DE3110525C2 - 2-chloroacetanilides and herbicides containing them - Google Patents

Abstract

The invention relates to a group of N-hydrocarbyloxymethyl-2-haloacetanilide compounds, herbicide preparations which contain these compounds as active ingredient, and methods for using these herbicides in various crops of useful plants, in particular soybeans, cotton, peanuts, rape and French beans. The herbicides according to the invention are particularly effective against perennial weeds that are difficult to kill such as couch grass and Cyperus esculentus, as well as against annual weeds such as Sida spinosa, Sesbania exaltata, Sorghum halepense seedlings, Sorghum bicolor, etc.

Description

The invention relates to 2-chloroacetanilides and herbicides containing them which are used in agriculture Find application. Numerous descriptions can be found among the publications related to this invention exercises of 2-haloacetanilides, which are unsubstituted or with a large number of substituents on the anilide nitrogen substance atom or may be substituted on the anilide ring, e.g. B. with alkyl, alkoxy, alkoxyalkyl, halogen or other groups.

The compounds according to the invention which are characterized by an alkoxymethyl group on the anilide nitrogen, an alkoxy group in one ortho position and a specific alkyl group in the other ortho position are, as far as known, most likely those of US-PS 34 42 945 and 35 47 620, and above all the compounds 2'-tert-butyl-2-chloro-N-methoxymethyl-6'-methoxyacetanilide and their bromine analog (cf. Examples 18 and 34 in US Pat. No. 3,547,620 and Examples 18 and 36 in US Pat. No. 3,442,945 ).

In US-PS 40 70 389 and 41 52 137 a general formula is shown which compounds of the type <cie they are described in US-PS 34 42 945 and 35 47 620, includes The only one described in an example ne compound which has an alkyl group in one ortho position and an alkoxy group in the other has ortho position, but carries an alkoxyethyl group on the nitrogen atom; Connections of this kind are discussed in detail below.

Other less relevant publications are BE-PS 8 10 763 and DE-OS 24 02 983; to the Compounds described therein include compounds of the type disclosed in U.S. Patents 4,070,389 and 4,152,137 are described, and by an alkoxyalkyl group having two or more carbon atoms between the Anilide nitrogen atom and the oxygen atom of the alkoxy moiety are marked. The closest Specific statements in BE-PS 8 10 763 and DE-OS 24 02 983 are compounds which have an ethoxyethyl group on the anilide nitrogen atom, a methoxy or ethoxy group in one ortho position and a methyl or ethyl group in the other ortho position (cf. SE-PS 8 10 763, compounds No. 7, 13 and 18); it other less relevant homologues of these compounds are also described, e.g. B. the compounds No. 6, 9, 16 and 17, the methoxyethyl or methoxypropyl group on the nitrogen atom, a methoxy or Have ethoxy group in one ortho position and a methyl group in the other ortho position.

US Pat. No. 3,442,945 contains some herbicidal data relating to those compounds mentioned above whose chemical configuration is most closely related to the compounds according to the invention

so is; some data are also in the other patents for other analogous and homologous compounds indicated that are less closely related in their chemical structure, e.g. B. the compounds 6 and 9 of the BE-PS 8 10 763. In particular, these Druckschriiten described the herbicidal activity against a Large number of weeds, but they do not give any data for compounds that additionally and / or simultaneously the hard-to-kill perennial weeds such as couch grass and yellow sedge, as well as a broad spectrum annual weeds including annual broad-leaved weeds as difficult to kill as thorny ones Sida, hemp sesbania, thorn apple, and annual grass weeds such as sorghum pense seedlings, sorghum bicolor, Brachiaria, Panicum species, red rice and raoule grass under control while also controlling other harmful annual or perennial weeds such as knotweed, melde, amaranthus, foxtail, Digitaria sanguinalis and Echinochloa crus-galli.

An extremely useful and desirable property of herbicides is the ability to control weeds through a Keeping it under control for longer periods of time, the longer during each growing season, the better. With many known herbicides, adequate weed control is only achieved for 2-3 weeks, in some very good ones Cases may take up to 4 to 6 weeks before the chemical loses its phytotoxic effectiveness. A The disadvantage of most of the known herbicides is their relatively short lifespan in the soil.

Another disadvantage of some known herbicides, to some extent related to soil life under normal weather conditions, is a lack of persistence of weed control in severe ones Rains that inactivate many herbicides. Another disadvantage of many known herbicides is the limitation of their applicability to certain ones

Soil types, d. k, while some herbicides are effective in soils with low organic content, they are in other soils with high organic proportions ineffective, or vice versa It is therefore an advantage if a Herbicide is useful in all types of soil from light organic to heavy clays and loams.

Another disadvantage of many known herbicides is the restriction to a particularly effective application, d. H. Apply to the surface before emergence or work into the soil. The possibility, being able to apply a herbicide in any way, by applying it to the surface or Incorporation into the soil is very desirable. Finally, a disadvantage of some herbicides is the need to that, because of their toxicity, special precautions must be taken for their handling. A Herbicide should also be safe to use.

The object of the invention is to provide a group of 2-chloroacetanilides with herbicidal properties, which avoid the above-mentioned disadvantages of the known herbicides, a herbicidal activity in the soil for Allow 2 or 3 up to 18 weeks against leaching or dilution in high humidity, for example are resistant to heavy rains, are effective in a wide range of soils, including light ones to medium organic soils to heavy clay or loam, have flexible application options, for example, application to the surface before emergence and by working into the ground are ultimately harmless and do not require any special handling.

This object is now achieved by the herbicidally active substances specified in claims 1 to 3 2-Chloracetanilide, derived from the general formula below

"^

ii

ClCH ₂ CN-CH ₂ OR

25th

^R "T (D) - ^OR1

in the

R for ethyl, .l-propyl, isopropyl, isobutyl, selc-butyl, cyclopropylmethyl, allyl or propargyl,
R ^{1 stands} for methyl, ethyl, n-PropyJ ider isopropyl and
R ^{2 stands} for hydrogen, methyl or ethyl

35

stand, be embraced.

The invention further relates to herbicides which are characterized by a content of one of these 2-chloroacetanilides.

The invention therefore provides herbicides that are difficult to kill perennial and annual Control weeds, e.g. B. couch grass, yellow sedge, Sorghum halepense seedlings, Süa sponosa, hemp sesbania, Sorghum bicolor, Brachiaria, Panicum species, red rice and Raoul grass, as well as a broad spectrum other harmful weeds, such as B. knotweed, melde, amaranthus, thorn apple, foxtails, Echinochloa and Digitaria. They also enable resistant weeds such as Ambrosiaceae, Abutilon, bindweed and xanthium, while they are used for many crops such as soybeans, cotton, Peanuts, rapeseed and / or French beans remain harmless.

An essential property of the herbicide preparations according to the invention is their ability to produce a broad Keeping spectrum of weeds under control. This includes weeds caused by common herbicides Can be combated, as well as a variety of weeds, which individually or collectively so far Missed control by a single class of known herbicides. At the same time they are harmless to Cultures of one or more crops, including in particular soybeans, cotton, peanuts, rapeseed, Include haricot beans and others. While the well-known herbicides used to control a number of weeds and occasionally certain resistant weeds are useful, the unique ones have been shown to be Herbicides of the invention as being able to treat a variety of resistant perennial and annual weeds to control or largely to push back, such as the perennial weeds couch grass and yellow sedge, annual broad-leaved weeds such as thorny sida, hemp sesbania, thorn apple, knotweed plants, Melde, goosefoot plants, and annual grasses such as Shattercane, Brachiaria, Sorghum halepense seedlings, Panicum species, red rice, raoul grass, and other harmful weeds such as autumn panicum, foxtail, Barnyard grass and digitaria. There was also improved weed reduction in resistant weeds such as Ambrosiaceae, Abution, Winds, and Xanthium.

The preferred compound according to the invention is 2'-methoxy-6'-methyl-N- (isopropoxymethy!) -2-chloroacetanilide.

Further compounds according to the invention are:

2'-methoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide,

2'-methoxy-6'-methyl-N- (l-sec-butoxymethyl) -2-chloroacetanilide, 2'-ethoxy-6'-methyl-N- (allyloxymethyl) -2-chloroacetanilide,
2'-ethoxy-6'-methyl-N- (propargyloxymethyl) -2-chloroacetanilide,
2'-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide,

IU DLD

2'-methoxy-6'-ethyl-N- (isopropoxymethyl) -2-chloroacetanilide,

2'-ethoxy-6'-methyl-N- (1-methylpropoxymethyI) -2-chloroacetaniIid,

2'-n-propoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide,

2'-Isopropoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide and

2'-Isopropoxy-6'-methyl-N- (n-propoxymethyl) -2-chloroacetaniIide.

