LU83236A1 - N-HYDROCARBYLOXYMETHYL-2-HALOACETANILIDES COMPOUNDS AND HERBICIDE COMPOSITIONS CONTAINING THEM - Google Patents

Description

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

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

10 'As an advantageous prior art for the compounds of the present invention, which are characterized * by the fact that they have an alkoxymethyl or alkenyl-xymethyl radical on the anilide nitrogen, an alkoxy radical in an ortho position and a specific alkyl radical in the other ortho position, the closest prior art known to the Applicant is represented by US Pat. Nos. 3,442,945 and 3,547,620. The most interesting descriptions in US Pat. Nos. 3,442,945 and 3,547,620 are the 2'-t-butyl-2-chloro-N-methoxy-20 methyl-6'-methoxyacetanilide compounds and its brominated analogue ( Examples 18 and 34 of U.S. Patent No. 3,547,620 and Examples 18 and 36 of U.S. Patent No. 3,442,945, respectively).

US Patent Nos. 4,070,389 and 4,152,137 describe generic formulas which include compounds 2.

X'-r * sés of the type described in US Pat. Nos. 3,442,945 and 3,547,620. However, the only compound of the species described having an alkyl radical in an ortho position and an alkoxy radical in the other ortho position has an alkoxyethyl radical on the anilide nitrogen atom; compounds of this type are indicated in more detail below.

Other less interesting prior techniques are Belgian Patent No. 810,763 and published German patent application No. 2,402,983? the compounds of these references 10-include compounds of the type described in US Patents No. 4,070,389 and No. 4,152,137 and are characterized in that they have an alkoxyalkyl radical having 2 (or * more) carbon atoms between the anilide nitrogen atom and the oxygen atom of the alkoxy part. The most interesting specific descriptions in Belgian Patent No. 810,763 and in published German Patent Application No. 2,402,983 appear to be compounds having an ethoxy-ethyl radical on the anilide nitrogen atom, a radical methoxy or ethoxy in one ortho position and a methyl, ethyl or isopropyl radical in the other ortho position? referring to the Belgian patent n ° 810.763, we will consider the compounds n ° 7, 13, 18-20 and 26? other less interesting counterparts of these compounds are also described, for example compounds 6, 9, 16 and 17, which have methoxymethyl or methoxypropyl radicals substituted on the nitrogen atom, a methoxy or ethoxy radical in a position ortho and a methy- * radical, the in the other ortho position.

U.S. Patent No. 3,442,945 noted above * contains certain herbicidal results relating to the compounds mentioned above, having a chemical configuration most closely related to the compounds of the present invention, and certain data are presented for other homologous compounds and analogues less closely related from the point of view of chemical structure, for example compounds 35 and 6 in Belgian patent no. 810,763. More particularly, these most interesting references, while describing * herbicidal activity on a large number of bad f v · ** 3.

grasses, do not give results for compounds which are shown to control in addition and / or simultaneously narrow-leaved weeds, difficult to destroy, consisting of black grass, wild oats, and downy brome 5 , and other weeds such as the yellow fox tail, the annual perennial tares, backyard grass and wild grass, although Belgian Patent No. 810,763 presents data showing good control or good destruction of wild oats and undefined species of various other weeds in sugar beets. However, as presented herein, the compounds according to the present invention possess inherently superior properties as selective herbicides in sugar beets compared to the homologous compounds of the prior art.

Another disadvantage of many prior art herbicides is the limitation of their use in specified types of soil, i.e. while certain herbicides are effective in soils having small amounts of material organic, 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 some prior art herbicides * is the lack of persistence of weed control under heavy rain which results in leaching of the herbicide.

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

It is, therefore, an object of the present invention to provide a group of herbicidal compounds which overcome the above-mentioned disadvantages of the technique.

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than earlier and which provide a multiplicity of benefits for a single group of herbicides.

It is an object of the present invention to provide herbicides which selectively control various weeds, particularly annual grasses including narrow-leaved weeds which are difficult to destroy, such as black grass, wild oats and downy bromegrass, and other annual herbs such as the yellow fox tail, backyard grass, wild grass and annual perennial tares, particularly in sugar beets.

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

Another object of the present invention is to provide herbicides which are resistant to leaching under 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 objects indicated above and other objects of the present invention will become more apparent from the detailed description below.

The present invention relates to compounds with herbicidal activity, to herbicidal compositions containing these compounds as active ingredients and to the herbicidal method of using these compositions in particular crops.

30 'The Applicant has now found that a selective group of 2-haloacetanilides, characterized by specific combinations of alkoxymethyl or alkenyloxy-methyl radicals on the anilide nitrogen atom, of specific alkoxy radicals in an ortho position and d an alkyl radical 35, that is to say a methyl, ethyl or isopropyl radical, in the other ortho position have remarkable and superior selective herbicidal properties t 5.

unexpected as herbicides for sugar beets compared to herbicides of the prior art, comprising compounds homologous to the most advantageous prior art.

A main feature of the herbicidal compositions of the present invention is their ability to control or destroy narrow-leaved weeds in sugar beets, particularly hard-to-destroy species such as wild oats and black grass, as well than less resistant species such as the yellow fox tail, backyard grass, wild grass and other noxious weeds.

* The compounds of the present invention are characterized by the formula: 15?

C1CH., C \ ^ CH, OR

K2 ---- ------ ', K1 2 ° where R is the ethyl, n-propylu, isopropyl, isobutyl, allyl or butenyl group; is methyl, n-propyl, isopropyl, n-butyl, isobutyl or isoamyl, and R2 is methyl, ethyl or isopropyl; provided that: when R £ is the isopropyl group, R is ethyl group and R ^ is the n-butyl group; When R2 is the ethyl group, R is the ethyl, n-propyl or allyl group and r is the n-butyl or isobutyl group; when R is the propyl group, Ri is the n-butyl group <or, isobutyl; when R is the isopropyl group, Ri is the group: butyl; when R is the isobutyl group, R ^ is the n-propyl, isopropyl, isobutyl or isoamyl group, and when R is the butenyl group, ^ is the group _r J * f 6.

methyl.

Particularly interesting compounds and their usefulness here are those where, in the above formula, R is a C 2 -C 4 alkyl radical, preferably the ethyl, n-propyl or allyl radical, is a C 3 or C 4 alkyl radical, especially the n-butyl or isobutyl radical, and R2 is the methyl or ethyl radical.

Particular species of compounds according to the present invention are the following: N- (isobutoxymethyl) -2'-isopropoxy-6'-methyl-2-chloroacetanilide; N- (isobutoxymethyl) -21-isoamyloxy-6’-methyl-2-chloroacetanilidey N- (n-propoxymethyl) -2 * -isobutoxy-61-methyl-2-15 chloroacetanilide; N- (ethoxymethyl) -2'-n-butoxy-6'-isopropyl-2-chloroacetanilide; N- (isobutoxymethyl) -2'-isobutoxy-6'-methyl-2-chloroacetanilide; N- (isopropoxymethyl) -2'-isobutoxy-61-methyl-2-chloroacetanilide; N- (isobutoxymethyl) -2'-n-propoxy-6'-methyl-2-chloroacetanilide; N- (2-buten-1-yloxymethyl) -2'-methoxy-61-methyl-2-chloroacetanilide; N- (n-propoxymethyl) -2'-n-butoxy-6'-ethyl-2-chloro * roacetanilide; N- (allyloxymethyl) -21-n-butoxy-6'-ethyl-2- * chloroacetanilide; 30 'N- (ethoxymethyl) -2‘-isobutoxy-6'-ethyl-2-chloroacetanilide; and N- (allyloxymethyl) -2'-isobutoxy-6'-ethyl-2-chloroacetanilide.

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

7.

The compounds of the present invention can be made in many ways. For example, these compounds can be prepared by the azomethine process described in the aforementioned US patents Nos. 3,442,945 and 3,547,620. According to the azomethine process, the appropriate primary aniline is reacted with formaldehyde to obtain the corresponding methyleneaniline (substituted phenylazomethine), which is then reacted with a haloacetylating agent, such as chloroacetyl chloride or the chloroacetic acid anhydride, which in turn is reacted with the appropriate alcohol to obtain the corresponding N-alco-xymethyl-2-chloroacetanilide as the final product.

