DE3110452C2 - 2-chloroacetanilides and herbicides containing them - Google Patents

Abstract

The invention relates to a group of N-alkyl-2-halogenoacetanilide compounds, herbicide preparations which contain these compounds as a material, and methods for using these herbicides in various crops of useful plants, in particular soybeans, cotton, peanuts, rape, French beans, etc. The herbicides according to the invention are particularly effective against the difficult to kill annual weeds Panicum texanum, Rottboellia exaltata, Panicum miliaceum, Brachiaria plantaginea, Oryza sativa, Sorghum bicolor and Sorghum halepense seedlings.

Description

The invention relates to 2-chloroacetanilides and herbicides containing them for combating undesired ones Plants in crops of useful plants, especially in soybean, peanut, rapeseed, cotton, French bean, Alfalfa and vegetable crops.

Numerous descriptions are found among the publications related to this invention with 2-haloacetanilides which are unsubstituted or with a large number of substituents on the anilide nitrogen atom or may be substituted on the anilide ring, e.g. B. with alkyl, alkoxy, alkoxyalkyl, halogen or

45 other groups.

The compounds according to the invention, which by a methyl or ethyl group on the anilide nitrogen, a Alkoxy group in one ortho position and a methyl group in the other ortho position are, as far as known, most likely those of US-PS 32 68 584, 34 42 945, 37 73 492 and 41 52 137. The patents 37 73 492 and 41 52 137 describe general formulas for herbicide compounds, which in general form comprise the compounds according to the invention. The only N-alkyl substituted one 2-haloacetanilide compound specifically described by both US Pat. Nos. 3,773,492 and 4,152,137 is propachlor, d. H. N-isopropyl-2-chloroacetanilide, a well-known commercial herbicide; none of the both patents contain herbicide data for propachlor. US Pat. No. 2,863,752 (Re 26,961) describes Compounds of a class including propachlor (not specifically mentioned) and homologues and analogs thereof includes. Of the compounds within the scope of US Pat. No. 2,863,752, propachlor was found to be Herbicide is the most effective and has therefore been developed as a commercial herbicide. In the patent mentioned the compounds mentioned therein are described in amounts as low as 1.12 kg / ha can be used; however, the experimental data presented in Example IV are based on application rates limited to 5.6 kg / ha and 28 kg / ha. Furthermore, in US Pat. No. 2,863,752, N-ethyl-2-chloroacetanilide is used as an example compound called; however, US Pat. No. 4,137,070 describes this compound as an antidote in its example 406 against the herbicide EPTC. In contrast to the compounds of US Pat. No. 2,863,752, those are according to the invention Herbicides highly effective selective herbicides against extremely difficult to control weed species at application rates that are well below 1.12 kg / ha and z. B. can be lowered up to 0.07 kg / ha can.

More structurally relevant than propachlor and related compounds are for the compounds according to the invention possibly compounds described in U.S. Patents 3,268,584 and 3,442,945. So will in particular in Example 13 of US Pat. No. 3,268,584, the compound N-tert-butyl-2'-methoxy-2-chloroacetanilide, and in Example 67 of US Pat. No. 3,442,945, the compound 2'-methoxy-6'-tert-butyl-2-chloroacetanilide is described.

Propachlor differs from the compounds according to the invention in the nature of the substituted Radicals in two positions, d. H. both ortho positions of the molecule, as well as the special one to the Alkyl group attached to nitrogen atom. The compound of Example 13 of US Pat. No. 3,268,584 differs in the nature of the substituent in one ortho position, the particular alkoxy group in the other orthe position, and the particular alkyl group attached to the nitrogen atom; and the compound of Example 5 67 of US-PS 34 42 945 differs from the compounds according to the invention by the type of Substituents attached to the nitrogen atom, as well as the particular alkyl or alkoxy groups that appear in are in the ortho positions of the anilide molecule.

US Pat. No. 4,146,387 describes 2-haloacetanilide compounds containing alkyl groups on the nitrogen atom and can be substituted in both ortho positions. The compounds of US-PS 41 46 387 are as known herbicides of the type described such. B. in the above-mentioned patents 34 42 945 and 28 63 752 are shown, including propachlor.

US Pat. No. 3,268,584 contains some herbicide data relating to a compound, its chemical Configuration is most closely related to the proper connections; some dates are also for other homologous and analogous compounds are given that are less closely related in their chemical structure are.

In particular, while these relevant references describe herbicidal activity on a variety of weeds, but they do not give any data for compounds that are additionally and / or simultaneously difficult Annual weeds to be killed such as Panicum texanum, Rottboellia exaltata, Panicum miliaceum, Brachiaria Keep plantaginea, Oryza sativa, Sorghum bicolor and Sorghum halepense seedlings under control while they also control a wide range of other harmful perennial and annual weeds, or push back, such as B. Cyperus esculentus, Polygonum, Melde, Amaranthus, Foxtails, 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 a longer period of time, the longer during a growing period, the better. With many known herbicides, adequate weed control is only achieved for 2 to 3 weeks, in some very in good cases, maybe up to 4 to 6 weeks before the chemical worsens 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 lifespan In the soil under normal weather conditions, failure to persist weed control is severe Precipitation that inactivates many herbicides.

