FI73972C - 2-haloacetanilide compounds and herbicide compositions containing the same - Google Patents

Description

1,73972 2-Haloacetanilide Compounds and Herbicidal Compositions Containing Them

The invention relates to 2-haloacetanilide compounds and herbicidal compositions containing them.

Numerous 2-haloacetanilides have been described in the art, in which the anilide nitrogen atom and / or the anilide ring may be unsubstituted or substituted by various substituents such as alkyl, alkoxy, alkoxyalkyl, haloalkyl, halogen and the like.

Compared to the compounds of the invention in which the anilide top is substituted by a hydrocarbyloxymethyl radical and in which the trifluoromethyl radical in the second ortho position and the methyl radical or, in special cases, the ethyl radical or hydrogen in the second ortho position, the closest known technique is the closest of the compounds disclosed in the patent are the generally described N-alkoxyethyl or alkyl-substituted alkoxyethyl-2-chloroacetanilides, the anilide ring 20 of which may be substituted at the ortho and meta positions by one or more radicals selected from halogen, alkyl, alkoxy and trifluoro ^). In particular, Table II of the patent comprises compounds substituted with a -CF 4 radical in the second ortho position without any substituent in the second ortho position (Compounds Nos. 37-48), and compounds having a -CF 4 substituent. substitution at the meta position with the second ortho position being unsubstituted and the second ortho position being substituted with a methoxy radical (Compounds Nos. 22-25) or a chlorine atom (co-30 Nos. 33-36). However, BE Patent 810,763 does not provide any specific description or example of 2-haloacetanilides substituted with a -CF 4 radical at the second ortho position and a methyl or ethyl radical at the second ortho position, as in the present invention.

In addition, the compounds of BE Patent 810,763 are characterized in that the anilide nitrogen is substituted by an alkoxyalkyl group having at least two carbon atoms in the alkylene moiety between the nitrogen atom and the oxygen atom of the alkoxy moiety. In contrast, the compounds according to the invention are characterized in that the anilide nitrogen is substituted by an alkoxymethyl group. The significance of the differences between the compounds of BE Patent 810,763 and the compounds of this invention is evident from the results of the comparative experiments below, which clearly demonstrate superiority of the compounds of the invention in terms of unit activity, selectivity, Tor weed spectrum and yield.

Less relevant prior art is represented by U.S. Patents 3,966,811 and 4,152,137, DE Patent Application 2,402,983, GB Patent Application 2,013,188 and ZA Patent 15,747/0767. Although these publications generally describe 2-haloacetanilides, which may contain, among other substituents, a -CF 2 substituent on the anilide ring, only some such compounds are specifically described in U.S. Patent 3,966,811 and ZA Patent 74/0767. However, the two patents do not describe ortho-CF 2 -substituted compounds which are further substituted in the second ortho position by a methyl or ethyl radical. The only -CF 2 -substituted compounds blocked in these patents are meta-CF 2 -substituted compounds. In addition, the aforementioned patents BE 810 763, U.S. Pat. No. 3,966,811 and ZA 74/0767 stipulate that there are at least two carbon atoms between the anilide nitrogen and the oxygen of the alkoxy moiety, which is also disclosed in however, describe -CF 3 -30 substituted compounds at all.

Of the above-mentioned relevant publications, only BE Patent 810,763 and ZA Patent 74/0767 disclose some information on herbicidal properties for N-alkoxyalkyl-2-haloacetanilides having a -CF 4 -35 substituent on the anilide ring. However, this information is 3,73972 unclear, vague and incomplete. For example, BE patent 810,763 gives limited values for herbicidal properties for only one -CF 4 -substituted compound, namely compound no. 37 (which is the same compound as in Example 2), i.e. 2-trifluoromethyl-N- (2'-methoxyethyl) -2-chloroacetanilide. Table 3 of said patent shows the compound no. 37 destroy or seriously damage certain unidentified species of "Cupe-rus", Setaria, Digitaria and Echinochloa, while 10 damage to weeds Avena fatua and unidentified Lolium species in certain cereals is minor. Of the six weeds tested, five lack specific identification, making it impossible to assess the herbicidal activity of compound 37.

Similarly, ZA Patent 74/0767 briefly discloses information on herbicidal properties for only one -CF 4 -substituted compound, namely Compound no. 78, i.e. 2,6-dimethyl-3-trifluoromethyl-N- (2'-methoxyethyl) -N-2-chloroacetanilide. The only mention of the compound-20 I do no. 78 herbicidal activity occurs in Example 5, wherein the compound no. 78 is said to very strongly inhibit the growth of four weed species. However, said patent does not disclose any laboratory or field research values related to the compound no. 78 effects on cereals and does not indicate whether this compound selectively controls any weed in any cereal. Therefore, it is impossible to evaluate the effect of the compound. Although the above-mentioned relevant publications show the herbicidal activity of certain compounds against various weeds, they do not disclose any activity values for -CFg-substituted N-alkoxyalkyl compounds which have been shown to additionally and / or simultaneously inhibit or inhibit one or more cereal species. perennial weeds difficult to eradicate, yolk wheat, yellow 4 73972 and purple walnut, and a wide range of annual weeds comprising difficult-to-eradicate annual weeds of the grass-shrub (Sorghum) (Teksa-rin and wild "proso" millet), Red rice and scab (Raoul grass), while also controlling or preventing other harmful perennial and annual weeds, e.g., autumn shrubs. Persicara hydropiper, wild flour clay-10 kaa, pig grass, pound weeds (e.g. giant and yellow), crawling weeds, yard grass, some Ipomea species, Indian mallow, burdock, swamp grass, Sesbania hemp, hemp,

One very useful and useful feature of herbicides is the ability to maintain weed control for a longer period of time, the longer the better, during each harvest season. For many known herbicides, weed control is only sufficient for two or three weeks, or, in some special cases, perhaps 4-5 weeks, 20 before the chemical loses its effective phytotoxic properties. Thus, one disadvantage of the most common herbicides is their relatively short shelf life in soil.

Another disadvantage of some known herbicides, which is somewhat related to the long-term effect in soil under normal weather conditions, is the elimination of continuous weed control in heavy rainfall, which inactivates many herbicides.

An additional disadvantage of many known herbicides is their limited use to non-soil types, i.e.

While some herbicides are effective in growth layers with small amounts of organic matter, they are ineffective in other growth layers rich in organic matter, or vice versa. Therefore, it is preferred that the herbicide be useful in all types of growth layers from the fluffy organic layer to heavy clay and peat.

5,73972

Another disadvantage of many known herbicides is the limitation to any particular effective mode of application, i.e. surface application before sprouting or incorporation into a growth layer, application method before and / or after sprouting. It is highly desirable to be able to apply the herbicide by any method of application, either by surface application or by combining with a growth layer.

Finally, some herbicides still have the disadvantage of having to adopt and maintain special treatments due to their toxic nature. Thus, it is also desirable that the herbicide be safe to handle.

The object of the present invention was to provide a group of herbicidal compounds which do not have the above-mentioned disadvantages and which offer a number of advantages which have hitherto not been achieved with any single group of herbicides.

It is therefore an object of the present invention to provide herbicides which control and / or prevent perennial and annual weeds which are difficult to eradicate, as described above, while guaranteeing various cereals, in particular maize and soybeans, and others such as cotton, peanuts, oilseed rape, bush beans, wheat and / or millet, harvest.

It was a further object of the present invention to provide a herbicidal effect on the growth layer for periods of up to 12 weeks.

Another object of the present invention was to provide herbicides which are resistant to extraction and dilution under the influence of very humid conditions, e.g. heavy rain.

It was also an object of the present invention to provide herbicides which are effective over a wide range of growth layers, e.g. from a light to medium organic growth layer to heavy clay and peat.

6,73972

One advantage of the herbicides according to the invention is that they can be applied using different application methods, i. surface application before sprouting and by combining with the growth layer.

In addition, one of the advantages of the herbicides of this invention is that they are safe and do not require any special treatments.