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

Example 1 below illustrates the use of this N-alkylation to prepare a species of the present invention. A modified N-alkylation process is described in Example 2 to prepare another species of the present invention. The modified N-alkylation process described in Example 2 here involves the in situ preparation of the halomethyl and alkyl or alkenyl ethers used as starting materials in the N-alkylation process.

EXAMPLE 1

2'-isobutoxy-6'-methyl-2-chloroacetanilide, in the amount of 5.6 g (0.022 mole), chloromethyl ether and n-propyl ether in the amount of 4.75 g (0, 44 mol) and 2.0 30 g of benzyltriethylammonium chloride were mixed in 250 ml of methylene chloride and cooled. To the mixture at 15 ° C, 50 ml of 50% NaOH was added all at once and stirred for 2 hours, then 100 ml of cold water was added. the layers were separated, washed with water, then dried over MgSO 4 and evaporated by the device known as Kugelrohr to obtain 6.5 g (90% yield) of clear oil at a boiling point of 130 ° C. under 0.04 mm Hg.

"F 8.

Analysis calculated for C17H26C1N03 (%): C, 62.28; H, 7.99;

Cl, 10.81;

Find ; C, 62.27; H, 8.01;

Cl, 10.81.

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

EXAMPLE 2

This example describes a modification of the N-alkylation process described in Example 1. In this example of carrying out the process, the alkylating agent is formed in situ, thereby performing a more efficient, more efficient operation. economical and simpler.

at

To a cooled mixture of 4.6 g (0.1 mole) of ethanol, 1.5 g (0.05 mole) of anhydrous paraformaldehyde and 100 ml of methylene chloride, 6.1 g ( 0.05 mol) of acetyl bromide; the mixture was stirred until all of the para-formaldehyde had dissolved.

To the mixture was then added 5.1 g (0.018 mole) of 2'-n-butoxy-6'-isopropyl-2-chloroacetanilide, 2.0 g of benzyltriethylammonium chloride and 40 ml of methylene chloride. The mixture was cooled to 15 ° C and 50 ml of 50% NaOH was added all at once and cooled for 2 hours. The layers were separated, washed with water, dried over MgSO 4 and evaporated by a device called Kugel-25 rohr to obtain 4.6 g (77% yield) of a yellow liquid with a boiling point of 125 ° C under 0.07 mm Hg.

* Analysis calculated for ci8H28ClN03 (%): C, 63.24; H, 8.26;

Cl, 10.37; * Found: C, 63.23; H, 8.29; 30Cl, 10.37.

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

EXAMPLES 3-12

By following substantially the same procedure and the same conditions as those described in Examples 1 and 2, but by substituting the appropriate secondary anilide and the appropriate alkylating agent as starting materials and η.

appropriate quantities, the N- (aleoxymethy1 or alkenyioxymethyl) -2-hal.oacetani 1 corresponding ideas are ptepate: these compounds are identified in Table 1, with certain physical properties.

5 TABLE I

Exemr Compound Formula em- P.E. 1ël- Analysis J

pie j pirique ° C jinent Calcu- Found n ° (min i lée _________i _______jia) ______ I_______ 3 N- (isobutoxymé- C.ftH9ftClNÔ ^ 115 C 63.24 63.19 ln thyl -21 -iso- ± ö 0 i (0 , 02) H 8.26 8.30 butoxy-6 * -methyl- Cl 10.37 10.38 2-chloroacetani-lide "4 N- (isopropoxym- C._H0fclNO, J2u C 62.28 62.26 thyl) -21 -Isobu- w 2b 3 (0.01) H 7.99 7.99 toxy-6'-methyl- Cl 10.81 10.81, c 2-chloroacetanilide 5 N- (2-buten- l- CH ClNO 114 C 60.50 60.38 oxymethyl) -2 '- 1 b 2U 3 (0.01) H 6.77 6.83 methoxy-6'-me- Cl 11.91 11.85 thyl- 2-chloroacetanilide 20 6 N- (isobutoxyme- CH ClNO. - C 62.28 62.33 thyl) ~ 2'-iso- 1 / 2b i H 7/99 8.04 propoxy-6'-me- N 4.27 4.27 thyl-2-chloro- Cl 10.81 10.82 acetanilide 7 N- (isoamyloxy C II ClNO 120 C 64.12 63.98 methyl) -2'-iso- iy 30 3 (0.025) H 8.50 8.57 25 butoxy-6'-me- Cl 9.96 10.03 thyl-2-chloroacetanilide * 8 N- (isobutoxy- C H., CLNO, 127 C 62.28 62.20 methyl) -2 '-n- 3 (0.08) H 7.99 8.06 propoxy-6'-me- Cl 10.81 10.88 thyl-2-chloro-30 acetanilide 9 N- (n- propoxy- C . „C1N0. 117 C 63.24 63.31 methyl) -2'-n- 20 3 (0.02) H 8.26 8.27 butoxy-6 * - Cl 10.37 10.42 ethyl-2-chloroacetanlllde 10 N- (allyloxyme- C1uHo, ClN0_ 123 C 63.61 63.60 3b thyl) -21 -n-bu- 10 26 3 (0.04) H 7.71 7.74 toxy-6'-ethyl- Cl 10 , 43 10.42

2-chloroaceta-j Inilide I

10.

TABLE I (Continued) 11 N- (ethoxymethyl) - CJ C1N0 132 C 62.28 62.27 2'-isobutoxy-6'- L / 3 (0.07) H 7.99 8.02 2-ethyl-2-chloro - Cl 10.81 10.82 acetanilide c 12 N- (allyloxymé - C.fiH C1N0 124 C 63.61 63.61 thyl) -2'-isobuto- 10 3 (0.02) H 7.71 7.71 xy-6'-ethyl-2- Cl 10.43 10.45 _chloroacetanilide ______

The starting materials consisting of secondary anilides, used in the above examples, are prepared according to well known methods, for example by haloacetylation of the corresponding primary amine with agents; hydroacetylation such as a haloacetyl halide or a haloacetic acid anhydride. Typically, the appropriate amount of the appropriate primary amine is dissolved in a solvent, such as methylene chloride, containing a base, for example 10% NaOH, and stirred vigorously while mixing with a solution of the halide d haloacetyl, for example chloroacetyl chloride, with external cooling, for example at 15-25 ° C. The layers are separated 2o and the layer of organic solvent washed with water, dried and evaporated in vacuo.

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

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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 shown. The pre-emergence tests, which are referred to here, include both tests in greenhouses and tests in the fields.

35 In greenhouse tests, the herbicide is applied either by surface application after planting the seeds or vegetative propagules, or by incorporation into a 11.

a certain amount of soil to be applied as a covering layer on the experimental seeds in pre-sown experimental containers. In field tests, the herbicide can be applied by incorporation into the soil before the plant ("PPI"), i.e. the herbicide is applied to the soil surface and then incorporated into it by mixing means, followed by planting the seeds of plants to be harvested, or the herbicide may be applied to the surface (surface application "SA") after the seed of the plant to be harvested has been planted.

'The experimental surface application process C'S.A. ") Used in the greenhouse is carried out with the following rod: containers, for example aluminum boxes, typically 24.13 x 13.34 cm x 6.99 cm, or plastic pots of 9.53 cm x 9.53 cm x 7.62 cm), having drainage holes 15 in the bottom, are filled at level with a loam soil soil called Ray, then compacted until '' at a level of 1.27 cm from the top of the pots. The pots are then sown with plant species to be tested covered by a 1.27 cm layer of the experimental soils. Herbicide 20 is then applied on the soil surface, for example with a belt sprayer, at the rate of 2 187 1 / ha, under 2.11 kg / cm. Each pot receives 0.64 cm of water in the form of irrigation by the above and the pots are then placed on greenhouse benches for subsequent irrigation · * 25 from below, as necessary. As an alternative procedure, p ar the top can be removed. Observations of herbicidal effects are made about three weeks after treatment.

The herbicide treatment by incorporation in the 30 'soil ("S.I.") used in 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 the various plant species are placed. The soil required to fill the boxes at the level after sowing 12.

or addition of vegetative propagules is weighed in a box. The soil 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 re-cover the prepared dishes. After treatment, the boxes are given an initial irrigation of water from above, equivalent to a rainfall of O> 64 cm, but they are humidified by irrigation from below, as necessary to give adequate humidity for germination and the growth. As an alternative procedure, overhead irrigation can be omitted. Observations are made approximately 2-3 weeks after seeding and treatment.