The compounds of the invention can be prepared in various ways. So you can z. B. on the azomethinewcg described in U.S. Patents 3,442,945 and 3,547,620 mentioned above In this azoraethine process, the appropriate primary aniline is converted into the appropriate primary aniline with formaldehyde Methylenaniline (substituted phenylazomethine) reacted, which is then treated with a halogen acetylating agent such as Chloracatyl chloride or chloroacetyl anhydride is implemented. Then use the appropriate alcohol converted to the corresponding N-alkoxymethyl-2-chloroacetanilide as the end product

Another method, described in more detail below, provides for the transetherification of the appropriate N-methylene ether-2-haloacetanilide with the desired alcohol to the corresponding unetherified N-hydrocarbylmethyl-2-haloacetanilide before.

Yet another process for the preparation of compounds according to the invention provides an N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent among basic Conditions before. The N-alkylation process is described in more detail in Examples 11-14.

example 1

This example describes the preparation of 2'-methoxy-6'-methyl-N- (isopropoxym '. 3iyl) -2-chloroacetanilide described.

0.025 mol of 2'-methoxy-6'-methyl-N- (methoxymethyl) -2-chloroacetanilide in 100-150 ml of isopropanol, which contained about 0.02 mol of methanesulphonic acid, was kept under reflux conditions in a Soxhlet extraction apparatus g of activated 3A molecular sieve to absorb the released methanol. The course of the reaction was followed by gas-liquid chromatography. After the reaction had ended, the excess alcohol was removed in vacuo and the residue was taken up in ether or chloroform. The solution was washed with 5% sodium carbonate solution, dried (Mg ₂ SO-d O ^{un ver} "evaporated The product was purified by Kugelrohr distillation yield 55%;. Pale amber solid, mp 40-41 ⁰ C.

Elemental analysis for C | ₄ H ₂₀ ClNO ₃ (%):

Calculated: C58.34; H7.05; N4.90; Cl 12.41 Found: C, 58.55; H 7.08; N 4.89; Cl 12.45

The product was identified as the compound mentioned at the outset

Examples 2 to 9

Practically the same procedures, amounts of reactants and described in Example 1 were used general conditions were used, but the one suitable for transetherification to the final product was used Alcohol substituted by other N-hydrocarbyloxymethyl-2-haloacetanilide corresponding to the above formula to manufacture; these compounds are listed in Table I.

Table I.

example
No. link Empirical formula Kp. "C
(mbar) analysis
element Calculated Found 2 2'-methoxy-6'-methyl-N-
(ethoxymethyl) -2-chloro-
acetanilide C _n H ₁₈ ClNO ₃ 170
(0.13) C.
H
N 57.46
6.67
5.16 57.19
6.70
5.11 3 2'-methoxy-6'-methyl-
N- (I -methylpropoxymethyl) -
2-chloroacetanilide C ₁₅ H ₂₂ ClNO ₃ C.
H
N
Cl 60.10
7.40
4.67
11.83 59.90
736
4.62
11.97 4th 2'-ethoxy-6'-methyl-
N- (allyloxymethyl) -2-chloro-
acetanilide CioH ₂₀ ClN0 ₃ 110
(0.093) C.
H
N
Cl 60.50
6.77
4.70
11.91 00.30
6.80
4.64
11.69

Table! (Continued)

example No.

link Empirical formula

Kp. ° C (mbar)

Analysis element

Calculated Found

2'-ethoxy-6'-methyl-
N- (propargyloxymethyl) -
2-chloroacetanilide C ₁₅ H ₁₈ CINO ₃ 140
(0.13) C.
H
N
Cl 60.91
6.13
4.74
11.99 60.98
6.14
4.74
11.94 2'-ethoxy-6-methyl-
N- (1-methylpropoxy-
methyl) -2-chloroacetanilide C ₁₆ H ₂₄ CINO ₃ 135
(0.12) UXZU 61.24
7.71
4.46
11.30 60.98
7.69
4.42
11.22 2'-methoxy-6'-methyl-
N- (isobutoxymethyl) -2-
chloroacetanilide C ₁₅ H ₂₂ ClNO ₃ 140
(0.13) UXZU 60.10
7.40
4.67
11.83 59.88
7.41
4.62
11.82 2'-methoxy-6'-methyl-N-
(cyclopropylmethoxy-
methyl) -2-chloroacetanilide Ci ₅ H ₂₀ CINO ₃ 145
(0.13) UXZU 60.50
6.77
4.70
11.91 60.26
6.77
4.66
11.80 2'-methoxy-6'-ethyl-N-
(isopropoxymethyl) -2-
chloroacetanilide C ₁₅ H ₂₂ CINO ₃ oil QZXO 60.10
7.40
4.67
11.83 59.81
7.46
4.61
11.71

Example 10

Preparation of the tertiary N- (methoxymethyl) anilide starting materials used in Examples 1 to 9 above. The production of the starting material of Example 1 is described by way of example:

0.025 mol of 2'-methoxy-6'-methyl-2-chloroacetanilide, 0.05 mol of bromomethyl methyl ether and 2 g of benzyltriethylammonium bromide were dissolved in 70 ml of methylene chloride. 40 ml of 50% sodium hydroxide solution was then added in portions with stirring and cooling, whereby the temperature was kept between 20 and 25 ° C. When the addition was complete, the mixture was stirred for a further 1.5 hours. 100 ml of water were then added with cooling and the layers separated. The methylene chloride layer was washed twice with 30 ml of saturated sodium chloride solution, dried (Mg ₂ SO ₄ ) and evaporated. The residue was crystallized out or distilled in vacuo, giving a yellow liquid, boiling point 140 ° C. at 1.6 mbar.

Elemental analysis for Ci ₂ Hi _{5 CINO 3} ( ⁰ Zo):
Calculated: C, 55.92; H 6.26; N 5.44
Found: C, 56.15; H 633; N 536

The product was identified as 2'-methoxy-6'-methylene-N- (methoxymethyl) -2-chloroacetanilide.

The N-methylene ether-substituted 2-chloroacetanilide starting materials of Examples 2 were prepared in the same way to 9 prepared by alkylation of the corresponding secondary anilide with bromomethyl methyl ether; even the analogous chloromethyl and iodomethyl methyl ethers can be used.

The secondary used in this example to prepare the tertiary N-methoxylmethyl compound Aniline starting material was obtained by chloroacetylation of the corresponding primary amine as follows:

0.03 mol of 2-methoxy-6-methylaniline in 30 ml of methylene chloride was vigorously mixed with 0.05 mol of 10% sodium hydroxide solution stirred while a solution of 0.033 mol of chloroacetyl chloride in 20 ml of methylene chloride was added became; the temperature was kept between 15 and 25 ° C. with the aid of external cooling. That After the addition was complete, the reaction mixture was stirred for a further 30 minutes, the layers separated and the Methyienchioridschicht washed out with water, dried and evaporated in a vacuum. The product was crystallized from a suitable solvent to give white needles, m.p. 130-131 ° C

Elemental analysis for CiOHi ₂ CINO ₂ ( ⁰ A):
Calculated: C, 56.21; H 5.66; N 6.56; Cl 16.59 Found: C56.16; H5.66; N6.57; Cl 1635

The product was identified as 2'-methoxy-6'-methyl-2-chloroacetaniIide

The secondary anilides used as starting materials in Examples 2 to 9 were prepared in a similar manner
The primary amines used to prepare the above-mentioned secondary anilides can be used with

known methods are produced, e.g. B. by catalytic reduction of the corresponding substituted Nitrobenzene in ethanol using a platinum oxide catalyst.

The products according to the invention can also be obtained directly from the secondary anilide using the

mentioned N-Alkylierurigsver method can be obtained without that described in Example 10 first

N-alkoxytitethyl intermediate is prepared, which is then to the end product described in Example 1 jj

is reethered. In Examples 11 to 14, the preparation of compounds according to the invention with j

the N-alkylation process. ;

Example 11

4.35 g of 2'-n-propoxy-6'-methyl-2-chloroacetanilide, 3.4 g of chloromethyl ethyl ether, 1.5 g of benzycriethylammonium

chloride were mixed in 250 ml of methylene chloride and cooled. 50 ml of 50% strength NaOH were added to the mixture at 15 ^° C. and the mixture was stirred for 2 h, then 100 ml of water were added. The layers were separated, washed with water, then dried over MgSO4 and evaporated. The product was purified by Kugelrohr distillation to give 4.8 g (89% yield) of clear liquid, bp. 130 ⁰ C at 0.093 mbar.

Elemental analysis for Cr ₁ H _{22 CINO 3} ^ Zo):
Calculated: C60.10; H 7.40; Cl 11.83
Found: C, 59.95; H 7.39; Cl 11.79

The product was identified as, 2'-n-propoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide.

Example 12

5.55 g of 2'-isopropoxy-6'-methyl-2-chloroacetanilide, 4.4 g of chloromethyl ethyl ether, 2.5 g of benzyltriethylammonium chloride in 250 ml of methylene chloride were mixed and cooled to 0 ° C. To the mixture was added 50 ml 50% NaOH was added all at once while keeping the temperature below 15 ° C. The mixture was stirred for 2 h, cooled, then 100 ml of water were added. The layers were separated with water washed, dried over MgSO4, and evaporated to give 4.7 g (69% yield) of product in

Form of a yellow oil.