This invention relates to herbicidally active compounds and herbicidal compositions containing them.

It has surprisingly been found that a selective group of 2-haloacetanilides having a specific hydrocarbyloxymethyl radical attached to the antilide nitrogen atom and substituted by a trifluoromethyl (-CF 4) radical at the second ortho position and having a methyl or ethyl radical or a hydrogen radical in the ortho position, has excellent herbicidal properties compared to known herbicides and homologous compounds described in the above-mentioned relevant publications.

The main feature of the herbicidal compositions according to the invention is their ability to control a wide variety of weeds, including those which can be controlled by common herbicides, and a large number of weeds not affected by known herbicides, while guaranteeing different cereals, especially maize and soybeans. a good harvest of others such as cotton, peanuts, oilseed rape, millet, wheat and folding beans. Said known herbicides are also useful in some cases for controlling certain resistant / weeds of various weeds, but the unique herbicides of the invention have been found to be able to control or strongly inhibit large numbers of resistant perennial and perennial weevils, such as perennial and annual perennial weeds. weeds such as 35 prickly mauve plants, Sesbania hemp, Persicara hydro- 7,73972 piper, wild flour whey, pig grass and annual weeds such as evergreen millet growing from seeds, "shattercane", alexander grass, alexander grass, Texas wool , scab weed (Raoul grass), and 5 other harmful weeds such as autumn weevil, puntar heads, yard grass, creeping weed, etc. Weed reduction has also been achieved in persistent weeds such as Ambrosia-like weeds, Indian mallow , In Ipomea species, burdock, swamp grass, etc.

The 2-naloacetanilides of the invention have the formula 0

CICH ^ C ^ CH0OR

15 2 \ / 2

OF

R 1 -TqY CF 3 U) 20 wherein R is C 1-6 alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and R 1 is hydrogen, methyl or ethyl, provided that when R 1 is hydrogen, then R 1 is hydrogen, methyl or ethyl. is isopropyl, and when R 1 is ethyl, then R is ethyl, n-propyl or isopropyl.

Preferred compounds of this invention are those wherein R 1 in the above formula is methyl or ethyl and R is a C 1-4 alkyl radical. Individual preferred compounds of this invention include: N- (ethoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide.

N- (n-propoxymethyl) -2'-trifluoromethyl-6'-methyl-35-2-chloroacetanilide.

8,73972 N- (isopropoxymethyl) -21-trifluoromethyl-6'-methyl-2-chloroacetanilide.

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

5 N- (ethoxymethyl) -2 · -trifluoromethyl-61-ethyl-2-chloroacetanilide.

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

N- (isopropoxymethyl) -2'-trifluoromethyl-6'-ethyl-10-chloroacetanilide.

The invention also relates to herbicidal compositions which contain as active ingredient one or more 2-haloacetanilide compounds of the formula I.

The novel compounds of this invention can be prepared by N-alkylation of the amine of a suitable secondary 2-haloacetanilide with an alkylating agent under basic conditions, e.g., as described in Example 1. A variation of the N-alkylation process involves the in situ preparation of ethers used as starting materials in the N-alkylation process. it is described in Example 2.

Example 1 This example illustrates the preparation of N- (ethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-clocriastanilide.

2'-Trifluoromethyl-6'-methyl-2-chloroacetanilide, 4.02 g (0.016 mol), chloromethylethyl ether, 3.02 g (0.032 mol) and benzyltriethylammonium bromide, 2.0 g, (phase transfer catalyst) were stirred in 75 ml. methylene chloride in a 500 ml round bottom flask equipped with a mechanical stirrer and thermometer.

Sodium hydroxide (50%), 15 ml, was all added in one portion with vigorous stirring, raising the temperature to 26 ° C. After about five minutes, ice and water were added, the layers were separated and the organic layer was washed with 2.5% sodium chloride, dried, filtered and separated. The dark residue was distilled in a ball tube and 3.4 g of a yellow oil-5 fraction was collected, boiling at 110-115 ° C at 0.1 mm. This fraction was collected in cyclohexane and purified by HPLC using 20% ethyl acetate in cyclohexane. Further distillation of the peak fraction with a ball tube gave 3.2 g (65% yield) of a colorless oil, b.p. 100-110 ° C at 0.1 mmHg; after standing 10, a white solid crystallized, m.p. 41-43 ° C.

Analysis for C 13 H 15 ClF 3 NO 2:

Calculated: C 50.41 H 4.88 N 4.52 Found: C 50.02 H 4.81 N 4.38 Example 2 This example illustrates the use of an improved alternative method for preparing the compounds of this invention. The process of this example is characterized by the in situ formation of the alkylating agent which provides a more efficient, economical and simpler way of working.

A slurry of ethylene glycol monomethyl ether, 7.3 g (0.096 mol) and paraformaldehyde, 1.44 g (0.048 mol) in 100 ml of methylene chloride solvent was cooled in an ice-water bath and 5.9 g (0.048 mol) of acetyl bromide were added. After stirring for about 45 minutes, 4.03 g (0.016 mol) of 21-trifluoromethyl-6'-methyl-2-chloroacetanilide and 2.0 g of benzyltriethylammonium chloride were added. 50 mL of 50% NaOH was added all at once. Gas chromatography showed complete reaction after about five minutes.

Ice and water were added to the mixture to effect phase separation, and the organic phase was then separated, dried, filtered and separated. The residue was vacuum distilled on a short distillation apparatus to give 4.2 g (77% yield) of a clear, colorless oil, b.p. 150-160 ° C at 0.05 mmHg. 35 Analysis for C ^ ^ H ^^ CIF ^ NO ^ (%)

Calculated: C 49.49 H 5.04 N 4.12 Found: C 49.33 H 5.04 N 4.08 10 73972

The product was identified as N- (2-methoxyethoxymethyl) -2'-trifluoromethyl-61-methyl-2-chloroacetanilide.

If the N-alkylation process is allowed to develop too high or too low temperatures, 5 different impurities may develop, e.g., sec-anilide, the corresponding imidate, Of-alkoxyamide, or diketopiperazines. Such impurities are removed by washing the organic layer with dilute aqueous salt or acid solution, e.g. 2-3% NaCl or 5% HCl.

10 Examples 3-13

Following essentially the same procedures, amounts of reactants, and general reaction conditions described in Example 1 or 2, but substituting the appropriate starting sec-anilide and alkylating agent to give the final product, other compounds of the above formula were prepared; these compounds are shown in Table I.

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In the above examples, the secondary anilide starting materials used to prepare the compounds of this invention are conveniently prepared by conventional chloroacetylation of the appropriate primary amine, as exemplified in Example 16 below.

Example 16 This example illustrates the preparation of a secondary anilide starting material used to prepare the species of compound of this example, i.e., the compound of Example 13.

6.0 g (0.03174 mol) of 2-trifluoromethyl-6-ethylaniline were dissolved in 75 ml of toluene and 3.77 g (0.033 mol) of chloroacetyl chloride were carefully added. The resulting slurry was heated to reflux and held for four hours. The mixture was then diluted with an equal volume of hexane and allowed to stand. The product crystallized and the resulting solid was filtered and air dried to give 5.8 g (69% yield); an additional 2.7 g of a white solid was obtained from the filtrate, m.p. 121-124 ° C (closed tube).

Analysis for C 1 H 2 Cl 2 O 2 (%)

Calculated: C 49.73 H 4.17 N 5.27 Found: C 49.36 H 4.09 N 5.33 The product was identified as 2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide.

The primary amines used to prepare the secondary anilides by haloacetylation, as described above, are known in the literature; see. e.g., the aforementioned U.S. Patent No. 3,966,811 and GB Patent Application No. 2,013,188.

As mentioned above, the compounds of this invention have been found to be effective as herbicides, especially as pre-emergence herbicides, although post-emergence activity has also been demonstrated. The pre-sprouting tests referred to herein include both greenhouse and field tests. In greenhouse tests, the herbicide is applied either as a surface application after planting the seeds or growing root sludge or by combining it with a number of growth layers to be applied as a cover layer on top of the test tanks pre-sown in test tanks. In field trials, the herbicide can be applied by combining with a growth layer ("P.P.I.") prior to planting, i.e.