Tables II and III summarize the results of tests conducted to determine the pre-emergence herbicidal activity of the compounds of the present invention in these tests, the herbicides were applied by incorporation into the soil and humidification by irrigation from below only; a dash (-) indicates that the indicated plant has not been tested. The herbicide 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 Evaluation

0-24 O

25 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, 30 are identified by a letter according to the following legend: A Canada thistle G Walnut yellow sedge B Field nielle H Quack grass C Velvet leaf I Johnson grass D Garden volubilis j Fluffy brome 35 e Quarter lamb K Backyard grass F Beautiful grass 13.

TABLE II

Pre-emergence activity

i "'' 1 '" "1' 'I

, Composed of {Plant Species

example n ° kg / ha ABCDEFGHIJK

5 d UT2 3 1 2 2 3 3 T ~ 3 3 Γ ~ 3 ~ 5.6 30223233333 2 11/2 11223333333 5.6 0-213233333 1/12 0-101121033 »10 3 11.2 00032333133 5/6 00002113333 4 11.2 3022333323 3 5.6 21222233133 5 11/2 21013233133 15 c, '5/6 10031133033 6 11/2 21113333333 5/6 21123333033 7 11/2 30113233033 5/6 20213233133 8 11/2 31023333333 5/6 32023333333 9 11/2 30002132133 5.6 3 100 2 1 3 203 3 10 11/2 -0112 233 333 25 5.6 -0003223333. 11 U / 2 31223233333 5.6 21223233 133 s 12 11/2 3-013333333 5.6 20111132133 I. .1. ..... t ...... - <*! ' > ............

The compounds were also tested using the above procedure on the following plant species: L So3a r sesbania hemp 35 M Sugar beet E Quarter lamb N Wheat P Beautiful grass 0 Rice C Velvet leaf 14.

P Sorghum J Fluffy brome B Field nielle S Panicum Spp.

Q Wild buckwheat K Backyard grass D Garden volubilis T Wild grass 5 The results are summarized in Table III.

TABLE III

Pre-emergence activity

Composed of; kg / ha Plant species! -, n example n ° j_____LMNOPBQDREFCJ SKTj iü 1 5.6 '1333303033313333 1.12 0103301013203333 0.28 0002302000103333 0.06 0002200010003233 0.01 00010000-2100023 2 5.6 1233332322313333 ,, 1.12 0123332 032 06 00010000-0001131 0.01 00000-0000000010 3 5.6 0122300320003333 1.12 0013300000003333 0.28 0000000000001133 20 0.06 0000000100000112 4 5.6 1233301132113333 1.12 0133300131003333 0.28 0112300000002333 0.06 0001100000001133 5 5.6 223332233233 1.12 0223333222203333 0.28 0113133311003333 0.06 010001032000 2 133 0.01 0100000030000033 6 5.6 1233312023303333 1.12 0111303003303333 30 0.28 0111200000001233 0.06 00330000 233 , 06 010000-001001212 jc 8 5.6 2233322233303333 1.12 0111312132203333 0.28 0000100013201333 '0.06 01001-1010100033 0.01 10000100 00 00002 3 4 15.

I TABLE III (Continued) 9 5.6 123330312330333- 1.12 002320202010333- 0.28 00011000000033 3 - 0.06 000000000000103- 0.01 000000000000100- 5 10 5.6 023330301331333- 1.12 - 1 2 2 1 0 1 1 0 2 1 0 3 3 3 - 0.28 01 1210000100333- 0.06 000000000010003- 0.01 000000000000000- 11 5.6 123331233332333- 10 1.12 013330213222333- * 0.28 012220103200333- 0.06 0 0 0 1 0 0 0 0 0 1 5 0 3 1 3 - 0.01 00010-0030- 0000- 12 5.6 0333313133313333 1.12 0133302022103333 0.28 0121001002303333 15 0.06 0011000002301033 0.01 0000000002301011

The herbicides of the present invention have been found to unexpectedly possess superior properties as selective pre-emergence herbicides for use in sugar beets, particularly for selective control of narrow-leaved weeds , difficult to destroy, including black grass, wild oats and downy bromegrass and other weeds such as yellow fox tail, annual perennial tares, backyard grass and tall grass wild. Selective control and control of the above-mentioned weeds and other weeds with the herbicides of the present invention have been found in a large number of other crops, including soybeans, cotton, peanuts, brittle beans (white beans), rapeseed, cucumbers and tomatoes. However, the markedly remarkable herbicidal properties of the compounds of the present invention are more evident in their selective control of annual herbs in sugar beets.

In order to illustrate the superior properties in unexpected ways of the compounds of the present invention, in J b.

laws on an absolute basis and on um: i, at the rulutive, comparative tests were conducted in the greenhouse with (1) compounds homologous to ". most closely related chemically to the compounds of the present invention and (2) other compounds, which, while not being homologous, fall within the scope of the prior art and one of which has superior properties as herbicides for sugar beets and two of which are commercial herbicides.

All of the compounds in the comparative tests below are generically defined as substituted phenyl-N-hydrocarbyloxyalkyl-2-haloacetanilides. As used in the result tables here, the compared compounds of the prior art are identified as follows; 15 A. N- (methoxymethyl, -2'-methoxy-6'-t-butyl-2-chloroacetanilide (Example 18, US Pat. Nos. 3,442,945 and 3,547,820).

B. N- (metnoxymethyl) -2'-methoxy-6'-t-butyl-2-bromo-acetanilide (example 34 of American patent n ° 20 3,547,620 and example 36 of American patent n ° 3,442,945).

C. N- (isobutoxymethyl) -2 ', 6'-dimethyl-2-chloroaceta-nilide; common name "delachlor".

(example 31 of the American patent n ° 3,442,945 and 25 example 24 of the American patent n ° 3,547,620).

D. N- (allyloxymethyl) -21,6'-dimethyl-2-chloroacetani-. lide (example 47 of American patent n ° 3,547,620).

E. N- (methoxymethyl) -2 ', 6'-diethyl-1-2-chloroacetanili- "from (Example 5 of US Pat. Nos. 3,547,620 and No. 3,442,945); common name" alachlor ", ingredient active in the commercial herbicide known as LASSO, which is a registered trademark of the company known as Monsanto Company.

P. N- (methoxyethyl) -2 '-methoxy-6' -methyl-2-chloro-35 acetanilide (compound n ° 6 of Belgian patent n *

JlO.763; also indicated in the published German patent application No. 2,402,983).

17.

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

H. N- (1-methoxyprop-2-yl) -2'-methoxy-61-methyl-chloroacetanilide (compound no. 9 of Belgian patent no. 810,763).

I. N- (methoxyethyl) -2 '-ethoxy-6'-methyl-2-chloroaceous-tanilide (compound no. 16 of Belgian patent no. 810,763).

10 J. N- (ethoxyethyl) -2'-ethoxy ~ 6'-methyl-2-chloroacetanilide (compound no. 18 of Belgian patent no. 810,763).

K. N- (methoxyethyl) -2'-methoxy-61-isopropyl-2-chloro-acetanilide. (compound n ° 26 of Belgian patent n ° 810,763).

15 L. N- (isopropoxyethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide.

M. N- (1-methoxyprop-2-y1) -2'-ethyl-6'-methyl-2-chlo-roacetanilide. (American patent n ° 3,937,730 and German patent application n ° 2,402,983); name cou-20 rant "metolachlor" active ingredient in the commercial herbicide known as "Dual", a registered trademark of the company called Ciba-Geigy Corporation.

Although Compound C above has a structure less similar to the herbicidal counterparts mentioned in U.S. Patent Nos. 3,442,945 and 3,547,620, due to the fact that it lacks an alkoxy substituent in an ortho position, it is included in the tests here because it exhibited superior properties as a sugar beet herbicide compared to other compounds in U.S. Patent Nos. 3,442,945 and 3,547,620. Likewise, compounds E and M are included in tests here because they are within the scope of the relevant prior art indicated and have obtained commercial status. The F-L compounds are included in the tests here due to a certain structural similarity with respect to certain compounds of the present invention.

18.

In the pre-emergence herbicide tests, the compounds of the present invention were compared with the AM compounds of the prior art in relation to the control of various weeds, with emphasis on the annual narrow-leaved species, which are predominant infestations. in sugar beets. The experimental results are presented below.