Another disadvantage of many known herbicides is the limitation of their applicability to certain ones Soil types, d. i.e., while some herbicides are effective in soils with low organic content, they are in ineffective in other soils with high organic proportions, or vice versa. It is therefore an advantage if a Herbicide is useful in all types of soil from slightly organic soils to heavy clays and peat soils.

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 before Plants. The ability to apply a herbicide in any way, i. H. by applying to the Surface or incorporation before planting is very desirable.

Finally, a disadvantage of some herbicides is the need to remove them because of their toxicity must take special precautions for their handling. So a herbicide is also supposed to be safe to use be.

The object of the present invention is to provide a group of herbicidal compounds which avoid the above-mentioned disadvantages of known herbicides and offer a multitude of advantages that were not previously united in a single herbicide group, as well as the provision of a herbicide whose herbicidal effectiveness in the soil is maintained for longer periods of up to at least 12 weeks, against leaching or dilution at high humidity, e.g. B. is resistant to heavy rainfall, in is effective on a wide range of soils, from light organic soils to heavy clays or Peat soil, and is harmless and does not require any special handling precautions.

This object is now achieved by the 2-chloroacetanilides according to the main claim and the herbicide according to Claim 10. The subclaims relate to particularly preferred embodiments of this subject matter of the invention.

The 2-chloroacetanilides according to the invention are selectively effective against annual weeds that are difficult to kill, such as Panicum texanum, Rottboellia exaltata, Panicum miliaceum, Brachiaria plantaginea, Oryza sativa, Sorghum bicolor and Sorghum halepense while they control a wide range less enable resistant perennial and annual weeds and thereby for a large number of crops, such as soybeans, cotton, peanuts, rapeseed, French beans, alfalfa and / or vegetables are harmless are.

The 2-chloroacetanilides according to the invention develop due to their specific combination of alkyl groups on the anilide nitrogen atom in one ortho position and specific alkoxy groups in the other ortho position unexpectedly superior and excellent herbicidal properties compared to known herbicides, including the most closely related of the most relevant known compounds.

The 2-chloroacetanilides according to the invention correspond to the following general formula
O

10 "'I Π" ^0Ri

Sx!

R ₃

where mean:
15 either R ethyl and Ri η-butyl, R2 methyl and R3 hydrogen; or R methyl and Ri isopropyl or η-butyl, R2 methyl and R3 methyl in a meta position;

or R methyl and Ri ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, 2-methylbutyl,

1-methylpentyl, 2-methylpentyl or 13-dimethylbutyl, R _{2 is} methyl and R _{3 is} hydrogen;

or R methyl and Ri isopropyl, R2 ethyl and R3 hydrogen or methyl in a meta position;
20 or R is methyl and Ri is methyl, R _{2 is} tert-butyl and R _{3 is} hydrogen or methyl in a meta position.
Preferred compounds according to the invention are the following:

N-methyl-2'-isopentyloxy-6'-methyl-2-chloroacetanilide

N-methyl-2'-n-propoxy-6'-methyl-2-chloroacetanilide 25 N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide

N-methyl-2'-sec-butoxy-6'-methyl-2-chloroacetanilide, N-ethyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide N-methyl-2'-isopropoxy-6'-methyl-2-chloroacetanilide

N-methyl-2'-isobutoxy-6'-methyl-2-chloroacetanilide 30 N-methyl-2'-isopropoxy-6'-ethyl-2-chloroacetanilide

The compounds of the invention can be prepared in various ways. So can the production these compounds z. B. be done with a method that the N-alkylation of the anion of the appropriate provides secondary 2-haloacetanilide with an alkylating agent under basic conditions. That 35 N-alkylation procedures are described in Examples 1 and 2.

example

The preparation of N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide is described here. In this at-40 game is dimethyl sulfate as an alkylating agent for the preparation of the N-alkyl-2-chloroacetanilide from the corresponding secondary amide anion used.

4.9 g (0.02 mol) of 2'-n-butoxy-6'-methyl-2-chloroacetanilide, 2.6 g (0.02 mol) of dimethyl sulfate and 2.0 g of triethylbenzylammonium bromide were dissolved in 250 ml of CH 2 Cl 2 with cooling mixed 50 ml of 50% NaOH were ^{added all at once at 15 °} C., and the mixture was stirred for 2 h. 100 ml of water was added and the resulting 45 layers were separated. The organic layer was washed out with water, dried over MgSO4 and evaporated with Kugelrohr. A clear liquid, boiling point 135 ° C. at 0.09 mbar, was obtained in a 78% yield (4.2 g); A colorless solid crystallized out on standing, m.p. 41-42.5 ° C.

Elemental analysis for Ci ₄ H _{2 OCINO 2} ( ⁰ Zo):

Calculated: C, 62.33; H 7.47; Cl 13.14; Found: C, 62.34; H 7.49; Cl 13.16.

