a time of up to 12 SAT, indicating that, among the three experimental compounds, the compound of Example 2 had the greatest safety factor in peanuts under the conditions of this test.

Other tests were also carried out in the field to determine the relative efficacy of the compounds of Examples 1, 3 and 4, against wild prosomillet in soybeans, for a period of up to 12 weeks after the treatment in l '' applying either in the form of surface applications (SA) or by incorporation before the plant (PPI). The soil was sandy soil with 1.7% organic matter; 6.35 cm of rain occurred 2 days after treatment; the results of this test are presented in table VII.

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The results in Table VII show that a rate of 3.36 kg / ha of each compound selectively controlled wild prosomillet in soybeans for 3.8 and 12 SAT in surface applications. Thus, certain treatments of the plan-5 to be harvested with the compounds of the present invention provided long seasonal controls of the wild prosomillet, since the germination and the emergence of this species progressively increase as the season is passing. The greatest degree of soy damage in PPI treatments has been estimated to be due to excessively deep and uneven incorporation by the sprayer and to the rain that occurs two days after treatment. In this test, surface application treatments provided superior weed control and superior safety for the plants to be harvested.

In another field test, the compounds of Examples 1, 3 and 4 were tested to determine their herbicidal activity on the very resistant annual weed consisting of young Johnson grass plants, with herbicide treatments per application. on the surface and incorporation before the plant. This field test was conducted in clay soil (58% clay and 3.1% organic matter). Observations were made after 4 and 8 weeks after treatment; the results are shown in Table VIII.

TABLE VIII

/ Q

____Percentage of inhibition ___ -. [___ boI grass seedlings) a .______ Johnson_____

Com- Rate _4 SAT___8 SAT_____SAT I 8 SAT

30 kg / ha PPI SA PPI T ~ SA PPI T ~ SA ‘PPI ~~ SÂ ~

Ex. 1.12 5 '3' 12 3 7 ‘23 - 10 2.24 13 12 28 10 75 67 85 80 3/36 23 15 22 17 78 85 87 80 4.48 30 18 38 22 80 85 93 78

Ex. 3 1.12 10 3 13 5 17 25 O 23 „2.24 22 13 13 7 47 67 70 60 3.36 28 18 22 15 70 82 85 78 4.48 32 22 32 23 78 78 90 68 31.

TABLE VIII (Continued)

Ex. 4 1/12 10 0 8 0 ~ T 23 33 8 2.24 13 13 8 12 60 68 85 78 3.36 23 12 20 13 73 82 87 88 4.48 22 17 28 15 75 85 88 85 5 a . Average of 3 tests carried out in duplicate ”

The compound of Example 4 selectively controlled young Johnson grass plants in soybeans at the rate of 2.24 kg / ha, for as long as 8 weeks after treatment under PPI conditions and at the rate of 10 3.36 and 4.48 kg / ha under surface application conditions. The compounds of Example 1 selectively controlled the young Johnson grass plants at the rate of 3.36 kg / ha for at least 4 weeks after the treatment, under surface application conditions.

As indicated by the results in the above tables, the compounds according to the present invention are suitably used by surface application treatments or incorporation into the soil, the preferred treatments depending on various factors such as the soil, climate, etc.

Generally, however, surface application of herbicides is preferred over incorporation into the soil.

In laboratory tests to determine the resistance of the herbicide to leaching into the soil and the resulting herbicidal efficacy, the compound of Example 1 was formulated in acetone and then sprayed at different concentrations on an amount weighing of silty loam known as Ray contained in pots having a filter paper covering the drainage holes in the bottoms of the pots. The pots containing the treated soil were subjected to leaching by placing them on a rotary table which turned under two nozzle tips of a calibrated water container to supply 2.5 cm of water per hour to simulate a fall rain. The leaching rates were adjusted by varying the time on the rotary table. Water was supplied to the soil in the pots and allowed to percolate through filter paper and the drainage holes. The jars were then left to stand for three days at room temperature. The treated soil in the pots was then removed, disintegrated and placed as a surface layer on top of other pots containing the soils known as Ray potting soil sown with seeds of backyard grass. The pots were then placed on greenhouse benches, irrigated from below 5 and the seed growth allowed to proceed for 2-3 weeks. Visual evaluations of the percentage of growth inhibition, relative to the control pots (untreated) and to the fresh weights for backyard grass, were carried out 18 days after the treatment and recorded; , the results from three duplicate tests for these tests are shown in Table IX.