In the discussion of the results indicated below, reference is made to the rates of application of sym-10 herbicides bolised by "GR ^ g" and "GRgg"; these rates are given in kilograms per hectare (kg / ha). GR ^ g ^^ init the maximum rate of herbicide required to produce 15% or less damage to the plants to be harvested and GRgg defines the minimum rate required to obtain 85% inhibition of weeds. The GR ^ c- and GRgg rates are used as measures of potential commercial performance, it being understood of course that suitable commercially available herbicides can cause more or less large plant damage within reasonable limits.

Another guide to the effectiveness of a chemical as a selective herbicide is the "selectivity factor" ("F.S.") for a herbicide in given crop plants and in given weeds. The selectivity factor is a measure of the relative safety of the plants to be harvested and of damage to weeds and is expressed as a function of the ratio GR ^ g / GRg ^, i.e. * the rate GR ^ g for the plant to be harvested divided by the rate GR85 for the weed, the two rates being in kg / ha.

In the tables below, when used, the selectivity factors are presented in parentheses after the weed; the symbol "NS" indicates "non-selective"; a dash (-) after the weed indicates marginal or indeterminate selectivity, for example because the actual levels GR ^ g and / or GRgg were higher or lower than the maximum or minimum rates used in the tests indicated.

35

Since tolerance for crops and weed control are linked, a 19.

brief discussion of this relationship as a function of selectivity factors is significant. In general, it is desirable that the safety factors for the plants to be harvested, i.e. the herbicide tolerance values, be high, since higher concentrations of herbicide are frequently desired for some reason or another. for a . other. Conversely, it is desirable that weed control rates be low, that is, that the herbicide has high unit activity, for economic reasons and possibly for 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 which control the greatest number of weeds with the least amount of herbicide and which provide the greatest degree of safety for the plants to be harvested, i.e. tolerance plants to harvest. Consequently, the 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 the tables below, unless otherwise indicated, the results have been averaged for the compounds which had been tested in several trials at common application rates in the range of 0.14 to 2.24 kg / ha. Otherwise, 30 'the various tables include data from single experimental trials for application rates falling to 0.07 kg / ha or rising to 4.48 kg / ha.

In a first series of tests, the results of pre-emergent herbicidal activity are presented in Table IV, by comparing the relative efficacy of representative compounds of the present invention with compounds of interest from the prior art as dry herbicides \ 20.

lectures against specific weeds commonly associated with sugar beets. The weeds used in the tests here have the following abbreviations in the tables: wild oats (WO), backyard grass (BYG), 5 large wild grass (LCG), black grass (BG) and yellow fox tail ( YFT).

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Referring to the results in Table IV, it will be seen that, with respect to safety for the plants to be harvested (as indicated by the rate GR ^ 5 for sugar beets), the compounds of the present invention present 5 were a remarkable superiority over the compounds of the prior art. More particularly, compared. to the compounds of the prior art, the most closely related from a structural point of view, that is to say the compounds A and B having the configuration of N-alkoxymethyl-2'-10 alkoxy-6'-alkyl-2- haloacetanilide, the compounds of the present invention in the test were 5.8 to more than 8.0 times safer on sugar beets than compound B and about 2.8 to more than 4.0 times safer than compound A. Even more remarkably, the compounds of the present invention were 22 to more than 32 times safer on sugar beets than the homologous compounds of the prior art P, G and L, each of which caused more than 15 % damage to sugar beets at a very low rate of less than 0.07 kg / ha.

Although not a homologue of the compounds of the present invention, it is known that Compound C has superior properties as a herbicide for sugar beets over other compounds described in the US Patents No. 3,442,945 and No. 3,547,620 mentioned above, which also describe Compounds A and B. Similarly, although Compound N is not a homolog of the compounds of the present invention, it is included in the field of published German patent application No. 2,402,983 which also describes the compounds F and G and generally comprises the compound L; Compound M is the active ingredient in a commercial herbicide, as indicated above. In

referring to the results of the GR rates, in Table IV

1b for compounds C and M, it will be noted that these compounds had a higher safety factor than the other compounds of the prior art. However, for compound C, the safety was only about 1/3 to half that of the compounds of the present invention and, for corn 23.

asked M, the safety was only about half to two thirds of that of the compounds of the present invention.

Concomitantly with the indicated high degree of safety for harvesting plants, the compounds of the present invention exhibited unitary activities (i.e. phytotoxicity per unit of herbicide) against experienced weeds (such as indicated by the levels GRg ^) more or less comparable to the compounds of the prior art. The combination of the high safety factor 10 for crop plants and the high unitary activity against weeds provided remarkably higher selectivity factors for the compounds of the present invention than they are for the compounds of the present invention. prior art, with the sole exception of the compound of Example 4 against black grass.

It is particularly noted in Table IV, comparing the selectivity factors of the compounds of the prior art with those of the compound of Example 1 against the respective weeds in sugar beets, that the compound of Example 1 was more selective than the compounds of the prior art, according to factors of approximately 2.4 to more than 4.7 times against wild oats, from 2.1 to more than 14.6 times against backyard grass and the tail of yellow fox and about 1.8 to more than 14.6 times 25 against wild grass and black grass.

Additional tests with selected compounds of this insert have shown control of backyard grass, wild grass, black grass and yellow fox tail for such low application rates. -30 wheats and even less than 0.07 kg / ha. Thus, the compound of Example 1 showed control of each of the preceding weeds at the rate of 0.07 kg / ha or less; the compound of Example 4 showed the control of backyard grass, wild grass and yellow fox tail 35 to less than 0.07 kg / ha, and the compound of Example 3 presented the control of backyard grass and wild grass for 0.07 kg / ha or less.

"24.

In other comparative tests, the pre-emergence herbicidal activities and the selectivity factors of the prior art compounds, c, E, H and M were determined and compared with those of the compounds of Examples 1-8; the results from these tests are presented in Table 5.

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26.

Referring to the results in Table V, it is noted that each compound of the present invention had a significantly higher safety factor, in sugar beets, than those of all compounds of the prior art. Particular attention is drawn to the safety factors of the compounds of Examples 1, 3 and 6-8 which are from 2.2 to more than 16 times greater than those of the compounds of the prior art. In addition, in addition to having superior safety factors, the compounds of the present invention exhibited selectivity factors uniformly and remarkably superior to the compounds of the prior art, except in isolated cases. Thus, the selectivity factors of compound C were marginally greater than that of Example 7 against wild oats, somewhat greater than that of the compound of Example 4 and equivalent to that of Example 6 in grass black. It will be noted that the prior art compounds E, H and M did not show selectivity for the plants to be harvested against wild oats and black grass and that the selectivity of compounds E and H against the remaining weeds was questionable or at best marginal; in any case, the low safety factors of these compounds make them unsuitable as herbicides for sugar beets.

Since the pre-emergence herbicidal results presented in Tables IV and V were obtained according to e- identical routine procedures, a comparison of the herbicidal efficacy of the compounds of the present invention in Table IV can also be performed, compared to that for the compounds of the prior art in Table V, not indicated in Table IV and vice-ver sa. Here again, it is clearly demonstrated that each of the compounds of the present invention was remarkably superior to all of the most interesting compounds of the prior art from the point of view of safety for the plants to be harvested, without exception, and control selective for weeds, as highlighted by 27.

safety factors, again, with exceptions in isolated cases. Thus, the selectivity factor of a particular compound of the prior art against a certain particular weed may be higher than that of a particular compound of the present invention but, in each case, the low safety factor for beet - • ves à sucre makes the prior art compound unsuitable as a herbicide for sugar beets. For example, the selectivity factor (2.0) of compound (B) 10 (Table IV) against wild oats in sugar beets is higher than that for the compounds of Examples „7 and 8 (respectively 1.0 and 1.3, as shown in Table V). However, the safety factors for the two compounds of the present invention are 8 times greater than for the compound B in sugar beets and the selectivity factors for the compounds of the present invention are at least 4 times those of compound B against backyard grass, wild grass and yellow fox tail and equivalent to that of compound B against black her-20 be.

In yet another comparative test of herbicidal efficacy, the compound of Example 1 and compounds I and J were tested against wild oats, backyard grass, large wild grass, black grass and the fox tail 25 yellow. The results of this test (representing the average of two tests carried out in duplicate) are presented in Table VI; observations were made approximately 18 days after treatment; the selectivity factors are presented in parentheses after the GRg levels. for each weed 30.