Elemental analysis for C ₁₅ H _{22 ClNO 3} ^ Zo):

Calculated: C, 60.10; H 7.40; N 4.67; Cl 11.83
Found: C, 60.10; H 7.40; N, 4.64; Cl 11.73

The product was identified as 2'-isopropoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide.

Example 13

Practically the same procedure as described in Examples 11 and 12 was used, however chloromethyl propyl ether was used as the alkylating agent. 5.0 g (88% yield) of a yellow one were obtained Oil.

Elemental analysis for C ₁₆ H _{24 CINO 3} ^ Zo):
Calculated: C, 61.24; H 7.71; N 4.46; CIlUO
Found: C, 61.18; H 7.76; N 4.43;

The product was identified as 2'-isopropoxy-6-methyl-N- (n-propoxymethyl) -2-chloroacetanilide.
Example 14

The same procedure as described in Examples 11-13 was followed, except that the suitable secondary anilide and halomethyl ailyl ether substituted. A yellow oil, boiling point 134 ° C., was obtained 0.11 mbar (spherical tube).

Elemental analysis for Ci ₄ H _{18 CINO 3} ^ Zo):
Calculated: C 593; H 639; N 634; Cl 12.49
Found: C59.20; H 6.41, N635, CI 1232

The product was identified as 2'-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide

It has been found that the herbicides according to the invention are unexpectedly superior as pre-emergence herbicides, especially for the selective control of perennial and annual weeds that are difficult to kill, in addition include perennial weeds such as couch grass and yellow sedge, annual broad-leaved weeds such as thorny sida, hemp sesbania, thorn apple, knotweed plants, melde, goosefoot plants, as well as annuals Grasses such as Sorghum halepense seedlings, Shattercane, Brachiaria plantaginea, Texas panicum, red rice, wild Millet, raoule grass, foxtails (e.g. green and large), barnyard grass and large digitaria. Also was im Compared to known Acetaniiiden an improved reduction of the weed population of other resistant ones Types such as B. Ambrosiaceae, Abutilon, Winde and Xanthium achieved

Selective control and improved suppression of the mentioned weeds with the inventive Herbicide has been observed in a wide variety of crops including soybeans, cotton, peanuts, canola and French beans. Selectivity was also found in some tests for sugar beet, field maize, sweet maize, wheat, Barley and sorghum shown; however, these cultures are generally opposed to those according to the invention Herbicides less tolerant than the above crops.

To the unexpectedly superior properties of the compounds according to the invention both on absolute As to be presented on a relative basis, comparative greenhouse and field tests were conducted, viz with:

1. Known compounds which, in their chemical structure, correspond to the compounds according to the invention on next related;

2. other homologues from the area of the known compounds mentioned, the outstanding herbicidal Possess properties;

3. Commercially available herbicide compounds whose chemical structure is generally similar to that of the invention Connections is related. All compounds in the comparison tests listed below are in the generally defined as substituted phenyl-N-alkoxyalkyl-2-haloacetanilides. In the tables are the compared known compounds identified as follows:

A. 2'-Methoxy-6'-tert-butyl-N- (methoxymethyl) -2-chloroacetanilide (Example 18, U.S. Patent 3,442,945 and 35 47 620).

B. 2'-ivicinoxy-6'-icri.-butyi-N- (rneihuAynicihyi) -2-brorriaceianilide (Example 34 of US Pat. No. 3,547,620 and a Example 36 of US-PS 34 42 945).

C. 2 ', 6'-Diethyl-N- (methoxymethyl) -2-chloroacetanilide (Example 5 of U.S. Patents 3,547,620 and 3,442,945; these Compound is known under the name »Alachlor« and represents the active ingredient in the commercially available one LASSO herbicide, registered trademark of Monsanto Company).

D. 2'-Methyl-6'-ethyl-N- (ethoxymethyl) -2-chloroacetanilide (Example 53 of U.S. Patent 3,547,620; general Designation »acetochlor«).

E. 2 ', 6'-Dimethyl-N- (isopropoxymethyl) -2-chloroacetanilide (Example 31 of US Pat. No. 3,547,620 and Example 33 of US-PS 34 42 945).

F. 2'-Methoxy-6'-methyl-N- (methoxyethyl) -2-chloroacetanilide (Compound No. 6 of BE-PS 8 10 763).

G. 2'-Methoxy-6'-methyl-N- (ethoxyethyl) -2-chloroacetanilide (Compound No. 7 of BE-PS 8 10 763). H. 2'-Methoxy-6'-methyl-N- (1-methoxyprop-2-yl) -2-chloroacetanilide (Compound No. 9 of BE-PS

8 10 763) and

I. 2'-Methyl-6'-ethyl-N- (1-methoxyprop-2-yl) -2-chloroacetanilide (US Pat. No. 3,937,730; general name "Metolachlor"; this compound is the active ingredient in the commercially available herbicide »Dual«, registered trademark of Ciba-Geigy Corporation).

In pre-emergence herbicide tests, compounds according to the invention were compared with the known compounds A to! hirssichtüch the control of various multilateral or annual weeds compared, the difficult be killed species that primarily so important cultures ^{w 's} soybeans, cotton, peanuts, rape and bush beans infested were given special consideration. The test results are summarized below.

In the following discussion of the data, reference is made to herbicide application rates starting with »GR15« and "GRk" are displayed; these amounts are given in "pounds per acre" (lbs / A), which is achieved by multiplying 1.12 can be converted into kg per hectare (kg / ha). GRi 5 defines the maximum amount of herbicide where damage occurs to 15% or less of the crops, while GRss the necessary The minimum amount with which an 85% inhibition of weeds is achieved. The GR15 and GRes sets are used as a measure of the possible performance of commercially available products, of course suitable commercial herbicides, within reasonable limits, greater or lesser damage to plants can have.

A further indication of the effectiveness of a chemical as a selective herbicide is the »selectivity factor« (»SF«) for a herbicide on starry crops and weeds. It is a measure of the degree of harmlessness to crops and is expressed as the ratio GRis / GRgs, ie GR _{] 5} amount for the crop divided by GR «amount for the weed, both amounts expressed in lbs / A and kg, respectively /Ha. In the tables, the selectivity factors, if used, are given in brackets after the weed; "NS" means "not selective"; insignificant or indeterminate selectivity is indicated with a dash after the weed, an empty space means that the plant species was not involved in a particular test, that the data for some reason was not obtained or was less significant than existing data; for example, shorter-term observations are not given in favor of longer-term data, or longer-term data are omitted because data for a shorter period were definitive for a certain herbicidal activity.

Since crop tolerance and weed control are related, a brief discussion is eo this ratio, expressed as the selectivity factor, is appropriate. In general, it is desirable that the Harmlessness factors for the cultivated plant are high, because for one reason or another often higher Herbicide concentrations are desired.

Conversely, the quantities for weed control are said to be economical and possibly ecological Reasons to be small, d. that is, the herbicide should have a high unit activity. Small application rates however, a herbicide may not be sufficient to control certain weeds and it becomes a Larger Amount Required The best herbicides are therefore those that require the least amount of application Control the greatest number of weeds and the greatest possible harmlessness for the crop, d. H.

Crop tolerance, provide. The selectivity factors (defined above) are therefore used to determine Yes To quantify the relationship between harmlessness to the crop and control of weeds; for the selectivity factors given in the tables apply: the higher the numerical value, the greater the Selectivity of the herbicide for weed control in a given crop.

The listed preliminary tests include both greenhouse and field tests. In the greenhouse tests, the herbicide is applied either or after planting of the seeds or cuttings to the surface, e ^r is incorporated into a specific amount of soil that is to be spread as a cover layer over the test seeds sown in test containers. In the field tests, the herbicide is incorporated into the soil before planting (R PI) d. That is, it is applied to the surface of the earth, then mixed with the earth, then the crop seeds are planted out.

The surface test procedure used in the greenhouse is carried out as follows: Container, e.g. B. Aluminum pans with about 24 χ 13x7 cm, or plastic pots with about 9.5 χ 9.5 χ 8 cm, with drain holes in the bottom, are filled to the brim with Ray silt loam, which is then up to a height of 1.3 cm is knocked down below the edge of the pot. The pots are then sown with a plant species to be tested and covered with a 1.3 cm high layer of the test soil. The herbicide is then applied to the surface of the earth with a belt sprayer (187 l / ha, 2.11 kg / cm ² ); on occasion, other spray devices, such as. B. used a DeVilbiss sprayer. Each pot is doused with 0.64 cm of water from above, then the pots are placed on greenhouse tables and watered from below as required. In an alternative method, watering from above can also be omitted. The effect of the herbicide is determined about 3 weeks after the treatment.

Herbicide treatment by working it into the soil is done as follows in greenhouse tests:

Guier topsoil is placed in aluminum pans and up to 1 to 1.3 cm below the edge knocked down. A number of seeds or cuttings of various types of plants are distributed on the earth. The for Complete filling of the pans after sowing or planting soil is necessary in a pan weighed. The earth and a known amount of active ingredient in the form of a solution or suspension of wettable powder are mixed thoroughly and used to cover the prepared pans. To after treatment, the pans receive an initial watering from above, which corresponds to 0.64 cm of rainfall, then they are watered from below as needed, leaving adequate moisture for germination and the growth is present. Irrigation from above can also be omitted. Assessment takes place around 3 Weeks after sowing and treatment.