TABLE IX

"; Backyard grass 15 _______________________________________________ ^ ____________

Compo- Rate Rain Percentage Fresh weight Percentage së of (kg / (cm) inhibition 1 of controls per example) (Average of 3 tests reali-.

_ple_l ses in duplicate) 2.24 0 100 T * ö ......... Y 0 0.64 100 O = 0 20 1.27 100 O j o

2.54 100 0, O

5.08 100 0 'W

10.16 95 O J O

0.56 0 100 O 0

0.64 100 O O

ς 1.27 100 O O

2.54 100 0 0 5.08 95 0 0 10.16 95 0 0 0.14 O ÎOO 0 0 0.64 100 0 0 1.27 100 O 0

on 2.54 95 0 O

5.08 95 0.20 3.3 __110.16 I_90 __0.83 ______ 14.1

The results in Table IX indicate that the compound of Example 1, by way of illustration of the compounds of the present invention, was very resistant to leaching into the soil under conditions of heavy rain and exhibited no less 90% backyard grass control, at application rates as low as 0.14 kg / 33.

ha under 10.16 cm of rainfall.

A distinct advantage of a herbicide is its ability to work in a large number of soil types. Consequently, data are presented in Table X mon-5 showing the herbicidal effect of the compounds of Examples 1 and 3 on Alexander grass (AG) and backyard grass (BYG) in soybeans. in a large number of soil types and organic matter contents. The herbicide treatments were applied by surface application with irrigation. The top, as described above; the selectivity factors for weeds are presented in parentheses after the GRoc rate for weeds.

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PAINTINGS

! 'Rate Rate GRoca i GR. , a: (kg / ha) 85 | Ifrg / flaLi _______ t______________

Soil type Material) Clay) Sojas; AG i BYG

and organic compound% l t __que,% ________________

Soil li- j moneux dit 20 Ray 1.0 I 9.6

Example 1! 1.12 <0.14 (> 8.0) 0.14 (8.0)

Example 3 1.12 <0.14 (> 8.0) <0.14 (.-> 8.0)

Clayey soil known as Sarpy 2,3

Example 1 <2.24 0.28 (> 8.0) 0.96 (> 2.3) {25 Example 3 <2.24 0.21 (> 10.7J 0.42 (> 5.3) {

Soil-like clay loam

Drummer 6.0 37.0

Example 1 2.24 <0.14 (> 16.0. 0.24 (> 9.3) - Example 3 <2.24 <0.14 (> 16.0! 0.28 (> 8.0)

Sand of

Florida 6.8 1.8

Example 1 1.12 <0.14 (> 8.0) 1.12 (1.0)

Example 3 1.12 0.28 (4.0) 2.24 (NS)

Florida manure 22.1 35 Example 1 2.24 1.12 (2.0) 2.24 (1.0)

Example 3 2.24 2.24 (1.0) <2.24 (NS) 34.

TABLE X (Continued)

Brazilian sandy clay soil (Sao Paulo) 17.6 20.0

Example 1 1.12 <0.14 (> 8.0) 0.14 (8.0) 5 Example 3 _I ___ jl, 12 0.14 (8.0) 0.14 (8.0) a. The results represent the means of two tests carried out in duplicate. Observations were made 13 days after treatment.

The results in Table X show that the compounds of the present invention were largely insensitive to the type of soil. More particularly, the compound of Example 1 exhibited a positive selective control of the Alexander grass and of the backyard grass in the soybeans in all the soils in the test containing organic matter whose content will from 1.0% of organic matter in the silty soil known as Ray to 22.1% of organic matter in the soil made up of Florida manure. Similarly, the compound of Example 3 exhibited positive selective weed control in the test in soybeans 20 in all types of soil, except the iest against backyard grass in the sand from Florida (6.8 '1 organic matter) and from Florida manure. Since the compound of Example 3 selectively controlled both Alexander grass and backyard grass in soil made up of loamy clay soil known as Drummer, having approximately the same organic content as Florida sand, but a much higher clay content (37.0%) and in soils with a higher organic matter content and a higher clay content, such as in Brazilian sandy clay soil, it is believed that the low clay content (1.8%) in the Florida sand contributed to the non-selective control of backyard grass in this soil.