TABLE VI

28.

GR I rate GRßl- rate (kg / ha) ______ (kg / ha) ΰ__

Bettera-

5 Coxnpo- ves â WO BYG LCG BG YFT

dried sugar

Ex. 1 <1.12 0.35 <0714 <Ô7Ï4 <0.14 <0.14 (> 3.2) (> 8.0) 08.0) 08.0) 08.0) I <0, 28 ~ 0.99 <0.14 <0.14 0.21 <0.14 (NS) 02.0) 02.0) 01.3) 02.0) 10 J <0.21 0.28 <0 , 14 <0.14 0.21 <0.14 _ (NS) _I 01.5) 1 01.5) (NS) 01.5)%

The remarkable superiority of the compound of Example 1 compared to compounds I and J is evident from the point of view of the safety factor for the plants to be harvested and of the selectivity against each weed in the test; Compound 15 J was non-selective against wild oats and black grass and Compound I was non-selective against wild oats and tightly selective against black grass in sugar beets.

In a test, the compound of Example 1 and components I and J were further tested against fluffy bromine (DB), red-rooted anserine (RRP) and annual perennial tares (AR) in sugar beets for application rates in the range of 0.07 to 1.12 kg / ha; observations were made 18 days after treatment; The results of this test are presented in Table VII; the selectivity factors are noted in parentheses under each weed.

TABLE VII

| GR.Z rate GR rate ~ 30 (kg / ha) 15 ___ (kg / ha) 85_

Compound Beets DB RRP AR

___5 sugar______

Ex. 1> 1.12 0.07> 1.12 0.09 (> 16.0) (-) (> 12.0) I 0.07 <0.14 0.07 0.28 35 (NS) (1.0) (NS) J <0.07 <0.09 <0.07 <0.07 __ [____ (NS) __ (-) _ (-)

The experimental results show that the compounds of 29.

Prior Art 1 and J caused damage to sugar beets at levels as low as 0.07 kg / ha or less, and that Compound I was non-selective against downy bromine and annual perennial tares, 5 then that compound J was non-selective against fluffy bromine and had marginal or indefinite levels. below 0.07 kg / ha. In contrast, the compound of Example 1 was safe on sugar beets at the rate of 1.12 kg / ha (maximum experimental rate), while selectively controlling downy bromine and annual perennial tares with selectivity factors of approximately 16 and 12 respectively, although control of red root anserine is marginal or indeterminate above 1.12 kg / ha.

Another test was conducted in the greenhouse to compare the compounds of the present invention of Examples 2 and 5 with compounds K and D, respectively, i.e. the most intimately related compounds in the art anterior. Example 2 and compound K are characterized by the fact that they have an isopropyl radical in an ortho position, an alkoxy radical in the other ortho position and an alkoxyalkyl radical on the anilide nitrogen atom. Compound D and the compound of Example 5 are characterized in that they have alkenyloxymethyl radicals attached to the nitrogen atom and a methyl radical in a gold-25 th position. Herbicides have been applied to plants at rates in the range of 0.07 to 1.12 kg / ha; observations were made 19 days after treatment; the results are presented in table VIII.

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VIXI TABLE

30.

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(kg / haL - ^ _ _ (kg / ha) 0 _;

Bette-Γ * "^ 5 Compo- MO BYG LCG BG YÏT j r‘ ^ __ cre_______________

Ex. 2> 1.12 0.14 <0.07 <0.07 0.24 <0.07 08.0) 016.0) 016.0) 04.7) 016.0) K 0.19 0 , 07 <0.07 <0.07 0.49 <0.07 (2.7) (2.7) (2.7) (NS) (2.7) 10 Ex. 5 1.12 0.14 <0.07 <0.07 0.78 0.09 (8.0) (> 16.0 (> 16.0) (1.4) (11.1) D 0.19 0.19 <0, 07 <0.07 0.56 <0.07 __ (1.0) 02.7) (> 2.7) (NS) 1 (> 2.7)

Referring to the results in Table νΐΐι, αη clearly sees the remarkable superiority of the compounds of the present invention over compounds D and K. In particular, the compounds of Examples 2 and 5 were safe on sugar beets at the rate 1.12 kg / ha and above, while compounds D and K had GR15 rates only equal to 0.19 kg / ha. In addition, the selectivity factors of the compounds of the present invention exceeded by several times the selectivity factors of the prior art compounds against each weed in the test in sugar beets; the prior art compounds were non-selective against black grass in sugar beets.

Other tests were conducted to demonstrate the superior herbicidal properties of other compounds according to the present invention. In a series of greenhouse tests, the compounds of Examples 9-12 were tested against wild oats, barnyard grass, large wild grass, black grass and yellow fox tail in sugar beets; the results of these tests are presented in Table IX.

TABLE IX

31.

Rate GR.-1 Rate "GRo c (kg / ha) _ (kg / ha) 85 ___

5 Compound jacket “7 W0 I BÏG I LCG BG I

___sugar j____________

Ex. 9a 1.0 0.55 <0.14 <0.14 0.19 <0.14 (1.8) (7.1) · (7.1) (5.2) (7.1) y

Ex. 10> 1.12 0.34 <0.14 <0.14 <0.14 <0.14> 3.3) 08.0) (> 8.0) 08.0) 08.0) 10 Ex. 11C> 1.12 0.19 <0.14 <0.14 <0.14 <0.14 (> 5.9) (> 8.0) (> 8.0) 08.0) 08, 0)

Ex. 12> 1.12 0.84 <0.14 0.14 0.14 0.14 01.3) (> 8.0) (> 8.0) (> 8.0) (> 8.0 ) at. The results represent the average of four tests performed in double b. The results represent the average of two tests performed in double c. The results represent the average of three duplicate tests.

Again, the superior pre-emergence herbicidal activity of the compounds according to the present invention has been demonstrated both on an absolute basis and on a relative basis with respect to the performance of interesting compounds of the prior art, as presented in Tables IV to VIII with regard to the safety factors for the plants to be harvested, the unitary activities, the control of weeds and the factors of selectivity of the crop / weed.

As noted above, the results for the compounds tested in several trials were taken from tests with rates of herbicide application in the range of 0.14 to 1.12 kg / ha. However, additional tests with selected compounds of the present invention have shown safety for sugar beets at rates of at least 4.48 kg / ha and selective control of various weeds for such low rates than 0.07 kg / ha.

For example, the compound of Example 1 showed selective control of the more resistant weeds, 32.

by black grass and downy bromegrass, and less resistant weeds consisting of backyard grass, large wild grass, yellow fox tail and annual perennial tares, at rates as low as 0 .07 kg / ha 5 and less. Similarly, other compounds according to the present invention also controlled one or more of the above less resistant weeds, at the rate of 0.07 kg / ha.

In a field test for weed control performance and relative safety for sugar beets, the compound of Example 1 and the prior art compounds C, E and M were tested against backyard grass and green fox tail under surface application conditions ("SA") and before incorporation conditions ("PPI") at rates between 1.12 and 4.48 kg / ha. The treatments were applied to a loam soil known as Ray with 1.8% organic matter; conditions were relatively dry since only 0.03 cm of rain fell in the first 7-20 days after treatment; the results of the test in the fields are presented in table X.

PAINTINGS

Inhibition percentage 25 Compo- Rate Beets Backyard grass Dry fox tail (kg / green sugar ha) tPPÏ SÄ ”PPI SA TPÏ SÄ“

Ex. 1 1, Ï2 O 0 85 ΊΤ 85 57 2.24 10 3 92 48 92 65 4.48 12 13 98 78 98 85 »9 C 1.12 10 5 78 42 88 77 30 2.24 22 18 87 77 93 87 4.48 57 25 98 90 98 88 E 1.12 30 30 87 68 88 85 2.24 80 63 100 95 100 95 4.48 100 90 100 98 100 97 M 1.12 15 15 95 40 95 62 2.24 30 23 100 78 100 85 35___ 4.48 63 1 45 1 100______93 100 92

Referring to the results in Table x, we note that, among all the compounds tested, only that of the example? 33.

1 was safe (i.e. damage up to 15%) on sugar beets for rates up to at least 4.48 kg / ha (maximum experimental rate), while exhibiting selective control both backyard grass and 5 green fox tail at the rate of 1.12 kg / ha under PPI conditions; none of the prior art compounds selectively controlled either weed, even at the rate of 2.24 kg / ha; Compound M selectively controlled the two weeds under PPI conditions at the rate of 1.12 kg / ha, but this is a narrow margin of tolerance for the plant to be harvested.