The herbicide is applied to the surface of the growth layer, then combined with mixing means, followed by sowing of cereal seeds, or the herbicide can be applied to the surface ("S.A.", surface application) after the cereal seed has been sown.

10 The surface application ("SA") test method used in a greenhouse is carried out as follows: containers, eg aluminum trays, typically measuring 24.13 cm x 13.34 cm x 6.99 cm or plastic pots 9.53 cm x 9.53 cm x 7.62 cm with counting holes in the bottom are filled to the edge 15 with Ray loamy clay soil soil and then compacted to a level of 1.27 cm from the top of the pots. The pots are then inoculated with the test plant species, covered with a 1.27 cm layer of test soil. The herbicide is then applied to the surface of the growth layer, e.g., with a band spray, 20 to 20 gallons / acre, 30 psi (187 L / ha, 2.11 kg / cm 2). The already soaked pot receives 0.64 cm of water to cover the surface and the pots are then placed in greenhouse benches for subsequent underwater irrigation as needed. As an alternative procedure, top end irrigation can be omitted. Observation of 25 herbicidal effects is made approximately three weeks after treatment.

The herbicide treatment by combination with the growth layer ("S.I.") used in the greenhouse tests is as follows:

Good quality topsoil is placed in aluminum trays 30 and compacted to a depth of 3/8 to 1/2 inch from the top of the tray. A number of seeds or vegetative rootstocks of different plant species are placed on top of the soil. The soil needed to fill the fish after sowing to the top level or adding vegetative root sludge is weighed into the distal 35. The mold and a known amount of the active ingredient applied in a solvent or wettable powder suspension are thoroughly mixed and used to cover the prepared distal 739 72 lots. After the treatments, the troughs are subjected to an initial irrigation of the upper end with water corresponding to 0.54 cm of rain, then watered as an irrigation of the lower end as necessary to provide sufficient moisture for germination and growth. As an alternative to procedure 5, top end irrigation can be omitted. Observations are made about 2-3 weeks after sowing and treatment.

Tables II and III summarize the results of tests performed to determine the herbicidal activity of the compounds of this invention prior to sprouting; in these tests, herbicides were applied to the growth layer by pooling and using lower end irrigation alone. Herbicidal evaluation was performed using a fixed scale based on the percentage of damage to each plant species. Reviews are assigned to 15 as follows:

Control% Rating 0-24 0 25-49 1 50-74 2 20 75-100 3 unspecified 5

The plant species used in one set of tests and for which the data are given in Table II are marked with the letter according to the following list: 25 A Canadian thistle B Burdock C Indian mallow D a Pomea species E wild flour whey F Persicara hydropiper G yellow walnut butterh H Bromus grass 30 K yard grass 35 m 73972

Table II Before emergence

Compound pre- Plant species

from mark no kg / h ABCDEFGHIJK

5 1 11.2 53333333333 5.6 52233333333 2 11.2 21132233333 5.6 32132302233 3 11.2 31233333233 10 5.6 20233233133 4 11.2 53233333333 5.6 52123333333 5 11.2 53233333333 5.6 50033333133 15 6 11.2 521333333 2 31223023133 5.6 10113013133 8 11.2 32023333333 20 5.6 31033333233 9 11.2 22233333333 5.6 32122333133 10 11.2 32133333333 5.6 31123333033 25 11 11.2 31133333033 5.6 31123313133 12 11.2 32023333033 5. 11 31023333033 , 6 32233333233

The compounds were further tested using the above procedure on the following plant species: L soybean R Sesbania hemp M sugar beet E wild flour whey 35 n wheat F Persicara hydropiper 0 rice C Indian mallow P millet J soft Bromus grass 17 73972 B burdock S röy

Q wild buckwheat K yard D a Ipomea species T creeping weed

The results are summarized in Table III.

5 Table III

Before germination

Compound

e.g. No. kg / h LMNOPBQDREFCJSKT

1 5,6 1233303333323333 10 1,12 0112301223203333 0,28 0102101033302333 0,056 0000000011100223 0,0112 0000000001100122 2 5,6 1323312333303335 15 1,12 0323201312203335 0,28 0201100111003335 0,56 01000000000011 12 0113310313003333 0.28 0002200003001333 0.056 0001000002300333 0.0112 0000000001000333 0.0056 0000000003000101 25 4 5.6 2333323333313333 1.12 1323313233313333 0.28 0122101013302333 0.056 0111221021100223 0.0112 0100000001000333 30 5 5.6 123331333 3 313333 1.12 0223303032203333 0.28 0213322323303333 0.056 0101212013102333 0.0122 0100011003101233 35 ie 73972

Table III (continued)

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5 No. kg / h LMNOPBQDREFCJSKT

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Table III (continued)

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12 5.6 1223312202103333 1.12 1212302212203333 0.28 0101001001001232 0.056 0500005000000020 10 13 5.6 2333323333323333 1.12 1233302232303333 0.28 2233101031303333 0.056 0111001000002333 in the selective control of perennial and annual weeds that are difficult to eradicate, such as perennial weeds such as rye wheat, yellow and purple nut butter; annual broadleaf weeds such as prickly mallow plant, Sesbania hemp, Persicara hydropiper, wild flour whey, swine grass and annual 25 grasses such as "shattercane", alexander grass, red-green grass, evergreen millet, Texas "prosciutto" grass, Rottboellia exaltata), weightlocks, (e.g. green, yellow and giant) grasses, and broad creeping weeds. Weed reduction has been achieved with 30 other sustainable species such as Ambrosia-like weeds, Indian mallow, one species of Ipomea, burdock, swollen grass, etc.

The selective control and increased suppression of the above-mentioned weeds with the herbicides 35 of the invention has been observed in a number of different cereals, of particular interest to maize and soybeans, but also in others such as cotton, peanuts, oilseed rape, folding beans (shrubs and bushes), wheat ; whereas, however, the latter two cereals are generally less tolerant of the herbicides of the invention than the other named cereals; such reduced tolerance can be improved by the use of preservatives, i.e. herbicide antidotes.

In this specification and in the following tables, the application rates of the herbicide are indicated by the symbols "GR15" and "GRg, -"; these amounts are given in kilograms per hectare (kg / ha) and can be converted into pounds per acre (10 lbs / A) by dividing the amount per kg by 1.12. GR ^ g defines the maximum amount of herbicide required to apply 15% or less damage to cereals, and GRgg defines the minimum amount required to achieve 85% weed control. The amounts of GR ^ g and GRgg are used as a measure of potential commercial performance, it being to be understood, of course, that suitable commercial herbicides can provide greater or lesser plant damage within reasonable limits.

Another guideline for the efficacy of a chemical as a selective herbicide is the "selectivity factor" ("SF") in cereals and weeds applied to a herbicide, which is a measure of the relative safety of cereals and weed damage and is expressed as a GR ^ g / GRgg ratio, i.e. ^ g for 25 cereals divided by GRgg for weeds, both amounts in kg / ha The following tables show the selectivity factors in brackets after GRgg for each weed, the symbol "NS" means "non-selective". indicated by line-30 la (-).

Since the tolerance of cereals and the control of weeds are interrelated, a brief reflection in this respect is appropriate from the point of view of selectivity factors. In general, it is desirable for cereal safety factors, i.e., herbicide tolerance values, to be high because higher herbicide concentrations are often desired for one reason or another. Conversely, it is desirable that the amounts of herbicide be small, i.e. the herbicide has a high unit activity, for economic and possibly acological reasons. However, small application rates of a herbicide may not be sufficient to control certain weeds and a higher amount is required. Thus, the best herbicides are those that control the largest number of weeds with the least amount of herbicide and give the grain the highest levels of safety, i.e., tolerance to the grain. Thus, selectivity factors (defined above) are used to determine the relationship between cereal safety and weed control. With reference to the selectivity factors listed in the tables, it is meant that the higher the numerical value, the greater the selectivity of the herbicide for the herbicide.