The compounds of the present invention have their most important application in soybeans and in arachis. However, selective weed control has been established in many other crops, 35.

as shown in Table III above. In yet other tests, the compound of Example 1 has also been shown to be useful in brittle beans and in garden peas at rates of up to 1.12 kg / ha. in cotton, rapeseed, carrot and red beet at rates of up to 0.56 kg / ha or more and in alfalfa, flax and cabbage at rates of the order of 0 , 28-0.56 kg / ha.

Toxicological studies on the compounds of Examples 1, 3 and 4 indicated the following properties:. 10_____________________

Toxicology _____ Composed of Example No _ 13 4 DL05q, mg / kg 3370 2300 2400 DLD, mg / kg> 2000> 1000: 1260> 3100 <5010 15

Eye irritation Mild Significant Moderate

Skin irritation None Corrosive Corrosive

The corrosive nature of the compound of Example 3 may be due to a contamination product, dimethyl sulfate, found in the preparation of the sample on which toxicological studies have been carried out. It appears that the above compounds can be used safely with the normal degree of care required for compounds having the indicated toxicological properties. The indicated relative degree of safe handling characteristics for the compounds of the respective examples appears to be: example l> example 4> example 3.

Consequently, it will be appreciated from the foregoing detailed description that the compounds according to the present invention have shown unexpected and remarkably superior herbicidal properties both in absolute terms and relative to the most interesting compound in terms structure of the prior art, one of which (Compound C) is a commercial herbicide. More particularly, the compounds of the present invention have proved to be remarkable selective herbicides, particularly for the control of annual herbs which are difficult to destroy in the 36.

soybeans, peanuts and other plants to harvest. More particularly, the compounds according to the present invention exhibit remarkable control of the annual grasses constituted by Texas panicum, stinging grass, wild prosomillet, Alexander grass, young grass plants. of Johnson, brittle cane and red rice, while controlling and / or suppressing other less resistant annual herbs and perennial herbs including those mentioned in Tables II and III above and others, such as „ 10 than the little hairy star burdock, the so-called Florida pusley grass, etc.

The herbicidal compositions of the present invention, comprising concentrates which require dilution before application, contain at least one active ingredient and an adjuvant in liquid or solid form. The compositions are prepared by mixing the active ingredient with an adjuvant comprising diluents, extenders (fillers) / carriers and conditioning agents to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any what a suitable combination of these products.

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

37.

Preferred wetting agents are alkyl benzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, sodium sulfosuccinate esters , sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, acetylene glycols, ditertiary, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenol), and these polyoxyethylene derivatives of esters higher monocarboxylic fatty acids of hexitol anhydrides (eg sorbitan). Preferred dispersion products are methylcellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkylnaphthalenesulfonates, sodium naphthalenesulfonate and polymethylene bisnaphthalenesulfonate.

Wettable powders are water dispersible compositions containing one or more active ingredients, an inert solid extension or dilution product and one or more wetting and dispersing agents. Inert solid extension products are ordinarily of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals from silica and the like. Examples of these extension or dilution products include kaolinites, so-called attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the present invention ordinarily contain from about 0.5 to 60 parts (preferably 5-20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1-15 parts). wetting agent, about 0.25 30 to 25 parts (preferably 1.0-15 parts) of dispersant and 5 to about 95 parts (preferably 5-50 parts) of inert solid extender, all the parts being by weight relative to the total composition. When required, about 0.1 to 2.0 parts of the inert solid extender can be replaced with a corrosion inhibitor or an anti-foaming agent or both.

Other formulations include 38 concentrates.

dust comprising 0.1 to 60% by weight of the active ingredient on a suitable extension product; this dust can be diluted for application at concentrations in the range of about 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 until they are uniform and then homogenized to give an emulsion stable of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size so that, when diluted and sprayed, the coating is very uniform. Suitable concentrations of these formulations contain about 0.1-60%, preferably 5-50% by weight, of active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent. .

In another form of aqueous suspension, a water-immiscible herbicide is encapsulated to form a microencapsulated phase dispersed in an aqueous phase. In an exemplary embodiment, tiny capsules are formed by bringing together an aqueous phase containing an emulsifier consisting of ligninesulfonate, a water-immiscible chemical and polyethylene glycol polyphenylisocyanate, by dispersing the phase immiscible with water. in the aqueous phase, followed by addition of a polyfunctional amine.