The product was identified as N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide. ⁵⁵ example

To a mixture, cooled to 15 ° C., of 5.6 g (0.022 mol) of 2'-n-butoxy-6'-methyl-2-chloroacetanilide, 4.0 g

(0.024 mol) diethyl sulfate and 2.2 g triethylbenzylammonium bromide in 250 ml methylene chloride were on 50 ml of 50% NaOH were added once and the mixture was stirred for 5 minutes. 150 ml of water were added

60 and the resulting layers separated; the organic layer was washed with water, dried with _MgSO4, then evaporated by Kugelrohr to give 4.1 g (66% yield) of a clear liquid, bp. 114 C ⁰

U ^ i u, vu7u iiiuai.

Elemental analysis for Ci ₅ H _{22 ClNO 2} (%): 65 Calculated: C 63.48; H 7.81; Cl 12.49; Found: C, 63.50; H 7.85; Cl 12.48.

The product was identified as N-ethyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide.

Examples 3-19

Practically the same procedures, amounts of reactants and general conditions described in Examples 1 and 2 were used to prepare further N-methyl-2-haloacetanilides according to the invention
to produce, but the appropriate secondary aniliide was used to obtain the corresponding N-alkylated end product; these compounds are identified in Table I.

Table I.

f'i

Ex.
No. link Empirical
formula Bp ° C
(mbar) Elemental analysis
Element calculated 63.48
7.81
12.49 Found 3 N- methyl-2'-isopentoxy-
6'-methyl-2-chloroacet-
anilide C ₁₅ H ₂₂ ClNO ₂ 120
(0.067) C.
H
Cl 61.05
7.09
13.86 63.38
7.80
12.44 4th N-Mcthy! -2'-n-propoxy-
6'-methyl-2-chloroacet-
anilide Ci ₃ Hi ₈ CINO ₂ 130
(0.20) C.
H
CI 62.33
7.47
13.14 60.88
7.12
13.70 5 N-methyl-2'-sec-butoxy-
6'-methyl-2-chloroacet-
anilide Ci ₄ H ₂₀ CINO ₂ C.
H
Cl 61.05
7.09
13.86 62.16
7.50
13.10 6th N-methyl-2'-isopropoxy-
6'-methyl-2-chloroacet-
anilide C ₁₃ H ₁₈ ClNO ₂ 127
(0.04) C.
H
Cl 62.33
7.47
13.14 61.05
7.09
13.83 7th N-methyl-2'-isopropoxy-
6'-ethyl-2-chloroacet-
anilide Ci ₄ H ₂₀ CINO ₂ 105
(0.013) C.
H
Cl 62.33
7.47
13.14 62.40
7.52
13.03 8th N - methyl-2'-isobutoxy-
6'-methyl-2-chloroacet-
anilide C ₁₄ H ₂₀ ClNO ₂ 115
(0.04) C.
H
Cl 62.33
7.47
13.14 62.32
7.49
13.12 9 N-methyl-2'-methoxy-
6'-tert-butyl-2-chloro
acetanilide C ₁₄ H ₂₀ ClNO ₂ 99-100
(Fp.) C.
H
Cl 59.63
6.67
14.67 62.25
7.51
13.14 10 N-methyl-2'-ethoxy-
6'-methyl-2-chloroacet-
anilide Ci ₂ H ₁₆ ClNO ₂ 57-58
(Fp.) C.
H
Cl 64.53
8.12
11.90 59.63
6.71
14.67 11th N-methyl-2 '- (l-methyl-
pentoxy) -6'-methyl-2-
chloroacetanilide C ₁₆ H ₂₄ ClNO ₂ 120
(0.11) C.
H
Cl 63.48
7.81
12.49 64.42
8.15
11.89 12th N-methyl-2'-n-pentoxy-
5'-methyl-2-chloroacet-
anilide C ₁₅ H ₂₂ ClNO ₂ 125
(0.16) C.
H
Cl 62.33
7.47
5.19 63.36
7.81
12.50 13th N-methyl-2'-n-propoxymethyl-
6'-methyl-2-chloroacet-
anilide Ci ₄ H ₂₀ ClNO ₂ 120-160
(0.067-0.13) C.
H
N 62.33
7.47
13.14 61.59
7.51 14th N-methyl-2'-isopropoxy-
5 ', 6'-dimethyl-2-chloroacet-
anilide C ₁₄ H ₂₀ CINO ₂ 121
(0.013) C.
H
Cl 63.48
7.81
12.49 62.65
6.84
13.17 15th N-methyl-2'-n-butoxy-
3 ', 6'-dimethyl-2-chloroacet-
anilide Ci ₅ H ₂₂ ClNO ₂ 108
(0.09) C.
H
Cl 63.48
7.81
12.49 63.54
7.80
12.48 16 N-methyl-2'-butoxy-
S'.o'-dimethyW-chloroacet-
anilide Ci ₅ H ₂₂ CiNO ₂ 46-47
(Fp-) C.
H
Cl 64.53
8.12
11.90 63.56
7.82
12.52 17th N-methyl-2 '- (2-methyl-
pentoxy) -6'-methyl-2-
chloroacetanilide Ci ₆ H ₂₄ ClNO ₂ 116
(0.04) C.
H
Cl 63.48
7.81
12.49 64.59
8.11
11.96 18th N-methyI-2 '- (2-methyI-
butoxy) -6'-methyl-2-
chloroacetanilide C ₁₅ H ₂₂ ClNO ₂ 120
(0.08) C.
H
CI 64.53
8.12
11.90 63.53
7.85
12.45 19th N-methy! -2 '- (l 3-dimethyl-
butoxy) -6'-methyl-2-
chloroacetanilide C ₁₆ H ₂₃ ClNO ₂ 128
(0.20) C.
H
CI 64.49
8.14
11.89