To illustrate the surprisingly excellent properties of the compounds of this invention on both an absolute and relative basis, comparative tests were performed in the greenhouse with prior art compounds that are most similar in chemical structure to the compounds of the invention. These prior art compounds are designated as follows (using the following nomenclature as for the compounds of the invention): A. N- (methoxyethyl) -2'-trifluoromethyl-2-chloroacetanilide.

B. N- (ethoxyethyl) -2'-trifluoromethyl-2-chloro-acetanilide.

Tables IV and V show the pre-emergence herbicidal activity values comparing the relative potency of the compounds of the invention and prior art compounds as selective herbicides against hardy and difficult perennial weeds against common wheat and yellow walnut butter in soybeans and corn, respectively. Such weeds are commonly associated with such major cereal species as corn and soybeans. The test values in Tables IV and V were obtained under similar conditions and represent the average of the repeated experiments (except for the compound of Example 13, which was present in one control test). The test procedure was the same as explained in Tables II and III, but modified by 22,73972 by initially applying a surface irrigation corresponding to a rainfall of 0.54 cm; subsequent irrigation was performed by sub-irrigation.

“NS” means non-selective within test limits.

Table IV

5 GR ^ 5 amount GRgg amount (kg / ha) (kg / ha)

Compound Soybeans Salt wheat Yellow walnut A> 2.24> 2.39 (NS) 1.13 (1.98) B 1.96 0.61 (3.21) 0.44 (4.45) 10 Eg 1 2, 67 0.17 (15.6) 0.17 (15.6)

Example 3 1.68 0.27 (6.22) 0.19 (8.84)

Ex. 4 1.12 0.13 (8.62) 0.17 (6.59)

Ex. 5 1.46 0.26 (5.62) 0.26 (5.62)

Eg 13 2.13 0.20 (10.65) 0.17 (12.53) 15

Referring to the numerical values in Table IV, it is found that each compound of the invention had spectacularly higher selectivity factors (values in parentheses) against both Juola wheat and yolk soybeans than the prior art compounds. In particular, it is found that the unit activities (relative toxicity to plants per unit of herbicide) of the compounds of the invention are significantly higher against common wheat and yellow walnut butter than the corresponding values of prior art compounds, while maintaining crop safety. In particular, the strikingly high selectivity factors of the compounds of Examples 1 and 13 should be noted.

Further reference values showing the relative efficacy of the compounds of the invention compared to the aforementioned prior art compounds against common wheat and yellow nut butter in maize are shown in Table V.

23 73972

Table V

GR ^ amount GRgg amount (kg / ha) (kg / ha)

Compound Maize Jolly wheat Yellow walnut 5 A> 2.24> 2.39 (NS) 1.13 (1.98) B 0.81 0.61 (1.33) 0.44 (1.84)

Ex. 1 0.76 0.17 (4.47) 0.17 (4.47)

Example 3 1.94 0.27 (7.19) 0.19 (10.2)

Ex. 4 0.75 0.13 (5.85) 0.17 (4.47) 10 Ex. 5 1.83 0.26 (7.04) 0.26 (7.04)

Ex. 13 2.24 0.20 (11.2) 0.17 (13.18)

Referring to the values in Table V, it is found that each compound of the invention had spectacularly higher selectivity factors against both juvenile wheat and yellow nut butter in corn than the prior art compounds. Again, it is found that the unit activities of the compounds of the invention were significantly higher against yolk wheat and yellow walnut butter than with prior art compounds sa-20 miles while maintaining crop safety. In particular, high selectivity factors are observed for the compounds of Examples 3, 5 and 13, especially compared to the corresponding values of previous compounds in the art.

The comparative data in Tables IV and V show that the compounds of the invention have a markedly higher and unexpectedly better herbicidal efficacy against herbicide-tolerant perennial weeds in downy wheat and yellow walnut on two major cereal species, i.e. soybeans and maize, than compounds 30, soybeans and maize. .

In addition, pre-sprouting herbicidal values from other tests have shown that the compounds of this invention also selectively control common wheat, yellow nut butter and / or other weeds in one or more of the 35 crops useful in cotton, peanuts, shrubs, wheat, millet and / or oilseed rape. For example, Table VI shows numerical values showing the herbicidal selectivity of the compounds of Examples 1 24 73972 and 3 against downy wheat, oilseed rape, millet beans, millet and wheat. Unless otherwise indicated, the greenhouse tests in Table VI and the following tables included herbicide treatments by incorporation into the growth layer and surface irrigation, followed by lower end irrigation as described above.

Table VI

GR ^, - amount GRgg amount (kg / ha) (kg / ha) 10 compound Rapeseed Folding beans Millet Wheat Salt wheat e.g. 1 0.86 - - 0.12 (7.2) 0.90 - - 0.12 (7.5) 0.24 - 0.12 (2.0) - 0.21 0.12 (1.8) 15 Example 3 1.9 - - 0.28 (6.8) 2.24 - - 0.28 (8.0) 0.84 - 0.28 (3.0) - 0.28 0.28 (1.0) The compound of Example 1 was also tested in the field to determine its selectivity before sprouting (pp ), yarrow and white “proso” millet among a variety of useful crops, the figures (representing three replicate experiments) are shown in Table VII for both surface application (SA) and growth layer incorporation (PPI, i.e. post-sowing incorporation) of the Herbi-25 binder. sown in a thin layer of loamy soil with moderate humidity.The seeds were planted to a depth of two inches (5.08 cm) The first rain (0.51 cm) 30 occurred the day after treatment, the second rain (0.64 cm) two days after treatment; after 1 day of treatment was 4.57 cm H key findings were made six weeks after treatment.

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The figures in Table VII show that, in general, the compound of Example 1 performed better as a selective herbicide by the surface application method than by the combination layer. In particular, in surface application tests, this herbicide 5 selectively controlled three test weeds at application rates above 0.58 kg / ha while maintaining crop safety (i.e. maximum damage up to about 15%) in field maize and soybeans up to 4.48 kg / ha and safety for sweetcorn, peanuts and oilseed rape at a rate of more than 10 bars at a rate of more than 2.24 kg / ha and for cotton, millet and shrubs at just under 2.24 kg / ha: 11a. In PPI tests, the compound of Example 1 selectively controlled weevil species and grasses at less than 1.12 kg / ha while maintaining crop safety in field maize, peanuts 15 and oilseed rape at rates of up to 2.24 kg / ha and slightly below 2.24 kg. / ha: 11a with soybeans.

Other field test values for the compound of Example 1 showed selective control prior to sprouting to other weeds on soybeans, corn, cotton and / or peanuts, such as purple nut butter, persian bean, persian ryegrass, yellow scabbardfish, wild flour clay, wild flour clay, batch against swell weeds, creeping weeds, spiral grass, Texas burp, 25 Florida swell weeds and / or bristles. It will be apparent to those skilled in the art that not all designated weeds can be selectively controlled on all designated crops under all climatic, soil, humidity conditions and / or all herbicide application methods.