Table II lists the data for herbicidal activity in a first series of pre-emergence tests; this shows the relative efficiency of compounds according to the invention with related known compounds in the control of yellow sedge and couch grass in soybean, cotton and maize crops.

Table II

Amount for G Rs;

(kg / ha)

Cyperus

Couch grass

Men ^ eforGP · « (kg / ha) "~ soybeans

cotton

A. > 2.2 1.6 3.1 (-)
0.28 (NS) > 2.2 (-) 0.17 (NS)
0.28 (NS) 45 B. 0.69 2.8 0.56 (NS)
1.1 (NS) > 2.2 (> 2.0) 0.034 (NS)
0.07 (NS) 50 C.
D. 0.45
0.2 0.56
0.18 1.7 (4)
1.1 (2)
0.39 (1.5)
0.39 (2) 0.25 (1) 0.78 (2)
0.84 (1.5)
0.22 (1)
0.22 (1) 55 E.
F. 0.17
034 0.27 0.21 (1)
0.21 (NS)
0.21 (NS) 0.48 (3)
0.21 (NS) 0.09 (NS)
<0.22 (NS)
<0.22 (NS) 60 G 0.25 0.20 <0.07 (NS)
<0.07 (NS) 039 (U) <0.07 (NS)
<0.07 (NS) H 1.5 0.36 2.2 (1.5)
2.2 (6) 2.9 (2)
2.7 (7.5) <1.5 (NS)
1.25 (3.5) 65 I. 1.7 0.9 <1.7 (NS)
U (U) <1.7 (NS)
U (U) <1.7 (NS)
<0.9 (NS)

Table II (continued)

link Amount for GRs5
(kg / ha)
Cyperus Quei example 1 0.10 0.20 Example 2 0.17 0.07 Example 3 0.26 0.13 Example 4 034 0.22

Quantity for GRi ₅

(kg / ha)

Soybeans

cotton

Corn

Example 5 Example ö Example 7 Example 8 Example 9 Example 12 Example 13 Example 14

03 0.26 0.22 037 0.56 0.12 0.22 036

028 0.28 0.56 0.17 0.47 0.11 0.28 0.50

028 (3)
0.28 (1.5)

0.17 (1)
0.13 (2)

0.77 (3)
0.81 (6)

1.0 (3.0)
1.0 (43)

3.4 (12.0)
3.4 (12.0)

2.0 (8.0)
2 ^ (8.0)

030 (4.0)
030 (1.6)

036 (13)
036 (33)

5.6 (10.0)
5.6 (113)

028 (2.5)
028 (23)

0.45 (2.0)
036 (2.0)

> 5.6 (> 15.6)

028 (3)

0.17 (1)
0.07 (1)

0.77 (3)

1.0 (3.0)

2.8 (10.0)

23 (10.0)

13 (63)

0.72 (13)

1.7 (3.0)

025 (2.0)

2.7 (12.0)

1.4 (33)

<0.07 (NS)

<0.07 (NS)

<0.17 (NS)

<0.07 (NS)

<026 (NS) <0.13 (NS)

<034 (NS)

<022 (NS)

<028 (NS)

<028 (NS)

<026 (NS)

<028 (NS)

<0.15 (NS)

<0.15 (NS)

<0.13 (NS)

<0.13 (NS)

<028 (NS)

<028 (NS)

<0.12 (NS)

<0.11 (NS)

<022 (NS)

<028 (NS)

5.6 (15.6) 5.6 (11.1)

From Table II it can be seen that, in general, the compounds of the invention are significant as a class are more active, d. H. have a higher unit activity against Cyperus esculentus and couch grass, and one higher harmlessness to soybeans and cotton than the reference compounds.

The control of Cyperus esculentus showed that each tested compound of the invention was remarkably more active than compounds A and B, which are structurally closest to the reference compounds are related, and also as compound H, which is less related than A and B, but which is to a certain extent Regard can be regarded as more closely related to the compounds according to the invention than the compounds C, D, E and I.

In particular, it should be noted that the compound of Example 1 at a GRgs level of 0.10 kg / ha approximately Was twice as active as the most active reference compound E (GR45 0.17 kg / ha), while it was 3 times as high Possessing a harmlessness factor like compound E for soybeans and an equivalent harmlessness for cotton. The compounds according to the invention of Examples 2 and 12 also had equivalent or greater values Unit activity as compound E against Cyperus esculentus. The reference compounds F and G have although fairly high unit activity, none of the compounds were selective towards Cyperus in Soybeans, nor was Compound F selective in cotton. Compound G controlled Cyperus in Cotton, but the harmlessness was lower than that of all compounds according to the invention, with the exception of Example 2, and markedly lower than that of Examples 5, 6 and 13. The selectivity factors of the compounds of Examples 9 and 14 against Cyperus in soybeans were particularly excellent.

For the couch grass control, the compound of Example 2 was nearly 3 times as active as the most active Reference chemical compound D, while equivalent soybean harmlessness was achieved. The compound according to the invention of Example 3 had a higher unit activity against couch grass and 3 times as high a level of harmlessness for soybeans as compound D. Here, too, it can be stated that each According to the invention, the tested compound of the present invention exhibited excellently superior unit activity against couch grass compared to Compounds A and B, which are the most closely related reference compounds tested represent. The unit activity of the compound H against couch grass was slightly higher than that of the Compounds of Examples 9 and 14, the selectivity factors of these latter compounds in Mercury in

weed % Control at 336 kg / ha C. D. link 35 73 example 1 0 69 Sida spinosa 93 62 88 Sesbania exaltata 100 64 76 Amaranthus 83 61 81 Polygonum 88 53 43 Report 75 68 98 Ambrosiaceae 72 Thorn apple 98

However, soybeans were about 2 times that of compound H, the most closely related reference compound. Incidentally, the reference compounds A, B, F and G were not against couch grass in soybeans selectively.

Table II also shows that of all the compounds tested, the compounds of Examples 5,6,9 and 14 by far the highest soybean safety factors relative to Cyperus and couch grass possessed. The compounds of Examples 5, 6 and 13 had by far the highest safety factors for Cotton, relative to Cyperus esculentus. It should also be noted that the extremely good safety factors of the compounds of Examples 5, 6, 9, 13 and 14 were associated with very low amounts of GRgs, indicating high unit activity against Cyperus and couch grass. In these tests, most were according to the invention Compounds not selective in corn, the same is true for all but three reference compounds. the Compound of Example 14, however, showed extraordinarily superior selectivity relative to mercury and Cyperus in corn.

In further comparative tests, the herbicidal pre-emergence activity of the reference compounds C and D and the compound of Example 1 on various annual broad-leaved weeds with one application rate of 336 kg / ha tested. The assessment took place 6 to 7 weeks after the treatment (WAT) and the percent control of weed growth was recorded. The data from this test are in the table III compiled

Table HI

20 Control of annual broad-leaved weeds

Pre-emergence test 6 to 7 WAT

From Table III it can be seen that the compound of Example 1 has excellent superior activity in the Comparison for Compound C versus each broadleaf weed tested. Equally shows the compound of example i markedly superior activity compared to compound D against Sida spinosa, Sesbania exaltata, Polygonum, and Ambrosiaceae, while having equivalent activity as opposed to Thorn apple, and exhibited slightly lower activity against Amaranthus and Melde.

For further comparisons, field tests were carried out to determine the relative pre-emergence activity and selectivity of the compound of Example 1 compared to the reference compounds C, D, E and I against Echinochloa, Sida spinosa and Sesbania exaltata in soybeans. These tests were carried out on individual plots using Sharkey clay containing 2.0% organics; this was treated with different concentrations of each herbicide, which was applied as an emulsifiable concentrate at an application rate of 280.6 l / ha. The assessment took place 4 weeks and 7 weeks after the treatment. The test data, which are based on 3 runs, show that after 7 weeks only the compound of Example 1 selectively controlled Sesbania exaltata; this control (GRgs) was achieved at only 1.96 kg / ha, while GR _{85 was} 5.6 kg / ha for each of compounds C, E and 1 and 5.0 kg / ha for compound D. GRi 5 in soybeans was 3.9 kg / ha which gave a 2.0 fold safety factor for compound of Example 1. In order to achieve the same GRgs value, about three times the amount of the compound of Example 1 was required of the reference compounds, but without selectivity in soybeans.

Compounds C and D were non-selective towards Sida spinosa in soybeans at 7 WAT. from Compound I was 4.2 kg / ha and Compound E 2.8 kg / ha to achieve GRgs and 1.1 or 1.5 times the selectivity factors are required. With the compound of Example 1, however, GRgs was 0.8 kg / ha and

55 achieved a 4.7-fold selectivity factor in soybeans.