The secondary anilides used as starting materials are produced using known processes, z. B. by means of haloacetylation of the corresponding aniline. That used as the starting material in Example 1 secondary anilide e.g. B. was made as follows:

27.4 g (0.0153 mol) of 2-n-butoxy-6-methylaniline in 250 ml of methylene chloride were vigorously stirred with 0.25 mol of a 10% sodium hydroxide solution, while a solution of 17.4 g (0.0154 mol ) Chloracetyl chloride in methylene chloride was added over the course of 30 minutes, the temperature being kept ^{between 15 and 25 ° C. with the aid of external cooling.} The reaction mixture was stirred for an additional 60 minutes. When the addition was complete, the layers were separated and the methylene chloride layer washed with water, dried and evaporated in vacuo to give 28.3 g of a white solid, mp 127-128 ° C.

Elemental analysis for Ci ₃ H _{18 ClNO 2} (° / o): Calculated: C 61.05; H 7.09; Cl 13.86; Found: C, 61.04; H 7.08; Cl 13.86.

15 The product was identified as 2'-n-butoxy-6'-methyl-2-chloroacetanilide.

The secondary anilides used as starting materials for Examples 3 to 19 were made in the same manner manufactured.

The primary amines used to prepare the above-mentioned secondary anilides can be mixed with known methods are produced, e.g. B. by means of catalytic reduction of the corresponding 2-alkoxy-6-alkyl-nitrobenzene in ethanol, using a platinum oxide catalyst.

The compounds according to the invention were found to be effective herbicides, in particular as pre-emergence

bicidal, although post-emergence activity has also been demonstrated. The pre-emergence tests listed include both greenhouse and field tests. In the greenhouse tests, the herbicide is either used after planting Seeds or cuttings applied to the surface, or it is incorporated into a certain amount of soil, which is to be spread as a top layer over test seeds in sown test containers. In the field tests that will Herbicide incorporated into the soil prior to planting (P.PI), d. i.e., it is applied to the surface of the earth,

then mixed in, 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 24 χ 13 χ 7 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 below the edge of the pot. The pots are then sown with the plant species to be tested and covered with an approximately 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 ). Each pot is watered from above with 0.64 cm of water, the pots are then placed on greenhouse tables and watered from below as required.

Watering from below can also be omitted. The herbicidal effectiveness is assessed, for example

3 weeks after treatment.

Herbicide treatment by working it into the soil is done as follows in greenhouse tests:
Good topsoil is placed in aluminum pans and pounded down to 1 to 13 cm below the edge. A number of seeds or cuttings of various kinds of plants are placed on the earth. The soil necessary to completely fill the pans after sowing or planting is weighed into a pan. The soil and a known amount of active ingredient in the form of a solution or suspension of wettable powder are thoroughly mixed and used to cover the prepared pans. After treatment, the pans are given an initial top watering equivalent to 0.64 cm of rainfall, then watering from the bottom as needed so that there is adequate moisture for germination and growth.

Irrigation from above can also be omitted. Appraisal takes place about 2–3 weeks after sowing and Treatment.

Tables II and III summarize the results of the tests used to determine pre-emergence activity the compounds according to the invention were carried out; in these tests the herbicides in the soil incorporated and watered only from below, a dash (-) means that the specified Plant has not been tested. The herbicidal rating was obtained using a fixed scale on the percentage of damage to each plant species. The ratings are defined as follows:

% Control rating

0-24 0

25- 49 1

50- 74 2

60 75-100 3

The plant species used in a test series for which the data are summarized in Table II, are marked with letters according to the following legend:

A. Canada Thistle Field thistle Cirsium arvense B. Cocklebur burdock Xanthium penslyvanicum C. Velvetleaf Semolina Abutilon theophrasti D. Morningglory Winch Ipomoea sp.