30 The selectivity values for the control of the above-mentioned weeds on crops soybeans, maize, cotton and peanuts, from a number of field tests under different soil, moisture, etc. conditions, are presented together in Tables VIII-XI, respectively. In the tables, 35 "WAT" means "weeks after treatment of the plants" with a herbicide, applied either by surface application ("S.A.") or by combining before planting ("PPI") in the growth layer; application rate- 2? 73972 rät for each beneficial plant / weed combination are shown as GR15 and GR8 (defined above); the ratio GR ^ g / GRgg gives a selectivity factor, "S.F."; "NS" indicates non-selectivity and the dash (-) indicates limit selectivity or selectivity that cannot be determined, e.g., because the actual amounts of GR1,., And GRgg were greater or less than the maximum or minimum. Tables VIII-XI indicate blank that the plant species was not included in any of the specific tests or that the value was not obtained or was less significant than the other values reported, e.g., some 3 WAT observations have been omitted. out of 6 in favor of WAT values or 6 WAT values have been omitted because 3 WAT values were accurate Table VIII 15

Compound Utility plant / sulfur- Application- WAT GR.e / GRgc S.F. blackberry-combination method

Eg 1 Soybeans / left- S.A. 3 20 volumetric head 5> 4.48 / <1.12 (> 4.0) P.P.I. 3 5> 4.48 / <1.12 (> 4.0) 3> 4.48 / <1.12 (> 4.0)

Soybeans / Giant 25 S.A. Δ 2.52 / 2.8 (NS) P.P.I. 6 1.4 / <1.12 (> 1.3)

Soybeans / Wild S.A. 6 2.52 / 2.52 (1.0) li powdery mildew P.P.I. 6 1.4 / 2.8 (NS)

Soybeans / Penn P.P.I. 3 4.48 / 2.52 (1.8) 30 sulvanian

Persicara hydropiper

The values in Table VIII show that the compound of Example 135 selectively controlled giant and yellowtail heads, wild flour whey and Pennsylvania Persicara Hydropiper with 6-8 WAT soybeans by either S.A. or P.P.I. application methods.

28 7 3 9 7 2

Table IX

Compound Utility / Sulfur- Application- WAT GR15 / GRg- S.F. barley-combination method 5 Example 1 Corn / giant S.A. Δ 4.48 / <1.12 (4.0) spot weight S.A. 6.5> 7.84 / 8.4 (NS) P.P.I. Δ 4.76 / 1.96 (2.5) P.P.I. 6.5> 6.72 / 4.48 (1.5)

Maize / Ipomea- S.A. 3> 4.48 /> 4.48 (-) 10 grass S.A. 6> 4.48 /> 4.48 (-) P.P.I. 3 4.76 /> 4.43 (-) P.P.I. 6 4.76 /> 4.48 (-)

Maisi / takiai- S.A. 3> 4.48 /> 4.48 (-) nen S.A. 6> 4.48 /> 4.48 (-) 15 P.P.I. 3 4.76 /> 4.48 (-) P.P.I. 4.76 /> 4.48 (-)

The numerical values in Table IX show that the compound of Example 1 selectively controlled giant pine head maize from 20 to 6.5 WAT by either SA or PPI application: The selectivity of Ipomea weed and burdock was not determined by test amounts, but suppression of these weeds was observed .

29 73972

Table X

Compound Utility / Sulfur- Application- WAT GR. c / GR.,. S. F. Rough Compound Method 5 Example 1 Cotton / Purple S.A. 6 3.64 / 1.68 (2.17) cross-colored nut S.A. 9 3.36 / 2.24 (1.5) Chinese pepper P.P.I. 6 3.36 / 4.2 (NS)

Cotton / Spike S.A. 6 3.64 / 3.08 (1.18) command mallow plant S.A. 9 3.36 / 4.76 (NS) 10 P.P.I. 6 3.36 / 4.76 (NS)

Cotton / Expansion S.A. 9 3.36 / 1.96 (1.7) grass

Cotton / Creep S.A. 7 1.4 / <1.12 (> 1.25) weed P.P.I. 7 0.84 / 1.12 (NS) 15 (soft and bitter)

Cotton / spiral P.P.I. 7 0.84 / <1.12 (-) Matara

The numerical values in Table X show that the compound of Example 1 selectively controlled purple walnut and swell grass up to 9 WAT, prickly mallow up to 6 WAT and creeping weed up to 7 WAT; the control of the tortoise was a borderline case or impossible to determine.

Table XI shows the activity values before germination against the compound of Example 1 against three durable annual weeds, i.e. Texas burp, bristle butterbur and Florida swollen grass, in peanuts up to 12 WAT cycles. The numerical values in Table XI represent the mean of 30 replicates in sandy clay soils with 1.3% organic matter, 79.2% sand, and 10% clay; herbicide surface application.

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The numerical values in Table XI show that the compound of Example 1 selectively controlled Texas lice in peanuts for up to eight weeks and gave a high degree of control in a further 12 WAT at about 4.48 kg / ha; selective control of bristle ta-5 was achieved at 3.36 kg / ha for eight weeks and complete control was maintained at 12 WAT at 4.48 kg / ha and selective control of Florida swollen grass was achieved at less than 2.24 kg / ha: at 8 WAT and 4.48 kg / ha achieved 95% control in 10 12 WAT.

In other greenhouse tests, the compounds of this invention have selectively controlled a number of annual and perennial weeds in a variety of useful plants. As a further illustration, the compound of Example 1 selectively repelled purple nut butter in both maize and soybeans, with corresponding crop / weed GR1 / GRg ratios (expressed in kg / ha) of 0.67 / 0.25 ( SF = 2.7) for maize and 1.12 / 0.25 (SF = 4.5) for soybeans. The compound of Example 11 has selectively controlled yellow walnut butter and jujube in corn and soybeans. The corresponding useful plant / yellow nut butter GR 1 / GR 8 ratios were> 2.24 / 0.95 (S.F. = 2.4) in maize; 2.24 / 0.5 (S.F. = 4.5) for soybeans and the corresponding GR ^ / GRgg ratios for both maize and soybean and beans in dairy wheat were> 2.24 / 0.5 (S.F. = 4.5). In one test against yellow walnut butter in cotton, the GRis / GRgg ratio (mean of two replicates) was 1.96 / 0.95 (S.F. = 2.1). Similarly, the compound of Example 13 selectively inhibited yellow nut butter in cotton and Juola-30 wheat in wheat, with GRR / GRgg ratios of 0.7 / 0.47 in cotton (SF = 1.7) and 0.58 / 0.47 in wheat ( SF = 1.2).

In a multi-crop greenhouse test, the compounds of Examples 1, 13, 14, and 15 were tested against 35 yellow walnut villas on cotton, soybeans, corn, and rice; each compound was non-selective for the yellow nut butter on rice. Significant 32,73972

however, high selectivities for yellow walnut butter on cotton, soybeans, and corn were obtained for each compound in the test; the corresponding amounts of GR 1 and GR 2 for these compounds are shown in Table XII; selectivity factors-5 are shown in parentheses after each useful plant. Table XII

GR85 GR15 (kg / ha) (kg / ha)

Compound Yellow Nut- Cotton Soybeans Corn 2Q Chinese Butter

Ex. 1 0.24 1.96 (8.2) 0.87 (3.6) 0.69 (2.9)

Ex. 13 0.21 2.52 (12.0) 1.96 (9.3) 2.52 (12.0)

Example 14 0.38 2.8 (7.4) 2.24 (5.9) 1.68 (4.4) 15 Example 15 0.44 2.8 (6.4) 1.96 (4 .5) 1.96 (4.5)

The compounds of Examples 1 and 13-15 were further tested against jow wheat in wheat, soybeans and corn; each compound was found to be non-selective in wheat. The selectivity values for the above compounds against common wheat in soybeans and maize are shown in Table XIII.

Table XIII

GR85 GR15 25 (kg / ha) (kg / ha)

Compound Salt Wheat Soybeans Corn

Ex. 1 0.07 0.81 (11.6) 0.69 (9.9)

Ex. 13 0.36 1.68 (4.7) 1.68 (4.7)

Example 14 0.45 1.46 (3.2) 2.52 (5.6) 30 Example 15 0.75 1.96 (2.6) 2.24 (3.0)

In still another herbicidal efficacy greenhouse tests, the compounds of Examples 1 and 3 were tested against a number of annual grasses comprising resistant weeds, such as Texas moth, perennial millet growing from seed, "shattercane", alexanth grass, wild milicaeum) 1 in, red rice and causative grass. The results of these tests are negated in Table XIV; selectivity factors are shown in parentheses; the line indicates boundary or indeterminate selectivity.

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The numerical values in Table XIV show that the compound of Example 1 selectively controlled each annual weed in the soybean test. The compound of Example 3 had a positive selective control against all weeds 5 except Texas burp, wild "proso" millet and scab, at a maximum test rate of 1.12 kg / ha; a larger amount would have been needed to determine the selectivity of the compound against these three weeds, which did not show selective control with the test amount.