Compounds C, D and E were not selective towards Echinochloa in soybeans at 7 WaT. Compound I and compound from Example 1 had practically equivalent harmlessness factors, ie 1.5 times compared to 1.4 times.
The field tests show that, with the exception of a comparable control of Echinochloa by compound I, the compound of Example 1 was significantly superior to the reference compounds CD, E and I in the selective control of all three annual weeds in soybeans 7 weeks after treatment.

In further tests to determine the relative herbicidal activities and selectivities over an even longer period Periods of time the same herbicides were re-examined in field tests as in the previous tests, this time in individual plots from silty clay to silty clay loam with a 3.0 to 3.5% share organic matter. In parallel tests, emulsifiable concentrates of the respective Herbicides applied to the surface or incorporated into the soil before planting, again with 280.5 l / ha, which contained the appropriate herbicide concentration as active ingredient. In these tests, the Herbicides in the control of the perennial couch grass and the annual broad-leaved weeds Ambro-

! 0

siaceae, Amaranthus and Polygonum in soybeans compared. These tests were heavy knockdowns exposed, 4.45 cm on the fifth day after treatment ("DAT"), and 2.29 cm, 1.52 cm, 1.27 cm on the following days. The data are summarized in Table IV

Table IV
Pre-emergence activity WAT 3
6th Incorporation before planting
GR & j amount (kg / ha)
Couch grass Ambrosiaceae 5.6
> 6.7. Amaranthus Polygonum GRi5 amount (kg / ha)
Soybeans link 3
6th
93 3
6th
9.5 22nd
23 > 6.7
> 6.7 23
3.4 1.7
23
> 3.4 example 1 3
6th
93 3
6th > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 > 6.7 > 6.7
> 6.7 > 43
> 43
> 43 C. 3
O
S3 3
6th
9.5 5.6
> 6.7
6.7 > 6.7
> 6.7 > 6.7 5.6
> 6.7 33
42
43 D. 3
6th
93 3
6th
9.5 > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 42 43
4.5 22nd
2.8
42 E. 3
6th
93 > 6.7
> 6.7
> 6.7 > 6.7 > 6.7
5.9 1.7
5.0 I. Surface treatment 43
5.0 example 1 2.5
23 > 6.7
> 6.7 43
3.4 3.4
4.8 13th
3.4 C. 5.9
> 6.7
> 6.7 > 6.7
> 6.7 43
5.0 > 6.7
5.9 3.9
22nd
> 4.5 D. > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 6.7
5.0 7.0
6.7 034
3.9
53 E. 5.6
> 6.7
> 6.7 > 6.7
> 6.7 5.6
5.0 4.5
5.6 23
2.0
4.8 I. > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 > 6.7
> 6.7 4.5
4.5
4.5

Table IV shows that when incorporated prior to planting, none of the reference bindings selectively controlled any of the tested weeds in soybeans at application rates of 6.7 kg / ha, the maximum test rate, 6 weeks and 9.5 weeks after treatment. As already mentioned, the selectivity is indicated by the selectivity factor, ie the ratio GR _i5 / GRg5, which gives a value of 1.0 or more; the higher the value, the greater the selectivity. In contrast, the compound of Example 1 showed selective control of couch grass, Amaranthus and Polygonum 6.0 WAT, and control of couch grass and Polygonum 9.5 WAT. The herbicidal activity of the compound of Example 1 is on the order of 3 times as great or greater than that of the reference compounds against couch grass and Polygonum (except for compound D), and about 2 times or more as active as the reference compounds (except for compound D 6 and 9.5 WAT and compound E 9.5 WAT). None of the herbicides selectively controlled Ambrosiaceae in this test, but the compound of Example 1 was 6 WAT more active against this weed than the reference compounds.

In the tests with the surface application of the herbicides, none of the reference chemicals controlled either one of the weeds in soybeans selectively at application rates of 6.7 kg / ha at 6 or 9.5 WAT, respectively Compound D at Amaranthus at 9.5 WAT. In these tests, selective weed control was used for the

Compound of Example 1 observed in couch grass and Polygonum at 6 WAT, and in Amaranthus at 9.5 WAT; the harmlessness factor here was slightly greater than that for compound D, i.e. H. 13-fold compared to 1.1 times. In these tests, too, the compound of Example 1 showed a significantly higher herbicidal rate Activity as the reference compounds.

It can be seen from the table that based on the following criteria, namely the unit activity against the weeds, the tolerance of soybeans to herbicides, the harmless factors and the application methods, the compound of Example 1 has significantly superior properties as a pre-emergence

herbicidal than the compared reference compounds.

The continued weed control by the compound of Example 1 under heavy rainfall showed

ίο. that the compound does not leach easily

In further comparative tests in the field, the compounds of Example 1 and the reference compounds D and E regarding the selective control of Sida. spinosa and Digitaria sanguinalis in cotton tested, applying the herbicide both to the surface and before planting in the Ground incorporated; yellow sedge was included in the test with pre-planting incorporation. the The soil used for the tests was silt loam with 1.7% organic content. Assessments were made 2, 6 and 9 Weeks after treatment. The data for the application on the surface, based on 3 passes, show that Compound 1 had more than 2 times the unit activity against Sida spinosa like that Compounds D and E at 6 WAT, and 1.5 times their activity at 9 WAT. Compound D was across from Sida spinosa in cotton at 6 or 9 WAT not selective. The selectivity factors for compound E at 6 resp.

9 WAT were 1.1 and 13, respectively, compared to 33 and 1.8 for the compound of Example 1. Although the unit activities of each compound tested were comparable to Digitaria at 6 WAT, - ^ ar the compound of Example 1 at 9 WAT more active than Compound E, and more selective (i.e. S.F. > 4.0) as compound D, the S. F. 2.8

exhibited.

In the pre-planting herbicide incorporated tests, the unit activity of the compound was Example 1 according to 9 WAT compared to Cyperus over 2 times as large as that of the reference chemicals, compared to Digitaria a little less than twice as large, and compared to Sida spinosa more than 1/3 times as large. With this one Field test controlled the compound of Example 1 Cyperus in cotton selectively up to 6 WAT while the Reference chemicals did not show selectivity even at 2 WAT. None of the test chemicals controlled Sida spinosa was selective in this PPI test; the compound from Example 1 was in comparison with the other compounds but much better. The compound of Example 1 and compound E controlled Digitaria just under 2 WAT, but were non-selective thereafter; the connection D was not opposite at any time Digitaria selective.

The most important conclusions from the above field tests in cotton are that the compound of Example 1 was significantly more active against the weeds Cyperus and Sida spinosa than the reference compounds, this activity being maintained over a longer period of time, and that the compound of Example 1 was compared with possessed selectivity factors superior to these weeds. Moreover, the compound of Example 1 had a superior unit activity when compared to Compound E, and a superior selectivity to Digitaria in cotton at 9 WAT when compared to Compound D.
Further comparative tests were carried out with the compound of Example 1 and the compounds Ii and E in order to determine their relative herbicidal effectiveness and the duration of action in the soil against the perennial weeds Cyperus exculentus and couch grass. Compounds D and E are among the most active selective herbicides of the known 2-haloacetanilides, and they were considered standards for this class in tests for other herbicides against cyperus and couch grass and other weeds. In the tests discussed here, 25 Cyperus tubers and 25 pieces of mercurial rhizomes were planted for 2 passes of each treatment. The herbicides were incorporated into the soil cover in amounts sufficient to determine the GRso-Menye, ie the minimum amount necessary to achieve 50% control of weeds; 11.2 kg / ha was the maximum amount and 1.4 kg / ha the minimum amount that was actually applied. Assessment took place 3, 6, 12 and 18 weeks after treatment. After each assessment, the soil cover layer was removed, the old tubers and rhizome fragments removed, planted again, then placed in the greenhouse for the next cycle. The test results are compiled in Table V, "WAT" means "weeks after treatment".

12th

Table V Duration of action in the soil

Compound C Rm kg / ha Cyperus esculentus

Couch WAT

example 1

<1.4 <1.4 3 <1.4 <1.4 6th 1.4 1.4 12th 8.4 11.2 18th <1.4 <1.4 3 U2 \ Ά 6th 5.9 5.6 12th IU > 11.2 18th <1.4 <1.4 3 1.4 IJ 6th 7.8 11.2 12th > U, 2 > 11 2 18th

The data for the control of Cyperus in Table V indicate that at 3 WAT the amount of GR 50 is each Compound was below 1.4 kg / ha, while at 6 WAT there were some critical differences. At 12 WAT essential differences in control of Cyperus were evident. While only 1.4 kg / ha of the compound of Example 1 were needed to control 50% of the weeds, 5.9 kg / ha of was needed Compound D and 7.8 kg / ha of Compound E to give the same level of control over Cyperus esculentus achieve. At 18 WAT, only 8.4 kg / ha of the compound of Example 1 became the 50% control of Cyperus needed compared to a mean who! over 11.2 kg / ha (the maximum amount used) of the compounds D and E.