E.
F.
G
H
I.
I.
K Lambsquarters
Smartweed
Yellow nutsedge
Quackgrass
Johnsongrass
Downy Brome
Barnyardgrass 11.2
5.6 Report
Water pepper
yellow cypergrass
Couch grass
Aleppo millet
downy bristle
Chicken millet 3
2 C. Chenopodium album
Polygonum sp.
Cyperus esculentus
Agropyrum repens
Sorghum halepense
Bromus tectorum
Echinochloa crus-galli E. F. G H I. J K. Table II
Pre-emergence test 11.2
5.6 1
0 3
2 3
3 3
3 3
3 3
3 3
3 3
3 3
3 Connection v. kg / ha
Example no. 11.2
5.6 2
1 1
1 D. 3
3 3
3 3
3 3
1 3
3 3
3 1 11.2
5.6 Plant species
AWAY 2
1 3
3 3
3 3
3 3
3 3
3 3
3 3
2 3
3 3
3 2 11.2
5.6 3
3 2
2 3
3 2
1 3
3 3
3 3
3 3
3 3
3 3
3 3
3 3 11.2
5.6 3
3 2
2 3
3 3
2 3
3 3
3 3
3 3
3 3
3 3
3 3
3 4th 11.2
5.6 3
3 3
1 2
2 3
2 3
3 3
3 3
3 3
3 3
2 3
3 3
3 5 11.2
5.6 3
2 2
2 3
2 3
3 3
3 3
3 3
3 3
3 3
3 3
3 3
3 6th 11.2
5.6
1.12 3
3 0
0
0 3
2 3
3 3
3 3
3 3
3 3
3 1
3 3
3 3
3 7th 11.2
5.6 3
3 2
1 3
2
2 3
3 3
3
3 3
3
1 3
3
2 3
3
3 3
3
1 3
3
3 3
3
3 8th 11.2
5.6 3
3 2
2 3
3 3
2 3
3 3
2 3
2 3
3 3
3 3
2 3
3 9 11.2
5.6 3
3 2
1 2
2 3
3
3 3
3 3
2 3
3 3
3 3
3 3
3 3
3 10 11.2
5.6 3
3
2 2
1 2
1 3
2 3
3 3
2 3
3 3
3 3
2 3
3 3
3 11th 11.2
5.6 2
3 1
0 2
1 3
2 3
3 3
3 3
2 3
3 3 3 3
3 12th 11.2
5.6 3
2 1
0 3
2 3
3 3
3 2
2 3
3 3
3 3
1 3
3 3
3 13th il, 2
5.6 3
3 1
0 2
1 2
1 3
2 3
1 3
3 3
2 3
0 3
3 3
3 14th IU
5.6 1
0 1
0 3
3 3
3 3
2 3
3 3
3 3
3 3
3 3
3 15th 11.2
5.6 3
0 2
2 1
2 3
2 2
3 3
2 3
3 3
3 3
3 3
3 3
3 16 11.2
5.6 1
2 1
0 3
2 2.
0 3
3 3
3 3
3 3
3 3
3 3
3 3 17th 3
2 2
2 0
2 3
3 3
3 3
3 3
3 2
1 3
3 3
3 18th 3
3 3
3 19th 3
3 2
2 3
3

5 The connections \ L. Soybean 31 10 452 Soybeans 5.6 Plant species M. N O P. B. Xanthium pensylvanicum D. R. E. F. C. J S. K T M. Sugarbeet Sugar beet 1.12 L. 3 3 3 3 3 Polygonum convulvulus 3 3 3 3 3 3 3 3 3 N Wheat wheat 0.28 3 3 2 3 3 1 Ipomoea sp. 2 3 3 3 1 3 3 3 3 O Rice rice 0.06 2 2 1 3 3 1 1 2 3 3 0 3 3 3 3 B. Sorghum Sorghum 0.01 0 1 1 1 3 1 Sesbania exaltata 0 1 2 2 0 3 3 3 3 10 B. Cocklebur burdock 0.006 0 0 0 0 0 0 Chenopodium album 0 1 1 1 0 0 1 3 3 Buckwheat 5.6 0 0 0 0 0 - Polygonum sp 0 1 1 0 0 0 2 3 2 r '' '' "' D. Morningglory 1.12 0 2 3 3 3 1 2 3 3 3 1 3 3 3 R. Hemp sesbania were also tested on the following plant species using the above procedure: 0.28 1 2 3 3 3 0 Abutilon theophrasti 0 3 3 3 0 3 3 3 - E. Lambsquarters 0.06 0 1 2 2 2 0 Bromus tectorum 0 3 1 1 0 3 3 3 15th F. Smartweed 0.01 0 0 0 2 0 0 Panicum spp. 0 3 0 0 0 1 1 3 C. Velvetleaf 0 0 0 1 0 0 0 1 0 0 0 0 0 1 - ^: t ^r " J Downy brome 5.6 0 S. 1.12 3 3 3 3 2 3 3 3 3 3 3 3 3 3 20th K 0.28 2 3 3 3 3 2 0 2 3 3 2 3 3 3 3 I. '-. T 0.06 1 2 2 3 3 0 0 0 3 3 0 3 3 3 Bindweed knotweed 0.01 1 1 1 1 0 0 0 0 3 1 0 0 3 3 3 25th Funnel winch 0.006 0 0 0 0 3 0 0 0 0 0 0 2 3 3 3 I " hemp 5.6 0 0 0 0 0 0 0 0 1 1 0 0 0 1 1 ι Report 1.12 0 3 3 3 3 3 Echinochloa crus-galli 3 3 3 3 2 3 3 3 3 0.28 2 2 2 3 3 1 Digitaria sanguinalis 2 3 3 2 2 3 3 3 3 I. 30th 0.06 0 2 3 3 3 3 3 3 1 1 3 3 3 3 Panicum species Water pepper 0.01 0 1 1 1 3 0 1 0 0 0 3 3 3 3 Barnyardgrass Semolina 5.6 0 0 0 0 0 0 - 0 0 0 0 0 1 2 3 Crabgrass 1.12 0 3 3 3 3 2 3 3 3 3 3 3 3 3 3 35 0.28 3 3 3 3 3 1 Q 3 3 3 3 2 3 3 3 3 0.06 2 2 2 2 3 1 3 1 3 3 3 2 3 3 3 3 0.01 0 1 1 2 2 0 2 0 3 3 3 1 2 3 3 3 I. 0.006 0 0 0 0 0 0 2 0 1 1 1 0 0 1 3 3 1 ·. downy bristle 0 1 0 0 0 0 2 0 2 1 1 0 0 0 1 2 40 Panicum 5.6 0 1 1.12 3 3 3 3 2 0 2 3 3 3 3 3 3 3 - Chicken millet 0.28 3 3 3 3 3 1 1 2 2 3 3 2 3 3 3 Fingergrass 0.06 2 2 1 3 3 0 1 1 2 3 2 2 3 3 3 0.01 0 1 0 0 0 0 0 0 1 3 1 0 3 3 3 - {. 45 0 0 0 1 0 0 0 0 1 1 0 0 2 0 3 0 0 3 50 2 1 0 1 55 0 3 3 1 0 60 0 3 3 1 0 65 The results are shown in Table III. 0 Table III 0 Pre-emergence test Verb, from kg / ha 3 ί Example no. 2 1 1 0 1
8th 2 3 4th 5 6th