10 The herbicide has a clear advantage in its ability to work in different soil types. Thus, Table XV shows numerical values showing the herbicidal activity of the compound of Example 1 against sage wheat in soybeans among a variety of soil types with varying organic matter and clay concentrations. Herbicide treatments were performed by combining the growth layer by planting the seeds to a depth of 0.95 cm and using 0.63 cm surface irrigation. Observations were made approximately three weeks after treatment. Selectivity factors are shown in parentheses.

The numerical values in Table XV show that the compound of Example 1 appears to be quite insensitive to soil types with varying organic matter concentrations, selectively controlling juvenile wheat with soybeans in growing layers containing 1.0 to 60% organic matter and having a clay content of at least 1.8 to 37. %. Numerical values for soybeans in Wabash loam clay were impossible to determine in this test. The selectivity factors shown in coarse and Drummer loam and Florida peat were also minimum values, as the maximum test amount was 2.24 kg / ha and the 30 herbicides were safe in beans in the same amount above 2.24 kg / ha.

Laboratory tests were performed to determine the resistance of the herbicides of this invention to extraction into the growth layer and to determine the effect of the resulting herbicide-35. In these tests, the compounds of Examples 1 and 4-6 were treated with acetone and then sprayed with a weighed amount of Ray-36,73972 loamy clay and Drummer loamy clay in pots with filter paper covering the wells. The pots containing the treated mold were extracted by placing them on a turntable rotating under the two mouth-5 tips of the water tank, sized to give an amount of water corresponding to 2.5 cm of rain per hour. Extraction rates were adjusted by varying the time on the turntable.

Water was fed into the mold in the pots and allowed to percolate through the filter paper and drain holes. Pot 10 was then allowed to stand for three days at ambient temperature. The treated mold in the pots was then removed, crushed and applied as a surface layer to the top surface of other pots containing the aforementioned soil layers sown with yard seeds. The pots were then placed in greenhouse benches, watered from below and allowed to grow for 2-3 weeks. Visual evaluations of growth inhibition percentage compared to control (untreated) pots and fresh weights for yard grass were recorded; the value obtained from the comparison represents six replicates 20 and the value of the test compounds three replicates; the test values are shown in Table XVI. Fresh weights of weed were not measured for tests in the Drummer loamy clay soil growth layer.

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The values in Table XVI indicate that the compounds of this invention were completely resistant to extraction into the growth layer under varying rainfall conditions. In particular, at an application rate of 2.24 kg / ha, each of the compounds 5 of the invention controlled yard grass with a corresponding rainfall of 10.16 cm in Ray loamy soil and Drummer loamy loam growth layer, except for the compounds of Examples 1 and 5 in Ray loamy, where control was maintained below 5.03 cm with the corresponding rainfall. Also at a low application rate of 0.14 kg / ha 10, the compounds of Examples 1, 4 and 5 controlled yard grass in Drummer loamy clay with a corresponding rainfall of 5.08 cm.

Toxicological studies with the compound of Example 1 have shown that the compound is completely safe. It is mildly toxic (OLD, .g 2300 mg / kg; MLDj-g> 5010 mg / 15 kg) and has a mild eye irritation but not skin irritation effect. No special handling measures other than normal precautions are considered necessary.

Thus, from the above detailed description, it is clear that the compounds of this invention unexpectedly and strikingly have better herbicidal properties, both in absolute and relative terms, compared to the most structurally advanced compounds of the prior art. In particular, the compounds of this invention have been shown to be strikingly selective herbicides, especially in the control of difficult-to-control perennial and annual grasses in soybeans and corn, but also in peanuts, cotton and other useful plants. In particular, the compounds of this Kek-30 invention strikingly control perennial weeds such as yolk wheat and walnut groves, as well as durable annual grasses such as Texas lichen, scabies grass, wild "proso" millet, Alexander's grass, seedlings, and / or red rice, while also controlling and / or suppressing other less durable annual grasses and perennials.

41 73972 The herbicidal compositions of this invention, including concentrates, which require dilution prior to application, contain at least one active ingredient and excipient in liquid or solid form. The compounds are prepared by mixing the active ingredient with an excipient comprising diluents, extenders, carriers and conditioning agents to give combinations in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions.

Thus, the active ingredient may be employed with an excipient such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, a disintegrating agent, or some suitable combination thereof.

The combinations of this invention, especially liquids and wettable powders, preferably contain, as a conditioning agent, one or more surfactants in amounts sufficient to make any given combination readily dispersible in water or oil. The combination of a surfactant with these combinations greatly improves their effectiveness. The term "surfactant" means that wetting agents, dispersing agents, suspending agents and emulsifying agents are included.

Anionic, cationic and nonionic agents can be used with equal advantage.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinyl sulphonate, sulphated or sulphonated fatty acid esters, rock oil fatty acid esters, rock oil. nonylphenol) polyoxyethylene derivatives and polyoxyethylene derivatives of mono-higher fatty acid esters of hexitol anhydrides (e.g. sorbitan). Preferred dispersants include methylcellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonate and polymethylene bisnaphthalenesulfonate.

42 7 3 9 7 2

Wettable powders are water-dispersible combinations containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents. Inert solid extenders are usually of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals derived from silica, etc. Examples of such extenders are kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powder-10 combinations of the present invention usually contain about 0.5 to 60 parts (preferably 5 to 20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1 to 15 parts) of wetting agent, about 0.25 to 25 parts (preferably 1.0 to 15 parts) of dispersant and 5 to n.

95 parts (preferably 5 to 50 parts) of inert solid extender, all parts being calculated by weight of the total combination. If necessary, 0.1 to 2.0 parts of the solid inert extender may be replaced by an anti-corrosion agent or an antifoam agent, or both.

Other formulations include dust concentrates containing 0.1 to 60% by weight of active ingredient with a suitable excipient; these dusts can be diluted for application to concentrations between about 0.1 and 10% by weight.

Aqueous suspensions or emulsions can be prepared by mixing an aqueous mixture of the water-insoluble active ingredient and the emulsifier until uniform and then homogenizing to give a stable emulsion of fines. The resulting concentrated aqueous suspension is characterized by its extremely small particle size so that the diluted and sprayed coating is very uniform. Suitable concentrations of these formulations are about 0.1 to 60%, preferably 5 to 50% by weight of the active ingredient, with the upper limit being determined by the solubility of the active ingredient in the solvent.

In another form of aqueous suspension, the water-immiscible herbicide is encapsulated to form a phase enclosed in microcapsules dispersed in the aqueous phase. In one embodiment, very 43,73972 small capsules are formed by combining an aqueous phase containing a lignin sulfonate emulsifier and a water-immiscible chemical and polymethylene polyphenyl isocyanate, dispersing a water-immiscible phase in the aqueous phase, followed by the addition of a polyvalent amine. The isocyanate and amine compounds react to form a solid urea shell wall around the water-immiscible chemical particles, thus forming its microcapsules. In general, the concentration of microencapsulated substance 10 is between about 480-700 g / l of the total combination, preferably 480-600 g / l.

Concentrates are usually solutions of the active ingredient in water-immiscible or partially water-immiscible solvents together with a surfactant. -15 with the substance. Suitable solvents for the active ingredient of this invention include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones. However, other very strong liquid concentrates can be formed by dissolving the active ingredient in a solvent and then diluting, e.g. with fuel oil, to a spray concentration.

The concentrate combinations disclosed herein generally contain from about 0.1 to 95 parts (preferably from 5 to 60 parts) of active ingredient to 25 parts, from about 0.25 to 50 parts (preferably from 1 to 25 parts) of surfactant and, if necessary, from about 4 parts. -94 parts of solvent, all parts being calculated on the total weight of the emulsifiable oil.