Similarly, the data on couch grass in Table V shows that at 6 WAT the compound of Examples 1 and Compound D showed slightly superior activity over Compound E. At 12 WAT shows however, the extraordinary superiority of the compound of Example 1 in that it only requires 1.4 kg / ha to achieve the same control over couch grass, for those of compound D 5.6 kg / ha and of Compound E 11.2 kg / ha are required. The superior herbicidal activity of the compound of Example 1 was also evident at 18 WAT.

A major benefit of a herbicide is its ability to act in a wide variety of soil types. Accordingly, in Table VI, data are compiled showing the herbicidal activity of the compound of Example 1 on Cyperus in cotton and soybeans in a variety of soil types which have different proportions of organic matter and clay. The herbicides were worked into the soil the seeds planted 035 cm deep from above were watered at 0.64 cm. The assessment took place for 18 days after treatment.

Table VI Compound

example 1

Soil type Organic Shares,% Ray silt loam 1.0 Sarpy clay loam 23 Ceorgeville 23 silty clay loam Wabash clay 43 Drummer 6.0 silty clay loam Florida sand 63

Volume,% GR ₈₅
(kg / ha)
Cyperus GR ₁₅
(kg / ha)
cotton Soybeans 9.6
37.0 0.22
0.07
0.12 0.73
0.95
0.47 0.56
035
0.56 33.0
37.0 0.22
0.22 1.12
035 035
0.87

1.8

0.27

0.56

0.48

From Table VI it can be seen that the compound of Example 1 is fairly insensitive to soil type and Appears to be proportion of organic matter; it shows selective control of Cyperus in both cotton and also in soybeans in soils with 1.0 to 6.8% organic matter and 13 to 9.6% clay. The selectivity factors were largest in Sarpy clay loam.

Further tests were carried out to determine the herbicidal performance of the compound of Example 1 in soils to determine a large proportion of organic substances. In three repeated field tests, the activity was the compound of Example 1 against Amaranthus and Melde in soybeans tested those in black Peat soils were planted. Compounds C. D. E and I were also tested for comparison purposes These tests were carried out with both application methods, namely working into the ground or applying on the surface carried out they were made in black peat soil, which contained 23% organic matter Tests showed the compound of Example 1 to be the highest in both the P.PI and S.A. methods

Unit activity against reporting at 4 WAT and, for the P.PI method, the highest selectivity factor in soybeans, d. H. greater than 2.7 versus 1.1 for each of compounds C and D; the connections E and 1 were non-selective at 4 WAT. All connections were non-selective to reporting at 7 WAT, namely in neither of the two application methods; Compound E was slightly more active than compound from Example 1 at 7 WAT for both application methods. Compared to Amaranthus, connection D had the highest unit activity and the highest selectivity factor (1.9) 7 WAT for both application methods; in the method of application to the surface, the selectivity factor of Compound D was almost 2 times T. as large as that of compound of Example 1 and of compound E; no other connections controlled /) Amaranthus at 7 WAT selectively in one of the two application methods. The compound of Example 1

ίο (S.F. 2.0) and the compounds C and E (S.F. each 1.0) controlled Amaranthus selectively 4 WAT with the P. P. L method.

The above tests show that, in comparison with the reference compounds in black peat, the best selective control of reporting in soybeans obtained when the compound of Example 1 is in the soil is incorporated; this compound had the highest unit activity and the highest selectivity factor at 4 WAT from all tested connections. In addition, the compound of Example 1 controlled selectively Amaranthus up to 7 WAT with the surface treatment, and up to 4 WAT with the P.P.! - method. the Compound D gave the best control of Amaranthus at 7 WAT with both application methods. the relative performance of compound of Example 1 and compound D in black peat soil should be compared further are using the relative performance of these two compounds in soils containing less organic matter contained, e.g. B. 3.0-3.5% in which the compound of Example 1 has superior unit activity and lifetime in the soil together with selectivity in soybeans in both application methods shows, as shown in Table IV can be seen.

The compounds according to the invention thus show in the control of perennial weeds and annual weeds broad-leaved weeds in soybeans and cotton have excellent herbicidal effectiveness. Further resulted z. B. in the tests with Echinochloa and Digitaria that the compounds according to the invention also have a excellent herbicidal effectiveness against annual narrow-leaved weeds, d. H. Grasses, and with it one clear superiority over the most herbicidally effective and / or commercially available known ones Have 2-haloacetanilides. The test data reveals cases where a related known one 2-Haloacetanilide in comparison with compounds of the invention with respect to certain annuals Weeds shows superior herbicidal effectiveness under comparable conditions. From the present However, comparative tests also show that compounds according to the invention are overall the best 2-haloacetanilides as selective herbicides for the control of annual and perennial narrow-leaved ones Weeds in soybeans, cotton, peanuts and other crops are at least comparable and common are superior, sometimes in excellent ways.

In a pre-emergence test in the greenhouse, the compounds of Examples 1 and 11 were combined with the compounds C and E (which are both commercially available 2-haloacetanilides) for their relative herbicidal effectiveness against annual narrow-leaved weeds, d. H. Grasses tested in soybeans. In this test the herbicides were incorporated into the soil prior to planting the seeds and the observation was made Performed and recorded 17 days after treatment; the test data are summarized in Table VII and represent the average of 2 runs.

Table VII

Compound GR »s amount (kg / ha) GR | ₅ -quantity

Sorghum h. Sorghum Brachiaria Panicum Oryza Rottboellia (kg / ha)

Seedlings bicolor miliaceum sativa exaltata soybeans

0.56 0.95 0.84 -1.1

0.56 1.1 0.28> 1.1

0.56 1.1 1.1> 1.1

> 1.1> 1.1> 1.1> 1.1

When looking at the data in Table VII, the following main points should be noted:

1) Compound I showed the lowest unit activity and selectivity of all compounds against any weed tested, and showed no selectivity in soybeans for Panicum miliaceum, Oryza sativa or Rottboellia;
2) Compound C was as active as the more active compounds of Examples 1 and 11 against Sorghum bicolor and Panicum miliaceum;
3) the compounds of Examples 1 and 11 were both similar to the known compounds in Sorghum halepen-

se seedlings and rottboellia superior and

4) the compound of Example 11 was more active against Brachiaria pl, and the compound of Example 1 was more active towards Oryza s. than the known compounds.

From the comparative data of Table VII it can be seen that one or the other or both of the invention Relationship to two annual narrow-leaved weeds (Sorghum bicolor and Panicum miliaceum) herbizid were as effective as the best known reference compounds, and clearly better against four narrow-leaved weeds (Halepense Sorghum seedlings, Brachiaria plantaginea, Oryza

example 1 0.14 example 11th 0.28 50 C 0.56 I. 1.1

0.84 0.28 0.28 0.14 0.28 0.28 1.1 0.56

sativa and Rottboellia exaltata).

The excellent unit activity of the compound of Example 1 is particularly noteworthy
Sorghum halepense seedlings GRs5 = 0.14 kg / ha), which gives an excellent selectivity factor of around 8.0
in soybeans, compared with a selectivity factor of> 2.0 for Compound C, which gives the better
of the known compounds tested. Likewise, the compound of Example 11 showed excellent unit activity against Brachiaria pl. and Rottboellia e., with selectivity factors of> 8.0 and> 4.0 in
Soybeans, compared with corresponding selectivity factors of> 4.0 or> 1.0 compound C.

Another test was performed in soybeans, in addition to the other annuals
Grasses, which are already mentioned in the previous test, also seeds of Texas and autumn panicum
were used. In this test, the compounds of Examples 1 and 12 were compared with the known compounds C, D and 1 with regard to their herbicidal pre-emergence activity. The herbicides were used in the
Soil incorporated and watered from below as required. The maximum amount of herbicide used in this test
was 1.2 kg / ha, so the exact GRes and GR | 5 amounts above 1.2 kg / ha are to some extent
Dimensions indefinite. Assessment took place two weeks after treatment, the data of this test are in
Table VIII compiled. 15th

Table VIII Connection GRes amount (kg / ha) Panicum tex. Sorghum h.

Sorghum bicolor

Bracharia pi.

Panicum m.

Autumn panicum oryzasativa Rottboellia e.

GRi5 amount (kg / ha) soybeans

example 1 1.1 <0.07 0.14 0.56 0.56 <0.07 0.28 0.56 Example 12 0.28 <0.07 0.14 0.14 0.56 <0.07 0.21 0.07 C. 0.56 0.07 0.28 0.56 1.1 <0.07 0.28 > 1.1 D. 0.14 0.07 0.28 0.07 0.56 <0.07 <0.07 0.56 I. > 1.1 0.28 0.50 0.50 1.1 <0.07 0.56 0.84

Table VIII shows that the compounds according to the invention of Examples 1 and 12 are the highest Unit activities and selectivities of all compounds tested against Sorghum halepense and Sorghum bicolor exhibited; the compound of Example 12 had the highest activity and selectivity against Rottboellia and the compounds of Examples 1 and 12 had the highest activities against Panicum miliaceum to be associated with compounds D, and against Herbstpanlcum together with each of the known Links. However, the compounds of the invention were more selective than compound D in soybeans in relation to Panicum miliaceum. The compound of Example 12 was also the second most active compound against Panicum texanum and Oryza sativa, and the compound of Example 1 had together with compound D the second highest activity compared to Rottboellia. Compound D was the most active test compound against Panicum texanum, Brachiaria p. and Oryza sativa.