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

Concentrates are ordinarily solutions of active ingredient in water-immiscible or partially water-immiscible solvents with a surfactant. Solvents suitable for the active ingredient of the present invention include dimethylformamide, di-39.

methyl sulfoxide, N-methylpyrrolidone, hydrocarbons and ethers, esters or ketones immiscible with water. However, other high concentration liquid concentrates can be formulated by dissolving the active ingredient 5 in a solvent and then diluting, for example with kerosene, to the spray concentration.

The concentrated compositions herein generally contain about 0.1 to 95 parts (preferably 5-60 parts) of active ingredient, about 0.25 to 50 parts (preferably * 10 1-25 parts) of surfactant. active and, when exi ge, about 4 to 94 parts of solvent, all parts being by weight based on the total weight of the emulsifiable oil.

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

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

40.

The compositions of the present invention may also contain other additive products, for example, fertilizers, other herbicides, other pesticides, safety products and the like used as adjuvants or in combination with any of the adjuvants described above.

Chemicals useful in combination with the active ingredients of the present invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like such as: Nitrogen / sulfur heterocyclic derivatives 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 15 2-chloro-4, 6-bis (isopropylamino) -s ~ triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 2,2-dioxide 3-isopropyl-ΊΗ-2, I, 3-benzothia-diazin- 4- (3H) -one 3-amino-1,2,4-triazole the salt of 6,7-dihydrodipyrido (1,2-a: 2 ', 1'-c) -pyrazininium 5- bromo-3-isopropyl-6-methyluracil 1,1'-dimethyl-4,4'-bipyridinium

Urea 25 N '- (4-chlorophenoxy) phenyl-N, N-dimethylurea N, N-dimethyl-N' - (3-chloro-4-methylphenyl) urea 3- (3,4-dichlorophenyl) -1 , 1-dixnéthyluré 1,3-dimethyl-3- (2 ~ benzothiazolyl) urea. 3- (p-chlorophenyl) -1,1-dimethylurea 1-butyl-3- (3,4-dichlorophenyl) -1-methylurea

Carbamates / thiolcarbamates 2-chloroallyl diethyldithiocarbamate Ν, Ν-diethylthiolcarbamate S- (4-chlorobenzyl) isopropyl N- (3-chlorophenyl) carbamate 35 Ν, Ν-diisopropylthiolcarbamate - allyl ethyl Ν, Ν-dipropylthiolcarbamate 4].

* I a d i prop / i. S-propyl f-hiolcarbamate Acetamides / acetanilides / anilines / amides la 2-chloro-N, N-diallylacetamide la N, N-dimethyl-2,2-diphenylacetamide 5 la N- (2,4-dimethyl-5- [ [(trifluoromethyl) sulfonyl] amino] phenyl) acetamide N-isopropyl-2-chloroacetanilide 2 ', 6' -diethyl-N-methoxymethyl-2-chloroacetanilide 21-methyl-6'-ethyl-N- (2- methoxyprop-2-yl) -2- * 10 chloroacetanilide 1'α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-p-tolui-dine la N- (1,1-dimethylpropynyl.) -3,5-dichlorobenzamide.

Acids / esters / alcohols Methyl 2,2-dichloropropionigue II acid 2-methyl-4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid 2 - [2,4 - (2,4-dichl.orophenoxy) phenoxy Jpropionate methyl 20 3-amino-2,5-dichlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid 11 2,3,6-trichlorophenylacetic acid 5- [2-chloro-4- (trifluoromethyl) phenoxy] - Sodium 2-nitro-benzoate 25 4,6-dinitro-o-sec-butylphenol N- (phosphonomethyl) glycine, its monoalkyl salts (as amines, its alkali metal salts and combinations thereof - Ethers 30 Ether of 2 , 4-dichlorophenyl-4-nitrophenyl

2-Chloro-a, a / a ~ trifluoro-p-tolyl-3-ethoxy- 4-nitrodiphenyl ether

Miscellaneous products 2,6-dichlorobenzonitrile 35 methanearsonate monosodium acid disodium methanearsonate

Useful fertilizers in combination with the ingredients i 42.

assets include, for example, ammonium nitrate, urea, potassium carbonate and superphosphate. Other useful additive products include materials in which plant organisms take root and grow, such as compost, fertilizer, humus, sand and the like.