Granules are physically stable particulate compounds that contain the active ingredient adhered or distributed throughout the base matrix of an inert, finely divided particulate extender. To facilitate extraction of the active ingredient from the particulate, a surfactant, such as those listed above, may be present in the combination. Natural clays, pyrophyllites, il-lite, and vermiculite are examples of useful classes of particulate mineral extenders. Preferred extenders are porous, absorbent, compressed particles such as compressed and screened particulate attapulgite or hot expanded particulate vermiculite and finely divided clays such as kaolin clays, hydrated attapulgite or bentonite clays. These extenders are sprayed on or mixed with the active ingredient to form herbicidal granules.

The granular combinations of this invention may contain from about 0.1 to about 30 parts, preferably from about 3 to 20 parts by weight of 10 active ingredients per 100 parts by weight of clay and from 0 to about.

5 parts by weight of surfactant per 100 parts by weight of particulate clay.

The combinations of this invention may also contain other additives, for example, fertilizers, other herbicides, other plant protection agents, preservatives, etc., which are used as adjuvants or in combination with any of the adjuvants described above. Chemicals useful in combination with the active ingredients of this invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, triazole benzoic acids, nitriles, biphenyl ethers, etc., such as:

Heterocyclic Nitrogen / Sulfur 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 3-Isopropyl-1H-2,1,3-benzothiadiazin-3- (3H) -one 2,2-dioxide 3-Amino-1,2,4-triazole 6,7-dihydrodipyrido (1 , 2-a: 2 ', 11-c) -pyrazidium salt 5-bromo-3-isopropyl-6-methyluracil 1,1'-dimethyl-4,4'-dipyridinium urea N' - (4-chlorophenoxy) phenyl) - N, N-Dimethylurea 35 N, N-Dimethyl-N '- (3-chloro-4-methylphenyl) urea 3- (3,4-dichlorophenyl) -1,1-dimethylurea 1,3-dimethyl-3- (2 -benzothiazolyl) urea 45 7 3 9 7 2 3- (p-chlorophenyl) -1,1-dimethylurea 1-butyl-3- (3,4-dichlorophenyl) -1-methylurea Carbamates / thiol carbamates 2-chloroallyl diethyldithiocarbamate 5 S - (4-chlorobenzyl) -N, N-diethylthiol carbamate isopropyl N- (3-chlorophenyl) carbamate S-2,3-dichloroallyl N, N-diisopropylthiol carbamate ethyl N, N-dipropylthiol carbamate 10 S-propyl -dipropyylitiolikarbamaatt i

Acetamides / acetanilides / anilines / amides 2-chloro-N, N-diallylacetamide N, N-dimethyl-2,2-diphenylacetainide N- <2,4-dimethyl-5- (trifluoromethyl) sulfonyl] -15-amino} phenyl> acetamide N-isopropyl-2-chloroacetanilide 2 ', 6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl-6'-ethyl-N- (2-methoxyprop-2-yl) -2-chloroacetanilide 20 « , ÄrOC-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide Acids / esters / alcohols 2,2-dichloropropionic acid 25 2 Methyl 4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid methyl 2- / 4- (2,4-dichlorophenoxy) phenoxy / propionate 3-amino-2,5-dichlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid 30 2.3 , 6-trichlorophenylacetic acid N1-naphthylphthalamic acid sodium 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate 4,6-dinitro-o-sec-butylphenol 35 N- (phosphonomethyl) glycine and its C -g-monoalkylamine and alkali metal salts and their combinations 46 7 3 9 7 2

Ethers 2,4-Dichlorophenyl-4-nitrophenyl ether 2-Chloro-η 4, β-trifluoro-p-tolyl-3-ethoxy-4-nitro-diphenyl ether

Fertilizers that are useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate. Other useful additives are substances in which plant organisms take root and grow, such as compost, livestock manure, humus, sand, etc.

Examples of herbicidal combinations of the type described above are given in several illustrative embodiments below.

I. Emulsifiable concentrates

% By weight A. Compound of Example No. 1 50.0 20 Calcium dodecylbenzenesulfonate / mixture of polyoxyethylene ethers (e.g. Atlox® 3437F) 4.85 Calcium dodecylbenzenesulfonate (FloMo 60H) 0.15 25 Cg aromatic solvent 45.0 100.00 B. Example No. 4 compound 85.0 calcium dodecyl sulfonate / alkyl aryl polyether alcohol mixture 4.0 Cg aromatic hydrocarbon solvent 11.0 100.00

Ci Compound of Example No. 6 5.0 calcium dodecylbenzenesulfonate / polyoxyethylene ether mixture 35 (e.g. Atlox® 3437F) 1.0 xylene 94.0 100.00 47 7 3 9 7 2 II. Liquid concentrates

% By weight A. Compound of Example No. 4 10.0 xylene 90.0 5 100.00 B. Compound of Example No. 5 85.0 dimethyl sulfoxide 15.0 100.00 C. Compound of Example No. 6 50.0 10 N-methylpyrrolidone 50 .0 100.00 D. Compound of Example No. 7 5.0 ethoxylated castor oil 20.0 rhodamine B 0.5 dimethylformamide 74.5 100.00 III. Emulsions A. Compound of Example No. 12 40.0 Polyoxyethylene / polyoxypropylene block copolymer with butanol (e.g. Terfitol® XH) 4.0 Water 56.0 100.00 B. Compound of Example No. 13 5.0 Polyoxyethylene / polyoxypropylene block - copolymer with butanol 3.5 water 91.5 100.00 IV. Wettable powders 30 A. Compound of Example No. 1 25.0 Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyl taurate 1.0 Amorphous silica (synthetic) 71.0 100.00 35 4β 73972

Weight% Β. Compound of Example No. 12 80.0 Sodium dioctyl sulfosuccinate 1.25 Calcium lignosulfonate 2.75 Amorphous silica (synthetic) 16.00 100.00 C. Compound of Example No. 13 10.0 Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyl taurate 1.0 10 kaolinite clay 86.0 100.00 V. Dusts A. Compound of Example No. 7 2.0 attapulgite 98.0 15 100.00 B. Compound of Example No. 8 60.0 montmorillonite 40.0 100.00 C. Compound of Example No. 9 30.0 20 bentonite 70.0 100.00 D. Compound of Example No. 10 1.0 diatomaceous earth 99.0 100.00 25 VI. Granules A. Compound of Example No. 1 15.0 granular attapulgite (screen number 20/40 mesh) 85.0 100.00 30 B. Compound of Example No. 6 30.0 diatomaceous earth (20/40) 70.0 100.00 C. No. 12 compound 0.5 bentonite (20/40) 99.5 35 100.00 49 7 3 9 7 2

% By weight D. Compound of Example No. 13 5.0 pyrophyllite (20/40) 95.0 100.00 5 VII. Microcapsules A. Compound of Example No. 1 encapsulated within a polyurea shell wall 49.2 sodium lignosulfonate (e.g. Reax 88®B) 0.9 water 49.9 10 100.00 B. Compound of Example No. 12 encapsulated within a polyurea shell wall 10.0 potassium lignosulfonate (e.g. Reax®C-21) 0.5 water 89.5 100.00 C. The compound of Example No. 13 encapsulated within a polyurea shell wall 80.0 magnesium salt of lignosulfate (Treax, LTM®) 2.0 water 18.0 100.00

When operating in accordance with the present invention, effective amounts of the acetanilides of the invention are applied to the growth layer containing the seedlings or combined with the aqueous medium in any suitable manner. Application of liquid and particulate solid combinations to the growth layer can be accomplished by conventional methods, e.g., power dusters, bar and hand sprayers, and nebulizers. The combinations can also be applied from aircraft as dust or mist due to their effectiveness in small doses. The application of herbicidal combinations to aquatic plants is usually carried out by adding the combinations to an aqueous medium in an area where control of the aquatic plants is desired.