From the previous comparative data about the herbicidal activity against other grasses goes therefore show that the compounds according to the invention have a herbicidal activity that of those of the leading related known compounds is superior to certain annual grasses so z. B. towards Eehionochloa, Digitaria (S. L), Sorghum bicolor and Rottboellia, and that they are equivalent or generally have comparable herbicidal activity against other weeds, e.g. B. to Digitaria (S.A.), Panicum species, Brachiaria and Oryza sativa.

Other greenhouse and / or field tests found selective control by the compounds of the invention of other weed species in soybeans, cotton and / or other crops. For example, B. the Compound of Example 1, selective control over purple sedge and Setaria faberi in cotton, and Setaria faberi and Abutilon th. in soybeans. Compared to known related acetanilide herbicides the compound of Example 1 showed improved suppression of weeds as resistant as Ambrosiaceae, Ipomoea, and Xanthium. Further weeds against which the invention Compounds proven to be herbicidally active include: Field thistle, bindweed, downy bristle and knotweed.

The compounds of the invention have been found to be effective herbicides in a variety of crops; mainly in soybean and cotton crops, which are of particular interest here. Further Tests have shown the usefulness of the compounds according to the invention in other cultures as well

In a greenhouse test, the herbicidal pre-emergence activity of the compounds of Examples 11 and 12 tested and worked into the soil against couch grass in rapeseed, French beans, sorghum and wheat. Both compounds tested controlled selective couch grass in canola and French beans, the selectivity factor of the compound of Example 11 was 3.5 in both cultures, that of the compound of Example 12 was 3.0 in both cultures. In this test, both compounds were not selective against couch grass in sorghum and wheat.

The compound of Example 1 was also tested for herbicidal activity in separate greenhouse tests compared to yellow sedge or couch grass in rapeseed, peanuts, sugar beet, sorghum, wheat and barley tested; the herbicide was incorporated into the soil. In these tests, compound D was used as the reference compound against couch grass, and the compound E used as a reference compound against yellow sedge In the test with couch grass was assessed 19 days after the treatment (DAT), in the test with yellow Sedge 18 DAT; the test data are summarized in Table IX; the selectivity factors for the herbicides are given in brackets after the GRis amounts for the respective cultures.

Table IX

link

Weeds GR ₈₅ (kg / ha) couch grass

Culture GRis (kg / ha)

peanuts

Rapeseed

Sugar beet sorghum

wheat

barley

example 1
D. 0.045
0.034 0.28 (6.0)
0.034 (1.0) 0.13 (3.0)
0.06 (U) 0.28 (6.0) <0.034 (NS)
<0.034 (NS) 0.06 (1.0)
0.034 (1.0) 0.07 (U)
0.11 (3.0) Cyperus
esculentus example 1
E. 0.12
0.12 0.87 (7.0)
035 (8.0) 0.48 (4.0)
0.87 (7.0) 0.022 (NS)
0.022 (NS) 0.13 (1.0)
0.011 (NS) 0.13 (1.0)
0.045 (NS) 0.28 (2.0)
0.13 (1.0)

From Table IX it can be seen that the compound of Example 1 and the compound D both selectively contain couch potatoes in peanuts, rapeseed, sugar beets, wheat and barley that controlled the selectivity factor of the compound of Example 1, however, was significantly higher than that of compound D in peanuts, rapeseed and sugar beet, equivalent in wheat and lower in barley. The compound of Example 1 selectively controlled Cyperus esculentus in the cultures tested, excluding sugar beets, while compound E Cyperus in Was not selectively keeping sugar beet, sorghum, or wheat under control.

The high unit activity of compounds D and E appearing in Table IX is characteristic of the short term greenhouse performance (i.e., 2 to 6 weeks) for these compounds against couch grass and Cyperus esculentus. With the relevant test data compiled here from both greenhouse and field tests however, it was demonstrated that the compound of Example 1 compared to compounds D and E a uniformly superior uniform activity against couch grass and Cyperus and a superior selectivity in Owns cultures for much longer periods of time. In this context, reference is made again to:

1) Table IV, which compares data from field tests up to 9.5 weeks for the performance of these compounds contains against couch grass and other weeds in soybeans; (neither connection D nor connection E controlled couch grass in soybeans selectively even at 3 WAT);

2) the above discussion of comparative data from field tests for the performance of these compounds against Cyperus esculentus and other weeds in cotton for up to 9 weeks (neither compound D nor E

controlled Cyperus selectively in cotton even at 2 WAT); and

3) Table V, in the comparative data for the duration of action in the soil of the compound of Example 1 and the Compounds D and E against Cyperus and Quecke for 3, 6, 12 and 18 weeks are included.

As a result, the compound of Example 1 showed unit activities higher than those of the compounds D and E at 3 WAT (by several orders of magnitude when observing 12 WAT) and by an indefinite one Value when observing 18 WAT. It should also be noted here that the combination of superior unit activity, duration of action in soil and selectivity in crops of the compound of Example 1 in comparison with the compounds D and E against Cyperus and Quecke also for the relative Performance of these compounds in many other weeds is true, especially sorghum halepense seedlings, Sesbania exaltata, Sida spinosa, Polygon um, Melde etc.

In a multiple culture test, the pre-emergence activity of the compound of Example 1 was also tested in the field against certain annual weeds in multiple crops
In parallel tests, the herbicides were either applied to the surface or before planting in

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* ^ - | _ _a - ^ jj ι ij ^ r ^ J ^ · a B * w ■ ■ ■ af "" hi M ■ B ^^ btB Vr ^ v \ m Ä ^^^ vlL ^ Λ HI ^ rIII Ί BI t ^ m uaiu s \ ΈΒ j Ji ^ i B ^ j B KSAVBAAIbL ^ B ^ h * KS ^^ BA V »^ vA Λ ^ b ■ *. » ■ ^ L » ^ * T ^ pr M u & w 1 B ^ B ^ J'B 1 *> % ^ ₁ - β WflHIlvl V * tk ^^^ v ·

tests with incorporation into the soil before planting, and for tests with 34 days after treatment Applying the herbicide to the surface. In both tests the compound of Example 1 controlled selectively Echinochloa and Setaria viridia in corn, soybeans, cotton, French beans, and peanuts; Report was also checked in soybeans. In the P. P. L tests, Echinochloa and Setaria were also found

25 selectively controlled in sorghum and sweet corn

Toxicological studies of the compound of Example 1 showed that the compound was quite harmless It was slightly toxic when ingested orally (single oral dose LD50-2600 mg / kg), slightly toxic when ingested single dermal application (dermal LD »- 5010 mg / kg), it also produced a slight eye and Skin irritation. Special handling procedures beyond normal precautionary measures are not used

30 deemed necessary.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty acid alcohols, Amines or acid amides, long-chain acid esters of sodium isothionate, sodium sulfosuccinate ester, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, Polyoxyethylene derivatives of alkylphenols (especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives the higher fatty acid monoesters of hexitol anhydrides (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonate, polymeric alkylnaphthalene sulfonate, sodium naphthalene sulfonate, and polymethylene bisnaphthalene sulfonate

Wettable powders are preparations that are dispersible in water and contain one or more active ingredients contain inert extender and one or more wetting and dispersing agents. The inert ones Extensive solids are usually of mineral origin, e.g. B. natural clays, diatomaceous earth and synthetic Minerals of silica and the like. Such extenders include kaolinites, attapulgite clay and synthetic Magnesium silicate. The wettable powders of the present invention usually contain about 0.5 to 60% Parts (preferably 5 to 20 parts) active ingredient, about 0.25 to 25 parts (preferably 1 to 15 parts) Wetting agent, about 0.25 to 25 parts (preferably 1.0 to 15 parts) of dispersant, and 5 to about 95 parts (preferably 5 to 50 parts) of inert stretch solids, all parts based on the weight of the related to the entire preparation. If necessary, about 0.1 to 2 parts of the inert extender solids can be added be replaced by a corrosion inhibitor or foam inhibitor, or both.

Other formulations contain dust concentrates that contain 0.1 to 60% by weight of active ingredient on eicim Contain extenders; these dusts can be used with a concentration of about 0.1 to 10 wt .-%

50 to be diluted.

Aqueous suspensions or emulsions can be prepared by adding an aqueous mixture of a water-insoluble active ingredient and an emulsifier until uniform, and then stir it homogenized so that a stable emulsion of very finely divided particles is obtained. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that after Thinning and spraying the coating is very uniform. Appropriate concentrations of these preparations contain about 0.1 to 60% by weight, preferably 5 to 50% by weight, of active ingredient, the upper limit being the Solubility limit of the active ingredient in the solvent is determined.