Table III (continued) Pre-emergence test

Verb, from kg / ha Plant species M. N O P. B. Q D. R. E. F. C. 3 S. K. T Bebp. No. L. 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 7th 5.6 1 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3 1.12 0 2 3 2 2 0 2 2 2 3 2 1 3 3 3 3 0.28 0 2 1 1 1 1 0 3 2 2 1 1 1 3 3 3 0.06 0 1 1 0 0 0 0 1 1 0 0 0 1 0 2 3 0.01 1 0 0 0 0 0 0 1 2 0 0 0 1 0 * ■ »
£. 2 0.006 0 3 3 3 3 1 2 3 3 3 3 3 3 3 3 3 8th 5.6 2 2 2 3 3 0 2 2 2 3 2 1 3 3 3 3 1.12 0 2 2 3 3 0 1 C. 2 3 2 0 3 3 3 3 0.28 0 1 0 2 3 0 1 0 0 1 0 0 1 2 3 3 0.06 0 1 0 0 0 0 0 0 1 3 2 0 0 1 3 3 0.01 0 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 9 5.6 3 2 3 3 3 1 2 2 2 3 1 1 3 3 3 3 1.12 1 1 2 2 2 0 1 3 2 3 2 1 2 2 3 3 0.28 0 1 2 1 1 0 0 0 2 0 2 0 0 2 3 3 0.06 0 1 2 0 0 0 0 0 2 1 1 0 0 0 2 3 0.01 0 2 3 3 3 0 3 3 3 3 2 3 3 3 3 3 10 5.6 2 2 2 3 3 1 1 2 3 3 2 2 3 3 3 3 1.12 0 2 1 3 3 0 2 2 2 3 0 2 3 3 3 3 0.28 0 1 0 1 2 0 0 0 3 2 0 2 3 3 3 3 0.06 0 1 0 0 0 0 0 0 1 0 0 1 0 0 0 3 0.01 0 3 3 3 3 1 3 3 3 3 3 1 3 3 3 3 11th 5.6 1 1 2 3 3 0 2 2 2 3 3 0 3 3 3 3 1.12 0 1 2 3 3 - 0 1 1 3 3 0 3 3 3 3 0.28 0 0 1 2 1 0 0 0 2 3 2 0 2 2 3 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 3 0.01 0 2 3 3 3 1 3 1 3 3 3 1 3 3 3 3 12th 5.6 2 2 3 3 3 1 3 2 3 3 3 1 3 3 3 3 1.12 0 2 3 3 3 0 0 0 1 3 2 0 3 3 3 3 0.28 0 0 2 3 3 0 2 0 0 1 2 0 3 3 3 3 0.06 0 0 0 0 0 0 0 0 2 0 0 0 1 0 3 3 0.01 0 2 3 2 3 2 3 3 3 3 3 2 3 3 3 13th 5.6 1 2 2 3 3 1 2 2 3 3 3 1 3 3 3 - 1.12 0 2 2 3 0 0 1 1 2 3 2 0 2 3 3 - 0.28 0 1 1 1 0 0 0 0 1 2 1 0 0 3 3 - 0.06 0 0 0 0 0 0 0 0 0 0 1 0 1 0 1 - 0.01 0 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 14th 5.6 3 3 2 3 3 C. 2 3 3 3 3 2 3 3 3 3 1.12 2 2 2 2 3 0 2 3 2 2 2 1 3 3 3 3 0.28 2 2 1 2 1 0 1 2 1 2 2 0 2 2 3 3 0.06 0 1 1 1 0 0 1 1 1 1 0 0 0 0 2 3 0.01 0 1 0 1 0 0 1 1 1 1 0 0 0 0 1 3 0.006 0 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 15th 5.6 2 2 3 3 3 1 2 1 1 3 2 0 3 3 3 3 1.12 0 1 1 1 1 0 1 0 0 1 1 0 3 3 3 3 0.28 0 1 0 0 0 0 0 0 0 1 0 0 0 2 3 3 0.06 0 0 0 0 0 0 η 0 η 1 1 O η η 2 2 0.01 0 3 3 3 3 1 2 2 3 3 3 1 3 3 3 16 5.6 1 2 2 3 3 0 2 1 2 2 3 0 3 3 3 - 1.12 0 2 1 3 3 0 0 0 1 3 3 0 2 3 3 - 0.28 0 1 0 1 0 0 0 0 3 1 0 0 3 2 3 - 0.06 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 0.01 0