The application of an effective amount of the compounds of this invention to a site of unwanted weed growth is essential and critical to the practice of this invention. The exact amount of active ingredient to be used depends on various factors, i.e. 73972 such as the plant species and its stage of development, the type and condition of the soil, the amount of precipitation and the specific acetanilide used. In selective pre-sprouting application to plants or growth layer, a dose of usually from 0.02 to about 11.2 kg / ha, preferably from about 0.04 to about 5.60 kg / ha and suitably from 1.12 to 5, is applied. 6 kg / ha acetanilide. In some cases, larger or smaller amounts may be required. One skilled in the art can readily determine the optimum amount to be applied in each particular case based on this description and the 10 examples above.

The term "soil" (soil, growth layer, soil) is used in its broadest sense to include all conventional "soils" as defined in Webster's New International Dictionary, 2nd Edition, unabridged (1961). This term thus encompasses any material or medium in which vegetation can take root and grow, and includes not only soil but also compost, livestock manure, peat, humus, sand, etc., adapted as a growing medium.

Although the invention has been described in terms of specific modifications, their details are not to be construed as limiting, except as to the scope indicated in the following claims.

25

Claims (29)

73972 1. A 2-haloacetanilide compound, characterized in that it has the formula 5 ° C 1 CH, C CH-OR / * wherein R is C 1-4 alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and R 1 is 15 hydrogen, methyl or ethyl, provided that when R 1 is hydrogen, then R is isopropyl, and when R 1 is ethyl, then R is ethyl, n-propyl or isopropyl. 2. A compound according to claim 1, which is selected from the group consisting of C 2 -C 4 alkyl. 2 X / 2 N 'Tor wherein R is N-alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and R1 is hydrogen, methyl or ethyl, provided that when Rx is hydrogen, then R is isopropyl, and when R 1 is ethyl, then R is ethyl, n-propyl or isopropyl. Compound according to Claim 1, characterized in that R is C 2-6 alkyl. 3. A method according to claim 2, which is described in R 2 and methyl. 4. A compound according to claim 3, which comprises N- (ethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Compound according to Claim 2, characterized in that R 1 is methyl. Compound according to Claim 3, characterized in that it is N- (ethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 5. A compound according to claim 3, which comprises N- (n-propoxymethyl) -2'-trifluoromethyl-61-methyl-2-chloroacetanilide. Compound according to Claim 3, characterized in that it is N- (n-propoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 6. A compound according to claim 3, which comprises N- (isopropoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Compound according to Claim 3, characterized in that it is N- (isopropoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 7. A compound according to claim 3, which comprises N- (isobutoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Compound according to Claim 3, characterized in that it is N- (isobutoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 8. A method according to claim 2, which is described in R1 and ethyl. A compound according to claim 2, characterized in that R 1 is ethyl. 52 73972 9. A compound according to claim 8, which comprises N- (ethoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 56 73972 Compound according to Claim 8, characterized in that it is N- (ethoxymethyl) -2'-trifluoromethyl-61-ethyl-2-chloroacetanilide. 10. A compound according to claim 8, which comprises N- (n-propoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. A compound according to claim 8, characterized in that it is N- (n-propoxymethyl) -21-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 11. A compound according to claim 8, which comprises N- (isopropoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. Compound according to Claim 8, characterized in that it is N- (isopropoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 12. Förening enligt patentkravet 2, kän n e -tecknad därav, att är väte. Compound according to Claim 2, characterized in that it is hydrogen. 13. A compound according to claim 12, which comprises N- (isopropoxymethyl) -2'-trifluoromethyl-2-chloroacetanilide. Compound according to Claim 12, characterized in that it is N- (isopropoxymethyl) -2'-trifluoromethyl-2-chloroacetanilide. 14. A compound according to claim 1, which comprises a C 1-4 alkenyl radical. A compound according to claim 1, characterized in that R is a C 1-4 alkenyl radical. 15. A compound according to claim 14, which comprises N- (allyloxymethyl) -2'-trifluoromethyl-2-chloroacetanilide. Compound according to Claim 14, characterized in that it is N- (allyloxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 16. A compound according to claim 1, which comprises a C 1-4 alkynyl radical. A compound according to claim 1, characterized in that R is a C 1-4 alkynyl radical. 17. A compound according to claim 16, which comprises N- (propargyloxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Compound according to Claim 16, characterized in that it is N- (propargyloxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 18. A compound according to claim 1, which comprises a alkoxyalkyl radical with a cholate 5. 19. A compound according to claim 18, which is N- (2-methoxyethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. A compound according to claim 1, characterized in that R is an alkoxyalkyl radical having up to 5 carbon atoms. Compound according to Claim 18, characterized in that it is N- (2-methoxyethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 20. Herbicidal composition comprising an active compound of the form 2-haloacetanilide, which comprises 30 active compounds in the form of an active compound of the formulation 57 7 3 9 7 2 O C1CH2C ^ ^ CH2OR 'TST * for R is C ^ _5 ~ alkyl or alkoxyalkyl or alkenyl or alkynyl having from 5 chapters and the like, methyl or 10 ethyl; for R 1, R 2, is R, isopropyl, or R 1 is ethyl, or R is ethyl, n-propyl or isopropyl. 20. Herbicidal composition comprising 2-haloacetanilide as active ingredient, characterized in that it contains, as active ingredient, one or more 2-haloacetanilide compounds of the formula 53 73972 ° C1CH-C CH-OR 21. The composition of claim 20, wherein R1 is selected from the group consisting of C2-6 alkyl. Composition according to Claim 20, characterized in that in the compound R is C 2-6 alkyl. 22. A composition according to claim 21, comprising -15 times, wherein R is used for methylation. Composition according to Claim 21, characterized in that the compound R 1 is methyl. A composition according to claim 22, which comprises N- (ethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Composition according to Claim 22, characterized in that the compound is N- (ethoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 24. A composition according to claim 22, which comprises N- (n-propoxymethyl) -2'-trifluoromethyl-61-methyl-2-chloroacetanilide. Composition according to Claim 22, characterized in that the compound is N- (n-propoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 25. A composition according to claim 22, which comprises N- (isopropoxymethyl) -21-trifluoromethyl-61-methyl-2-chloroacetanilide. Composition according to Claim 22, characterized in that the compound is N- (isopropoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 26. A composition according to claim 22, which comprises N- (isobutoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Composition according to Claim 22, characterized in that the compound is N- (isobutoxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 27. A composition according to claim 21, which comprises a mixture of R 1 and ethyl. Composition according to Claim 21, characterized in that R 1 is ethyl. 28. A composition according to claim 27, which comprises N- (ethoxymethyl) -21-trifluoromethyl-6'-ethyl-2-chloroacetanilide. Composition according to Claim 27, characterized in that the compound is N- (ethoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. Composition according to Claim 27, characterized in that the compound is N- (n-propoxymethyl) -2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 54 7 3 9 7 2 Composition according to Claim 27, characterized in that the compound is N- (isopropoxymethyl) -21-trifluoromethyl-6'-ethyl-2-chloroacetanilide. Composition according to Claim 21, characterized in that it is hydrogen. Composition according to Claim 31, characterized in that the compound is N- (isopropoxymethyl) -2'-trifluoromethyl-2-chloroacetanilide. Composition according to Claim 20, characterized in that the compound R has an alkenyl radical having up to 5 carbon atoms. Composition according to Claim 33, characterized in that the compound is N- (allyloxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Composition according to Claim 20, characterized in that the compound R has an alkynyl radical having up to 5 carbon atoms. Composition according to Claim 35, characterized in that the compound is N- (propargyloxymethyl) -2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. Composition according to Claim 20, characterized in that the compound R has an alkoxyalkyl radical having up to 5 carbon atoms. Composition according to Claim 37, characterized in that the compound is N- (methoxyethoxymethyl) -21-trifluoromethyl-6'-methyl-2-chloroacetanilide. 55 7 3 9 7 2 1. For 2-haloacetanilides, the compounds of which are derived from the formula 5 9 a compound, methyl or ethyl, a mixture of R 4, a compound, R 2 isopropyl, and R 15 is ethyl, R 2 ethyl, n-propyl or isopropyl. A composition according to claim 27, which comprises N- (n-propoxymethyl) -35-21-trifluoromethyl-6'-ethyl-2-chloroacetanilide.