The compound of Example 1 was also tested in the fields to determine its selectivity for pre-emergence against fox tail (spp), barnyard grass and white prosomillet in several plants to be harvested; the results (representing three tests carried out in duplicate) are presented in table XI for the application on the surface (SA) and the incorporation into the soil (PPI, that is to say incorporation before the plant) of the herbicide. The seeds were planted in a fine seedling layer of loam soil with intermediate moisture content. The seeds were planted at a depth of 5.08 cm. A first rain fall (0.51 cm) occurred the day after the treatment, the second rain (0.64 cm) 2 days after the treatment; the cumulative rainfall 22 days after treatment was 4.57 cm. Observations were made 6 weeks after treatment.

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The results in Table XI show that the compound of Example 1 generally behaved equivalently under SA and PPI conditions for rates of up to 4.48 kg / ha (except in tomato, co.ncom- 5 bre and prosomillet at the rate of 4.48 kg / ha PPI and against fox tails and backyard grass at the rate of 0.58 kg / ha). More specifically, under SA conditions, the compound of Example 1 selectively controlled fox tails and backyard grass in all experimental 1q crops, at rates from just over 1.12 kg / ha and prosomillet at the rate of 4.48 kg / ha. Under PPI conditions, backyard grass was selectively controlled at the rate of 1.12 kg / ha and fox tails between 1.12 and 2.24 kg / ha with safety for the 15 plants to be harvested up to '' at 4.48 kg / ha for all plants to be harvested, except tomatoes, cucumbers and white beans.

A distinct advantage of a herbicide is its ability to work in a large number of soil types. In sequence, data are presented in Table XII showing the comparative herbicidal effect of the compound of Example 1 and compounds C and M on various annual grasses in sugar beets in a large number of soil types , with various clay and organic content. In these 25 tests, the pots were filled with silty soil known as Ray, made compact up to 0.95 cm from the surface of the pot, then sown with sugar beets, wild oats, backyard grass, large wild grass, black grass and yellow fox tail. The seeds were covered, respectively, with 0.127 cm of Ray loam potting soil, Florida manure, Florida sand, Wabash potting clay potting soil, Drummer potting clay potting soil or Sarpy potting clay potting soil. Each herbicide was applied with a belt sprayer at the rate of 187 l / ha at 2.11 kg / cm, as a surface application. Each pot received 0.64 cm of top irrigation before 36.

to be placed in greenhouse benches for subsequent irrigation from below. Observations were made 15 days after treatment. The results of the soil tests, representing the average of 2 tests carried out in duplicate, are presented in Table XII; the selectivity factors are presented in brackets after the GRg5 rates for weeds. The composition of soil type was as follows: 2q ~ Percent

Soil type Material Clay Limon Sand pH

__organic________

Silty loam known as Ray 1.2 6.4 74.8 18.8 6.5

Manure 5 Florida 22.1 NAa NAa NAa 5.2

Sand of

Florida (Leon) 2.3 1.8 NA & NAa 6.1

Soily potting soil

Drummer 3.6 12.4 52.8 34.8 7.0 2q Clay called

Wabash_ 2.7__ 44.4 34.8 20.8 6.2 a. Not available. 1 37.

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39.

Referring to the results in Table XII, it will be seen that the compound of Example 1 exhibited remarkably superior safety factors for sugar beets and selectivity factors greater than the C and M compounds against each weed ( with two minor exceptions) in three of the five soils, that is, in the so-called Ray loam, in Florida sand and in Wabash clay. More particularly, the compound of Example 1 was the only compound to selectively control wild oats in the silty soil called Ray and clay called Wabash, backyard grass in Florida sand and grass. black in Wabash clay. Results were rather indeterminate in Florida manure (trash) (22.1% organic matter) at the experimental rate, but they indicate that soils with high organic matter content tend to decrease the activity of each of the experimental compounds . The compound of Example 1 did not perform as well in Drummer loam soil as the compounds of the prior art but did exhibit superior overall activity in a range of soil types.

Laboratory tests were conducted to determine the relative resistance of the herbicides according to the compounds of the present invention and the prior art compounds to leaching into the soil and the resulting herbicidal efficacy. In these tests, the compound of Example 1 and compounds C and M were formulated in acetone and then sprayed at different concentrations on a weighed amount of silty loam known as Ray contained in pots having filter paper covering holes of 30 drainage in the bottoms of the pots. The pots containing the treated soil were subjected to leaching by placing them on a rotary table which rotated under two nozzle tips of a water container calibrated to provide 2.5 cm of water per hour simulating a rain fall. The leaching rates were adjusted by varying the time on the rotary table. Water was supplied to the soil in pots and allowed to percolate through the filter paper and the drainage holes.

B

41.

TABLE XIII (Continued) 0.14 0 10 50 95 95 40: 95 1.27, 0 30 95! 85 40 85 2.54 0 30 85 60 20 85 5.08 O 30 65 40 20 75 5 10.16 O 30 0 30 0 40 M 2.24 0 40 85 100 100 95 100 1.27 30 95 100 100 85 100 2.54 20 85 100 100 60 100 5.08 10 30 95 85 30 95 10.16 10 30 60 50 15 50 0.56 O 15 85 100 100 95 100 10 1.27 15 40 100 100 65 100 2.54 0 50 95 95 30 95 5.08 O 20 75 85 20 75 10.16 0 0 30 40 O 20 0.14 OO 85 95 95 75 100 1.27 0 50 95 85 60 95 2.54 0 40 75 50 30 95 15 5.08 O 0 60 30 20 60

10.16 0 0 0 0 0 O

Referring to the results in Table XIII, it will be seen that the compound of Example 1 was safe on sugar beets up to at least 2.24 kg / ha and selectively controlled all weeds in the test under a simulated rainfall of 10.16 cm, except wild oats which was controlled until 7.62 cm of rain. For 2.24 kg / ha, compounds C and M were harmful to sugar beets until diluted with 5.08 cm of rain, and, under these conditions, neither another of the compounds selectively controlled wild oats, nor did compound M control the black grass. For the application rate. tion of the lowest herbicide (0.14 kg / ha), the compound of Example 1 selectively controlled all the weeds in the test under a rain fall of up to 1.27 cm, and the backyard grass, wild grass and yellow fox tail under a 5.08 cm rain shower.

In contrast to 0.14 kg / ha, neither Compound C nor Compound M selectively controlled black grass, nor did Compound C control wild oats under any rainfall condition and two compounds had lost selectivity against all weeds 42.

experimental bes in sugar beet under a 5.08 cm rainfall. It is thus clearly shown that the compound of the present invention was much more resistant to leaching into the soil, under various conditions of rain, than either of the compounds of the prior art, thereby providing a more reliable and longer lasting herbicidal activity.

Finally, to further demonstrate the non-obviousness and unexpectedly superior properties of the compounds of the present invention, additional herbicide pre-emergence results for other compounds of similar structure, including homologues of the compounds of the present invention , are presented in Table XIV. The N-T compounds in Table XIV are identified as follows: N. N- (isopropoxymethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide.

O. N- (isobutoxymethyl) -2'-ethoxy-2-chloroacetanili-de.

P. N- (isobutoxymethyl) t2'-methoxy-2-chloroacetanilide.

Q. N- (isobutoxymethyl) -2 '-methoxy-6 * -methyl-2-chlo-roacetanilide.

R. N- (ethoxymethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide.

S. N- (1-methylpropoxymethyl) -2'-methoxy-6'-methyl-, 2-chloroacetanilide.

T. N- (ethoxymethyl) -2'-isopropoxy-6'-methyl-2-chlo-roacetanilide.

43.

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It is indicated that the NT compounds, like the compounds of the present invention in Examples 1-12, are included in the genetic description of the previously mentioned U.S. Patent Nos. 3,442,945 and 3,547,620, but they do not exist. are not specifically described. As a result, it would be expected that the species of compounds included in the genera of compounds described in these US Patents 3,442,945 and 3,547,620 would have generally comparable herbicidal properties. However, the completely unexpected and remarkable properties of the species of compounds of the present invention, vis-à-vis homologous and intimately related species, are further demonstrated by referring to the results for N-T compounds in Table XIV. Again, it will be noted that the NT compounds (like other related prior art compounds, as shown particularly in Tables IV-VIII) had very low safety factors in sugar beets. , as evidenced by the low application rates GR15 ”In addition, none of the species in Table 20 XIV showed selective control of wild oats in sugar beets. It is also interesting to note that compound P was non-selective against any of the weeds in the test and, similarly, that compounds N, o, Q and R were completely non-selective and / or selective for marginally against all weeds in the test. Among the compounds in Table XIV, only compounds S and T exhibited selective control of backyard grass, wild grass, black grass and yellow fox tail.