III (continued) 10 18th 15th kg / ha Plant species M. N O 31 10 452 D. R. E. F. C. J S. K. T Tabel Pre-emergence test L. 3 3 3 1 3 3 3 1 3 3 3 Verb, from 5.6 0 2 2 3 0 2 2 2 0 3 3 3 - ₅ Example No. 1.12 0 2 1 3 0 1 0 1 0 3 3 3 - 17th 0.28 0 0 0 1 P. B. Q 0 1 1 0 0 1 1 3 - 0.06 0 0 0 0 3 0 1 0 0 0 0 0 0 0 1 - 0.01 0 3 3 3 3 0 1 3 3 3 3 2 3 3 3 3 5.6 3 3 3 3 2 0 0 3 3 3 3 2 3 3 3 3 1.12 0 2 2 3 0 0 0 0 2 3 2 1 3 3 3 3 0.28 0 2 0 0 0 - 0 0 0 2 3 0 3 3 3 3 0.06 0 2 0 0 3 3 3 0 0 0 0 0 0 3 3 0.01 0 3 0 3 3 0 2 2 0 2 0 0 0

The compounds according to the invention therefore have unexpectedly superior properties as pre-emergence herbicides, in particular for the selective control of the difficult-to-kill weeds Panicum texanum and sorghum halepense, Sorghum bicolor, Brachiaria, Panicum miliaceum, Oryza sativa and Rottboellia while they Control or reduce many other less resistant perennial and annual weeds as well.

Selective control and increased suppression of the above-mentioned weeds with the aid of the invention Herbicides have been found in a wide variety of crops including soybeans, cotton, peanuts, Rapeseed, and French beans. In some tests, selectivity was found in Sugar beet and garden peas detected; some cultures, especially cultures with plants from the Family of the grasses, however, are usually less tolerant of the herbicides according to the invention than the crops listed above.

To the unexpectedly superior properties of the compounds according to the invention both on absolute as to be shown on a relative basis, comparative tests were carried out in the greenhouse with known compounds, which are most closely related in their chemical structure to the compounds according to the invention. These are identified as follows:

A. N-tert-Butyl-2-methoxy-2-chloroacetanilide 35 (Example 13, US-PS 32 68 584)

B. i'-tert -Butyl-e'-metnoxy ^ -chloroacetanilide (Example 67, US-PS 34 42 945)

C. N-Isopropyl-2-chloroacetanilide (general term »propachlor«)

40 US-PS 28 63 752 (Re Patent No. 26,961)

Propachlor is referred to in the above-mentioned US Pat. Nos. 3,773,492 and 4,152,137; it is the active ingredient in the commercially available herbicide "Ramrod ⁸¹ ", a registered trademark of the Monsanto Company.

In the following discussion of the data, reference will be made to herbicide application rates beginning with "GR15" and "GRgs" are represented; these amounts are given in kg / ha, which is obtained by dividing by 1.12 in Ibs / A can convert GR15 defines the maximum amount of herbicide at which 15% or less of the crops Damage occurs while GRes is the minimum amount necessary to achieve 85% inhibition the weeds is reached. The GR15 and GRss quantities are becoming more commercially available as a measure of potential performance Products used, being of course suitable commercially available herbicides within reasonable limits Limits can show greater or lesser plant damage.

Another indication of the effectiveness of a chemical as a selective herbicide is the "selectivity factor"("SF") for a herbicide on certain crops and weeds. It is a measure of the relative degree of harmlessness to crops or the harm to weeds, and is expressed as the ratio GR15 / GR85, ie the GRis amount for the crop plant divided by the GR _g5 amount for the weeds, both amounts expressed in kg / ha. In the tables below, the selectivity factors are given in brackets after the amount of GRes for each weed; "NS" means "non-selective". Insignificant or questionable selectivity is indicated with a dash (-); a free space means that the specified plant was not tested in the respective test or that it had not sprouted.

Since crop tolerance and weed control are related, there is a brief discussion this ratio, expressed as the selectivity factor, is appropriate. In general, it is desirable that the Crop safety factors, d. H. the herbicide levels, are high, because of the one or For another reason, higher herbicide concentrations are often desired. Conversely, the quantities for weed control be small for economic and possibly environmental reasons; d. H. the herbicide should have a high unit activity. However, small application rates of a herbicide may not be suitable for control of certain weeds is sufficient and a larger amount is needed. The best herbicides are therefore the ones who control the largest number of weeds with the least amount of application and the greatest possible harmlessness for the crop d. H. Crop tolerance, provide. The (above

defined) "selectivity factors" are used to determine the relationship between harmlessness for the
Quantify crop and weed control. With respect to those contained in the tables
This means selectivity factors: the higher the numerical value, the higher the selectivity of the herbicide for weed control in a particular crop.