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

'10 I. Emulsifiable concentrates% by weight' A. Compound of Example 1 35.6 Mixture of calcium dodecylbenzenesulfonate / polyoxyethylene ethers (for example 15 product known under the registered trademark Atlox 3437F) 5.0

Monochlorobenzene 29.7

Aromatic hydrocarbons in Cq 29.7 100.00 B. Compound of Example 3 85.0 20 Mixture of calcium dodecylsulfonate / alkylarylpolyetheraleool 4.0

Solvent consisting of aromatic hydrocarbons in Cg 11.0 100.00 25 C. Compound of Example 4 5.0 Mixture of calcium dodecylbenzenesulfonate / polyoxyethylene ethers (for example product known as Atlox 3437F) 1.0. Xylene 94.0 30 100.00 II. Liquid concentrates% by weight A. Compound of Example 5 10.0

Xylene 90.0 35 100.00 B. Compound of Example 6 85.0

Dimethyl sulfoxide _15.0 100.00

JH

43.

C. Compound of Example No. 18 50.0 N-methylpyrrolidone 50.0 100.00 * D. Compound of Example No. 19 5.0 5 Castor oil, ethoxylated 20.0

Product called Rhodamine B 0.5

Dimethylformamide 74.5 100.00 III. Emulsions. 10% by weight A. Compound of Example 7 40.0

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

Water 56.0 100.00 B. Compound of Example 8 5.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol 3.5

Water 91.5 100.00 IV. Wettable powders% by weight 25 A. Compound of Example 9 25.0

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

Amorphous silica (synthetic) 71.0 100.00

M

30 B. Compound of Example 10 80.0 i Sodium dioetylsulfosuccinate 1.25

Calcium lignosulfonate 2.75

Amorphous silica (synthetic) _16.00 100.00 44.

C. Composed of Example No. 10/0

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

Clay called kaolinite 86.0 5 100.00 V. Dust% by weight A. Compound of example n ° 12 2.0

Attapulgite 98.0 * 10 100.00 B. Composed of Example 13 60.0

Montmorillonite 40.0 100.00 C. Compound of Example No. 14 30.0 15 Bentonite 70.0 100.00 D. Compound of Example No. 15 1.0

Diatomaceous earth 99, 0 100.00 20 VI. Granules% by weight A. Compound of Example No. 16 15.0

Granular attapulgite (passing through a sieve with a mesh opening between 25 0.841 mm and 0.420 mm, i.e. 20-40 mesh) 85.0 100.00 B. Compound of Example No. 17 30.0

Diatomaceous earth (passing through a sieve - with mesh opening between 0.841 m: r.

30 and 0.420 mm) 70.0 100.00 C. Composed of example 18 0.5

Bentonite (passing through a sieve with a mesh opening between 0.841 mm 35 and 0.420 mm) 99.5 100.00 9 45.

D. Compound of Example 19 5.0

Pyrophyllite (passing through a sieve with mesh opening between 0.841 mm and 0.420 mm) 95.0 5 100.00 VII. Microcapsules% by weight A. Compound of example n ° 1 encapsulated in a polyurethane wall of an a »10 49.2

Sodium lignosulfonate (for example product known under the trademark Reax 88B) 0.9

Water 49.9 15 100.00 B. Compound of Example 3 encapsulated in a polyurea envelope wall 10.0

Potassium lignosulfonate (e.g. product known under the trademark

Reax C-21) 0.5

Water 89.5 100.00 C. Compound of example n ° 4 encapsulated in a polyurea envelope wall 80.0

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

Water 18.0 30 100.00

When operating in accordance with the present invention, effective amounts of the acetanilides of the present invention are applied to the soil containing the plants, and are incorporated into aquatic media in any suitable manner. The application of liquid and of solid particulate compositions on the ground can be produced by conventional methods, for example with arrangements <46.4.

mechanical dust-forming devices, telescopic and hand-held spraying devices and spraying dust-generating devices. The compositions can also be applied from aircraft, in the form of a dust or a spray, owing to their effectiveness at low doses. The application of herbicidal compositions to aquatic plants is ordinarily accomplished by adding the compositions to the aquatic media in the area or surface where control of the aquatic plants is desired.

Application of an effective amount of the compounds of the present invention to the location of the unwanted weeds is essential and critical to the practice of the present invention. The exact amount of active ingredient to be used depends on various factors, including the species of plant and its stage of development, the type and condition of the soil, the amount of rainfall and the specific acetanilide used. In a selective pre-emergence application to plants or soil, a dose of 0.02 to about 11.2 kg / ha, preferably from about 0.04 to about 5.60 kg / ha, or suitably 1.12 to 5.6 kg / ha of acetanilide is ordinarily employed. Lower or higher rates may be required in some cases. A person skilled in the art can readily determine from this description, including the example above, the optimum rate to apply in any particular case.