'30 However, it is again indicated that the unacceptably low tolerance of sugar beets to compounds S and T, coupled with non-selectivity against wild oats and narrow selectivity against other weeds in the test make these compounds completely unacceptable as herbicides for sugar beets. Furthermore, it is noted (with reference to Tables IV-VIII) that the safety factors in sugar beets and the selectivity factors for the compounds of the present invention in 45.

the above weeds are considerably superior to those of compounds S and T.

Consequently, it will be appreciated from the foregoing detailed description that the compounds according to the present invention have demonstrated unexpectedly and remarkably superior herbicidal properties, both absolutely and relatively to the most common compounds. more interesting from a structural point of view, compared to other homologs and related analogs, including commercial 2-haloacetanilides, of the prior art. More particularly, the compounds of the present invention have demonstrated remarkable safety for. plants to be harvested from sugar beets and remarkable selectivity factors particularly in relation to hard-to-destroy weed species such as wild oats, black grass and downy bromegrass and other weeds causing problems, such as yellow fox tail, backyard grass, wild grass, annual perennial tares, etc., as presented in Tables II-X.

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, 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, a wetting agent, a dispersing agent, an emulsifying agent or any 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 46.

teisio-active agents in quantities sufficient to make a given composition easily dispersible in water or in oil. The incorporation of a surfactant into the compositions greatly enhances their effectiveness.

By the term "surfactant" it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included. Anionic, cationic and nonionic agents can be used with equal ease.

Preferred wetting agents are alkylbenzenes and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, sodium sulfosuccinate esters, sulfated and sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, polyoxyethylene derivatives of alkylphenols (particularly isooc-tylphenol and nonylphenol) and polyoxyethylene derivatives of esters of higher monocarboxylic fatty acids or of hexitol anhydrides (for example sorbitan). The preferred dispersion products are methylcellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkylnaphthalenesulfonates, sodium naphthalenesulfonate and polymethylene bisnaphthalenesulfonate.

Wettable powders are water dispersible compositions containing one or more active ingredients, an inert solid extender and one or more wetting or dispersing agents. Inert solid extension products are ordinarily of mineral origin, such as natural clays, diatomaceous earth, and synthetic minerals from silica and the like. Examples of these extension products include kaolini-tes, so-called attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the present invention ordinarily contain about 0.5 to 60 parts (preferably 5-20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1-15 parts) agent 47.

wetting, about 0.25 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 parts being by weight compared to the total com-5. When required, about 0.1 to 2.0 parts of inert solid extender can be replaced with a corrosion inhibitor or an anti-foaming agent or both.

Other formulations include dust concentrates containing 0.1 to 60% by weight of 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 homogenizing to give a stable emulsion 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 suspensions, a water immiscible herbicide is encapsulated to form a microencapsulated phase dispersed in an aqueous phase. In an exemplary embodiment, the tiny capsules are formed by bringing together an aqueous phase containing an emulsifier based on ligninesulfonate and a chemical immiscible with water, and polyphenylisocyanate of polymethylene, 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 pro- 48 particles.

chemical mix immiscible with water, thus forming microcapsules. Generally, the concentration of the microencapsulated material will range from about 480 to 700 g / l of the total composition, preferably 480 to 600 g / l.

Concentrates are ordinarily solutions of active ingredient in water-immiscible or partially water-immiscible solvents with a surfactant. Suitable solvents for the active ingredient of the present invention include dimethylformamide, di-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 in a solvent and then diluting, for example with kerosene, to the spray concentration.

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

The granules are physically stable particulate compositions comprising the active ingredient adhering to or distributed through a base matrix 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 indicated above, may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of well-functioning classes of particulate mineral extension products. Preferred extension or dilution products are absorbent porous pre-formed particles, such as pre-formed and sieved particulate attapulgite or thermally expanded particulate vermiculite and finely divided clays such as so-called kaolin clays. hydrated attapulgite or bentonite clays.

49.

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 3 to about 20 parts, by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surfactant per 100 parts by weight of particulate clay.

The compositions of the present invention may also contain other additives, for example fertilizers, other herbicides, other pesticides, safety products 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, nitrites, biphenyl ethers and the like, such as: Nitrogen / sulfur heterocyclic derivatives 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4, 6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 25 3-isopropyl-1H-2,1,3-benzothiadiazin 2,2-dioxide -4- (3H) -one 3-amino-1,2,4-triazole the salt of 6,7-dihydrodipyrido (1,2-a: 2 ', 1'-c) -pyrazidinium on 5 -bromo-3-isopropyl-6-methyluracil the 1,1'-dimethyl-4,4'-bipyridinium salt

Urea N '- (4-chlorophenoxy) phenyl-N, N-dimethylurea N, N-dimethyl-N' - (3-chloro-4-methylphenyl) urea 35 3- (3,4-dichlorophenyl) -1 , 1-dimethylurea 1,3-dimethyl-3- (2-benzothiazolyl) urea 3- (p-chlorophenyl) -1,1-dimethylurea 50.

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

Carbamates / thiolcarbamates 2-chloroallyl diethyldithiocarbamate Ν, Ν-diethylthiolcarbamate S- (4-chlorobenzyl) 5 isopropyl N- (3-chlorophenyl) carbamate N, Ν-diisopropylthiolcarbamate S-2,3-dichloro - allyl ethyl N, N-dipropylthiolcarbamate S-propyl dipropylthiolcarbamate

Acetamids / acetanilides / anilines / amides la 2 ~ chloro-N, N-diallylacetamide, N, N-dimethyl-2,2, diphenylacetamide la N- (2,4-dimethyl-5 - [[(trifluoromethyl) sulfonyl] amino ] phenyl) acetamide 15 N-isopropyl-2-chloroacetanilide 2 *, 6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl-6'-ethyl-N- (2-methoxyprop-2-yl ) -2-chloroacetanilide 1'a, a, a-trifluoro-2,6-dinitro-N, N-dipropyl ~ p-toluidi- ne la N- (1,1-dimethylpropynyl) -3 / 5-dichlorobenzamide Acids / esters / alcohols 2,2-dichloropropionic acid 2-methyl-4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetigue acid. methyl * 2- [4- (2,4-dichlorophenoxy) phenoxy] propionate 3-amino-2,5-dichlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid

3Q

2,3,6-trichlorophenylacetic acid Nl-naphthylphthalamic acid sodium 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitro-benzoate 4 f6-dinitro-o-sec-butylphenol N- (phosphonomethyl) glycine, its monoalkyl salts (as amines, its alkali metal salts and combinations thereof.

51.

Ethers 2,4-dichlorophenyl-4-nitrophenyl ether 2-chloro-a, a, a-trifluoro-p-tolyl-3-etho-xy-4-nitrodiphenyl ether 5 Various products 2,6 -dichlorobenzonitrile methanearsonate sodium monosodium acid methanearsonate disodium

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

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

I. Emulsifiable concentrates 20% by weight A. Compound of Example 1 50.0 Mixture of calcium dodecylbenzenesulfonate / polyoxyethylene ethers (for example product known under the trademark Atlox 25 3437F and Atlox 3438F) 5.0

Monochlorobenzene 45.0 100.00 B. Compound of Example 2 85.0 Cal 3-dium dodecylsulfonate / alkylarylpolyether alcohol 4.0 mixture

Solvent formed of aromatic hydrocarbons in C „11.0 J ---- 100.00 C. Compound of example n ° 11 5.0 35 Mixture of calcium dodecylbenzenesulfonate / polyoxyethylene ethers (for example product known as Atlox 3437F) 1.0 ”52.