Another type of aqueous suspension encapsulates a water-immiscible herbicide, see above that a microcapsule phase dispersed in an aqueous phase is formed. In one embodiment very small capsules are formed by adding an aqueous phase containing a lignosulfonate emulsifying agent water-immiscible chemical and polymethylene polyphenyl isocyanate that do not combine with Water-miscible phase dispersed in the aqueous phase and then a polyfunctional amine is added. The isocyanate and amine compounds react and form a solid urea shell around particles that do not interfere with Water-miscible chemical, so that microcapsules of the same are formed. In general, the concentration lies of the encapsulated material at about 480 to 700 g / liter, preferably 480 to 600 g / liter of the total Preparation.

Concentrates are usually solutions of active ingredient in water that is immiscible or only partially miscible with water Solvents, along with a surfactant. Suitable solvents for the active substance according to the invention

18th

fabric include Dimethylformide, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and not with water miscible ethers, esters or ketones. However, other strong liquid concentrates can also be dissolved by dissolving them the active ingredient in a solvent and subsequent dilution, e.g. B. with kerosene, for spray concentration be prepared.

The concentrate preparations generally contain about 0.1 to 95 parts (preferably 5 to 60 parts) Active ingredient, about 0.25 to 50 parts (preferably 1 to 25 parts) surfactant and, if necessary, about 4 to 94 parts Solvent; all parts are parts by weight and are based on the total weight of the emulsifiable oil.

Granules are physically stable, particulate preparations that contain an active ingredient that acts on a Matrix of inert, finely divided, particulate extender adheres or is distributed in the same. To that To support leaching of the active ingredient from the particles can have a surface effect in the preparation Means as listed above must be available. Natural clays, pyrophyllites, hats and vermiculites are there Examples of useful types of particulate mineral extenders. Preferred extenders are porous, absorptive, preformed particles such as preformed and sieved particulate attapulgite or Particulate vermiculite expanded by heat, as well as the finely divided clays such as kaolin clays, hydrogenated Attapulgite or bentonite clays. These extenders are used to produce the herbicidal granules with the Active ingredient sprayed or mixed

The granulate preparations according to the invention can contain about 0.1 to 30 parts by weight, preferably about 3 up to 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 Contains 100 parts by weight of clay particles.

The preparations according to the invention can also contain other conventional additives, eg. B. fertilizers, other herbicides, pesticides, or additives that act as adjuvants or in combination with any of the above listed adjuvants are used. Chemicals suitable for combination with the invention Active ingredients that are useful include: Triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, triazoles, benzoic acids, nitriles and biphenyl ethers.

In combination with the active ingredients, useful fertilizers are z. B. ammonium nitrate, urea, potash and superphosphate. Other useful additives are substances in which plant organisms take root and grow, e.g. B. compost, manure humus and sand.

For herbicidal preparations of the type described above, various examples are given below Embodiments indicated.

I. Emulsifier :; Concentrates

% By weight

A. Compound of Example No. '50 .0 Calcium Dodecylbenzoisulfonate /

(e.g. Atlox 3437 F and Atlox 3438 F) 5.0

Monochlorobenzene 45.0

100.0

B. Compound of Example No. 12 85.0 calcium dodecyl sulfonate / alkylaryl polyether alcohol mixture 4.0 C9 aromatic hydrocarbon solvent 11.0

100.0

C. Compound of Example No. 13 5.0 Calcium Dodecylbenzenesulfonate / Polyoxy-

ethylene

ether mixture (e.g. Atlox 3437 F) 1.0

Xylene 94.0

100.0

19th

II. Liquid concentrates

% By weight

A. Compound of Example No. 1 10.0 xylene 90.0

100.0

B. Compound of Example No. 2 85.0 dimethyl sulfoxide 15.0

ίο 100.0

C. Compound of Example No. 3 50.0 N-Methylpyrrciidone 50.0

100.0

5.0 20.0

0.5 74.5

15th D. Compound of Example No. 4 Ethoxylated castor oil Rhodamine B Dimethylformamide 20th III. Emulsions !. '■;

100.0

Wt%

A. Compound of Example No. 1 40.0

Polyoxyethylene / polyoxypropylene block

Copolymer with butanol (e.g. Tergitol XH) 4.0

Water 56.0

100.0 30

B. Compound of Example No. 5 5.0

Polyoxyethylene / polyoxypropylene block copolymer

with butanol 3.5

Water 91.5

100.0

IV. Wettable powders

Wt%

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

100.0

45

B. Compound of Example No. 6 80.00 Sodium Dioctylsulfosuccinate 1.25 Calcium Lignosulfonate 2.75 Amorphous Silica (synthetic) 16.00

so 100.00

C. Compound of Example No. 7 10.0 Sodium Lignosulfonate 3.0 Sodium N-methyl-N-Oleyl Taurate 1.0

Kaolinite clay 86.0

100.0

65

20th

V. Dusts

Wt%

A. Compound of Example No. 1 2.0 1 Attapulgite 98.0 5

100.0,

B. Compound of Example No. 8 60.0 Montmorillonite 40.0

100.0 10

C. Compound of Example No. 9 30.0 Bentonite 70.0

100.0

D. Compound of Example No. l 1.0 Diatomaceous earth 99.0

100.0

VI. Granules 20

Wt%

A. Compound of Example No. 1 15.0 Granulated attapulgite (20/40 sieve) 85.0

100.0

B. Compound of Example No. 12 30.0 Diatomaceous earth (20/40) 70.0

'00, 0

C. Compound of Example No. 13 0.5 30 Bentonite (20/40) J) W,

100.0

D. Compound of Example No. 14 5.0

Pyrophyllite (20/40) 95.0 35

100.0

VII. Microcapsules

Wt%

A. Compound of Example # 1 40 encapsulated in polyurea shell 49.2

Sodium lignosulfonate (e.g. Reax 88 B) 0.9

Water 49.9

100.0

B. Compound of Example No. 12

encapsulated in polyurea shell 10.0

Potassium lignosulfonate (e.g. Reax C-21) 03

Water 89.5

100.0 50

C. Compound of Example No. 13

encapsulated in polyurea shell 80.0

Magnesium salt of lignosulfate (Treax LTM) 2.0

Water 18.0 55

100.0

When used according to the invention, effective amounts of the acetanilides according to the invention are applied to the the soil containing the plants applied or appropriately taken up in aqueous media. That Application of the preparations as liquids and solid particles to the earth can be done with conventional 60 Procedures take place, e.g. B. with motorized atomizers, tank and hand sprayers or spray atomizers. The preparations Because of their effectiveness, they can also be distributed in small doses by airplanes as dust or spray will. The use of herbicidal preparations in aquatic plants is usually carried out by adding the Preparations for the aqueous medium in the area where control of aquatic plants is desired.

The application of an effective amount of the preparations according to the invention at the location of the unrelated 65 desired weeds is essential and critical to the application of the invention. The one to use exact amount of active ingredient depends on various factors, such as: B. on the type of plant and its stage of development, Type and condition of the soil, the amount of rain and the specific acetanilide used

21

Selective pre-emergence application to plants or soil will usually require an application rate of 0.02 to 11.2 kg / ha, preferably from about 0.04 to 5.60 kg / ha, or 1.12 to 5.6 kg / ha acetanilide is used. In some In some cases, larger or smaller quantities may be required. On the basis of the description, the person skilled in the art can including the examples, easily determine the optimal amount for each case.

The term "soil" is used in the broadest sense of the word and includes all common types of soil as described under "soils" in Webster's New International Dictionary, Second Edition, Unabridged (1961) are defined. The term refers to any substance or medium in which plants take root and can grow, and includes not only soil but also compost, manure, dung, humus and sand that Can sustain plant growth.

22nd

Claims (1)

Patent claims: 1. 2'-Methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetaniiide 2. 2'-Methoxy-6'-methyl-M- {ethoxymethyl) -2-chloroacetanilide. 5 3. 2'-Methoxy-6'-methyl-N- {1-methylpropoxymethyl) -2-chloroacetanilide. 4. 2'-Ethoxy-6'-methyl-N- (aUyloxymethyl) -2-chloroacetanide. 5. 2'-Ethoxy-6'-methyl-N- {propargyloxymethyl) -2-chloro-acetanide. 6. 2'-Ethoxy-6'-methyl-N- (1 -methylpropoxymethyl ^ -chloroacetanilide 7. 2 ^/ -Methoxy-6'-methyl-N- (isobutoxymethyl) -2-chloroacetanilide. 10 8. 2'-Methoxy-6'-methyl-N- ^ cyclopropylmethoxymethyl) -2-chloroacetanDicL 9. 2'-Methoxy-6'-ethyl-N-fisopropoxymethyl) -2-chloroacetanilide. 10. 2'-n-Propoxy-6'-methy] -N- (oxyxymethyl) -2-chloroacetanilide 11. 2'-Isopropoxy-6'-methyl-N- (ethoxyinethyl) -2-chloroacetaiilide. 12. 2'-Isopropoxy-6'-methyl-N- (n-propoxyniethyl) -2-chloroacetanilide. 15 13. 2'-Ethoxy-N- (allyloxymethyl) -2-chloroacetanilide. 14. Herbicide preparation containing a 2-chloroacetanilide according to claims 1 to 13 and usual Additives.