The term "soil" is used in its broadest sense to include all conventional "soils" as defined in the New International Dictionary of Webster 30 2nd edition, unabridged (1961). refers to any substance or medium in which vegetation can take root and grow, and includes not only soil but also compost, fertilizer, manure (garbage), humus, sand and the like, suitable for maintenance plant growth.

The present invention is not limited to the examples of *

U

47.

realization which have just been described, it is on the contrary susceptible of variants and modifications which will appear to the person skilled in the art.

y

Claims (16)

1. Compounds characterized in that they have the formula: 5? C1CH-C R: »r_ (3p‘ R3 where R is methyl or ethyl; R ^ is a C ^ _g alkyl radical, · 2. Compounds according to claim 1, characterized in that R ^ is a C3_5 alkyl radical and R and R2 are methyl radicals. 35 3 - Compound according to claim 2, characterized in that it is constituted by N-methyl-2'-isopentyloxy-6'-methyl-2-chloroacetanilide. ί m 9 49. 4. Compound according to claim 2, characterized in that it consists of N-methyl-2'-n-propoxy-6'-methyl-2-chloroacetanilide. 5. Compound according to Claim 2, characterized in that it consists of N-methyl-2'-n-butoxy-6'-m-thyl-2-chloroacetanilide. 6. Compound according to claim 2, characterized in that it is composed of N-methyl-2'-sec-butoxy-6'-mé-thyl-2-chloroacétanilide. ^ 10 7 - Compound according to claim 2, characterized * in that it is constituted by N-methyl-2'-isopropoxy-6'- methyl-2-chloroacetanilide. 8. Compound according to claim 2, characterized in that it consists of N-methyl-2'-isobutoxy-6'-methyl-2-chloroacetanilide. 9. Compound according to claim 1, characterized in that it consists of N-ethyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide. 10. Compound according to claim 1, characterized in that it consists of N-methyl-2'-isopropoxy-6'-ethyl-2-chloroacetanilide. 11. Herbicidal composition, characterized in that it comprises an adjuvant and a quantity, effective from the herbicidal point of view, of a compound having the formula: 25 0 C1CH „CR ^ N: 3o * 2 ~ (o ^ ° Rl R3 where R, R ^, R2 and R ^ are as defined in claim 1. 35 12 - Composition according to claim 11, characterized in that one applies the provisions of any one of claims 2-10. * 'Λ K 50. 13. Process for controlling undesirable plants in plants to be harvested, characterized in that it consists in applying to the place where these undesirable plants are found a quantity, herbicide-effective, of a compound having the formula: 0. It ClCH2C R Λ 10 R0 _ _____OR,; ► K3 where R, R ^, R ^ and R ^ are as defined in claim 1. 14. Method according to claim 13, characterized in that the provisions of any one of claims 2 to 10 are applied. 15. Method according to claim 13, characterized in that the plants to be harvested are leguminous plants. R2 is methyl, ethyl or t-butyl, and R3 is hydrogen or methyl in the meta position; provided that: when R is the ethyl group, R ^ is the n-butyl group, s0! * 1 the methyl group and R ^ is hydrogen; When R ^ is the methyl group, R and R ^ are also the methyl group and R ^ is the isopropyl or n-butyl group; when R ^ is hydrogen and R and R ^ are both methyl, R ^ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopen -tyle, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl; when R2 is the ethyl group, R is the same group. thyle and R ^ is the isopropyl group, and ^ when R2 is the t-butyl group, R and R. ^ are both methyl. 16. Method for controlling or destroying undesirable plants in soya beans, peanuts, rapeseed, cotton, brittle beans, alfalfa and vegetables to be harvested, characterized in that it consists in applying to the place where they are found these undesirable plants a herbicide effective amount of N-methyl-2'-isopentyloxy-6 '-methyl-2-chloroacetanilide or N-methyl-2'-n-propoxy-6'-t methyl- 2-chloroacetanilide or N-methyl-2'-n-butoxy-6'- t 3 ° methyl-2-chloroacetanilide or N-methyl-2'-isobutoxy-6'-methyl-2-chloroacetanilide.