Xylene 94.0 100.00 II. Liquid concentrates% by weight 5 A. Compound of Example 1 10.0

Xylene 9q, q 100.00 B. Compound of Example 2 85.0

Dimethyl sulfoxide 15.0 10 100.00 C. Compound of example n ° 11 50.0 N-methylpyrrolidone 50.0 100.00 D. Compound of example n ° 10 5.0 15 Castor oil ethoxylated 20, 0

Product called Rhodamine B 0.5

Dimethylformamide 74.5 100.00 III. Emulsions 20% by weight A. Compound of example ii ° 3 40.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol (for example product known under the trademark Tergitol 25 XH) 4.0

Water 56.0 100.00 B. Compound of Example 4 5.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol 3.5

Water 91.5 100.00 IV. Wettable powders% by weight 35 A. Compound of Example 5 25.0

Sodium lignosulfonate 3.0 N sodium methyl-N-oleyl taurate 1.0 53.

Amorphous silica (synthetic) 71.00 100.00 B. Compound of Example 6 80.0

Sodium dioctylsulfosuccinate 1.25 5 Calcium lignosulfonate 2.75

Amorphous silica (synthetic) 16.00 100.00 C. Compound of Example 7 10.0

Sodium lignosulfonate 3f0 1 10 Sodium N-methyl-N-oleyl-taurate 1.0

Clay called kaolinite 86.0 100.00 V. Dust% by weight 15 A, Compound of example n ° 1 2.0

Attapulgite 98.0 100.00 B. Composed of Example 8 60.0

Montmorillonite 40.0 20 100.00 C. Composed of Example 9 30.0

Bentonite 7q, q 100.00 D. Compound of Example No. 12 1.0 25 Diatomaceous earth 99.0, 100.00 VI. Granules% by weight A. Compound of example n ° 1 15.0 30 Granular attapulgite (passing through a sieve with mesh opening between 0.841 mm and 0.420 mm, i.e. 20-40 mesh) 85.0 100.00 B. Composed of example n ° 11 30.0 35 Diatomaceous earth (going to ta set with mesh opening between 0.841 mm and 0.420 mm) 70.0 i nn on 54.

C. Compound of example n ° 10 Bentonite (passing through a sieve with a mesh opening of between 0.841 mm and 0.420 mm) 99.5 - 5 100.00 D. Compound of example n ° 3 5 '°

Pyrophyllite (passing through a sieve with a mesh opening of between 0.841 mm and 0.4 20 mm) 95, Q— 10 100.00 VII. .Microcapsules% by weight A. Compound of example n ° 1 encapsulated in a polyurethane envelope wall 49.2

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

Water 49.9_ 20 100.00 B. Compound of example n ° 12 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 10 10 encapsulated in a polyurea shell wall 80.0

Lignosulfate magnesium salt (product known under the trademark Treax LTM) 2.0 Water 18.0 35 100.00

When operating in accordance with the present invention, effective amounts of the acetanilides of the present invention 55.

tion are applied to the soil containing the plants, or are incorporated into aquatic environments in any suitable manner. The application of liquid compositions and particulate solid compositions to the soil can be carried out by conventional methods, for example mechanical dust-forming devices, telescopic and hand-held spraying devices and spraying dust-forming devices. The compositions can also be applied from aircraft in the form of dust or spray due 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 where control of the aquatic plants is desired.

The 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 preemergence application to plants or soil, a dose of 0.02 to about 11.2 kg / ha, preferably about 0.04 to about 5.60 kg / ha, or suitably Typically 1.12 to 5.6 kg / ha of acetanidide is used. Lower or higher rates may be required in some cases. A person skilled in the art can readily determine from this description, including the above examples, the optimum rate to apply in any particular case.

The term "soil" is used in its broadest sense to include all conventional "soils", such as challenge-35 or in the New International Dictionary of Webster, 2nd edition, unabridged (1961). Thus, the term refers to any substance or environment in which vegetation can 56.

take root and grow and includes not only soil, but also compost, fertilizer, manure (garbage), humus, sand and the like, adapted to maintain plant growth.

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

The present invention is not limited to the examples. 10 of embodiment which have just been described, it is on the contrary susceptible of variants and modifications v which will appear to those skilled in the art.

Claims (20)

1. Compounds, characterized on what they have the formula; 5 \ 't C1C112C ^ Cll ^ üR "N ^ Λ, H * 2 — TbT ~ l 1 v io * where R is ethyl, n-propyl, isopropyl, isobutyl, allyl or butenyl; R ^ is methyl , n-propyl, isopropyl, n-butyl, isobutyl or isoamyl and R2 is methyl, ethyl or isopropyl; only that: when K2 is isopropyl group, R is ethyl group and either n-but group. ; When R., is the ethyl group, R is the ethyl, n-propyl or allyl group and either the n-butyl or isobutyl group; when R is the n-propyl group Ri or the n-butyl or isobutyl group when R is the isopropyl group R ^ is the isobui group 25 when R is the isobutyl group, R1 is the n-propyl, isopropyl, isobutyl or isoamyl group, and "when R is the butenyl group, R is the group * X methyl. 2. Compounds according to claim 1, characterized in that R is a C 2-4 alkyl radical or the allyl radical and is an or alkyl radical. 3. Compounds according to claim 2, characterized in that r ^ is an Isobutyl radical. 4. Compound according to claim 3, characterized in 1% I "that it is formed by N" (n-propoxymethyl) -2'-isobutoxy-61-methyl "2 ~ chloroacetanilide. 5. Compound according to claim 3, characterized * '> b. in that it would have formed pure N ~ (isubui "ixymeLhy 1) -2 1-isobuto-xy-6'-methy1-2-chloroacét uni I wiu. ü - Compound according to reseller ion j, characterized in that it is thundered by N- (j iPprcpoxyméthy1) -2'-isobutoxy-5 6 '-methyl-lî-ch ioroacétani 1 ide. 7. Compound according to claim 3, characterized in that it is formed by bl ~ (ethoxymet hyl) -2 '-lsobutoxy-6' -ethyl-2-chloroaoetanilide. 8. Compound according to revendtcalion 3, characterized in that it is formed by N- (allyloxymethyl) -2'-isobutoxy- 6'-éthy1-2-ehloroacétanilide. 9. Compound according to claim 2, characterized in that it is formed by N- (ethoxymethyl) -2 '-n-butoxy-6' -is opr opy 1 - 2 - <? H lor oac é t an i 1 ide. 15 10 Compound according to claim 2, characterized in that it is formed by N- (isobuLoxymethyl) -2'-iscpropo-xy-b '-nethyl -2-ch 1 oroaceousLanilide, 11. Compound according to claim 2, characterized in that it is formed by N- (isobutoxymethyl) -2'-n-propo xy-6‘-méthy1-2-chloroacétanilide. 12. Compound according to claim 2, characterized in that it is formed by N- (n-propoxymethyl) -2'-n-butoxy-6'-éthy1-2-chloroacétanilide. 13. Compound according to claim 2, characterized in that it is formed by N- (allyloxymethyl) -2'-n-butoxy- 6'-ethyl-2-chloroacetanilide. * 14. 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: 30 O ClCH-jCv. ^ CH-OR 2. jsj ^ i R2 ----- OBj 59. where R, R ^ and R2 are as defined in claim 1. 15. Composition according to claim 14, characterized in that the provisions of any one of claims 2 to 13 are applied. 16. Method for combating undesirable plants associated with plants to be harvested, characterized in that it consists in applying to the place where the plants are found a quantity, herbicide effective, of a compound having the formula: 0 ClCH2S \ N ^ CH2OR where R, R ^ and R2 are as defined in claim 1. 20 17 - Process according to claim 16, characterized in that the plants to be harvested are sugar beets, soybeans, cotton , peanuts, white beans, rapeseed, cucumbers or tomatoes. 18. The method of claim 17, characterized in that the plants to be harvested are sugar beets. 19. The method of claim 18, characterized * Λ in that one applies the provisions of any "* [* of claims 2 to 13. 20. Method for combating undesirable plants associated with sugar beets, characterized in that it applies to the place where these plants are found, a quantity, herbicide effective, of N- (n-pro- poxymethyl) -21-isobutoxy-6'-methyl-2-chloroacetanilide. 21. Process for combating undesirable plants associated with sugar beets, characterized in that it applies to the place where these plants are found a quantity, herbicide effective, of N- (ethoxymé- 60. " * *. * thyl) -21-isobutoxy-6'- ethyl-2-chloroacetanilide. 22. Method according to any one of claims 16 to 21, characterized in that the undesirable plants are annual weeds, with narrow leaves ~ 5 tes. i Ψ A i. i