Table IV shows the herbicidal pre-emergence data from a first greenhouse comparison test, in which the relative effectiveness of the compound of Example 1, an exemplary compound thereof
Invention, with relevant known compounds, ie compounds A, B and C as selective herbicides
against certain weeds commonly associated with soybeans. The data of the
Tables IV were obtained for all compounds under identical test conditions, ie the herbicide was used
incorporated into the soil and received an initial watering from above; the data represent the average of 2 runs for each link; two different samples of the compound of Example 1
were used and the data in the table are an average for both test samples. For the weeds
the following abbreviations are used in the tables: Panicum texanum (TP), Sorghum halepense seedlings (SJG), Sorghum bicolor (SC), Brachiaria plantaginea (AG), Panicum miliaceum (WPM), Herbstpanicum (FP), Oryza sativa (RR ) and Rottboellia exaltata (IG). 15th

Table IV link

GRis crowd

(l: g / ha)

Soybeans

GRes crowd

(kg / ha)

TP SJG

SC

AG

RR

IG

C Ex.

> 1.12

0.71

0.11 (6.5)

<0.07 (>! 0.2) <0.07 (> 10.2) 0.07 (> 10.2) 0.14 (5.1)

0.12 (> 9.3) <0.07 (> 10.2)

0.18 (3.9) 0.07 (> 10.2)

From Table IV it can be seen that at the highest application rate of 1.12 kg / ha none of the known
Compounds exercised a positive selective control of one of the weeds in soybeans, with the only one
Exception of compound C in Herbstpanicum, and even there the selectivity factor was smaller than for that
Compound of Example 1. In marked contrast, the compound of Example 1 controlled each ^! tested weeds with extremely low application rates, while the harmlessness for soybean 5
nen up to 0.71 kg / ha was retained. Of particular note is the fact that the compound of Example 1 'controlled Sorghum halepense, Sorghum bicolor, Brachiaria, Herbstpanicum and Rottboellia at 0.07 kg / ha (the minimum amount used) or less, as well as the remaining weeds, ie Panicum texanum , Panicum j.} Miliaceum and Oryza sativa with amounts of only 0,10,0,14 and 0.18 kg / ha, respectively. ?!

Further greenhouse tests were carried out to determine the relative herbicidal effectiveness of the known compounds fertilize A to C with the compounds of Examples 1, 3 to 5 and 8 to 17, which are representative compounds according to the invention. In the tests, the herbicide was incorporated into the soil, and '·> although with rates of 0.07 to 1.12 kg / ha, and an initial overhead irrigation followed by j) demand-irrigation. Observations were made 19 days after treatment. The data from the $, additional tests are summarized in Table V; the names of the weeds are abbreviated as for Table IV 15 | -, and the selectivity factors are given in brackets after the GRg ₅ amount for each weed. f;

Table V link

GR | 5 quantity (kg / ha)

Soybeans

GR85 quantity

(kg / ha)

TP

SC

AG

WPM

FP

A. > 1.12 B. > 1.12 C. > 1.12 example 1 > 1.12 Example 3 > 1.12 Example 4 > 1.12 Example 5 > 1.12 Example 8 > 1.12 Example 9 1.12 Example 10 > 1.12 Example 11 > 1.12 Example 12 > 1.12 Example 13 1.12 Example 14 0.56 Example 15 > 1.12 Example 16 1.12 Example 17 > 1.12

> 1.12 (-) > 1.12 (-) > 1.12 (-) 1.00 (> 1.0) > 1.12 (-) 1.00 (> 1.0) > 1.12 (-) OJ 1.12 (> 1.0) > 1.12 (-) > 1.12 (-) 1.12 (> 1.0) > 1.12 (-) 0.28 (> 4.0) 1.12 (> 1.0) <0.07 (> 16.0) <0.07 (> 16.0) <0.07 (> 16.0) 0.07 (> 16.0) <0.14 (> 8.0) <0.07 (> 16.0) 0.38 (> 3.0) O 0.07 (> 16.0) <0.07 (> 16.0) 0.14 (> 8.0) 0.07 (> 16.0) 0.14 (> 8.0) <0.07 (> 16.0) 0.25 (> 4.5) Ul 0.09 (> 12.0) <0.07 (> 16.0) 0.07 (> 16.0) 0.07 (> 16.0) 0.28 (> 4.0) <0.07 (> 16.0) 0.13 (> 8.6) 0.07 (> 16.0) <0.07 (> 16.0) <0.07 (> 16.0) <0.07 (> 16.0) 0.14 (> 8.0) <0.07 (> 16.0) 0.14 (> 8.0) 0.14 (> 8.0) 0.07 (> 16.0) 0.09 (> 12.0) 0.14 (> 8.0) 0.28 (> 4.0) <0.07 (> 16.0) 1.12 (> 1.0) 0.28 (4.0) 0.14 (8.0) 0.50 (2.2) 0.28 (4.0) 1.12 (1.0) <0.07 (16.0) > 1.12 (NS) 0.56 (> 2.0) 0.07 (> 16.0) 0.28 (> 4.0) 0.09 (> 12.0) 0.28 (> 4.0) <0.07 (> 16.0) 0.50 (> 2.2) 0.28 (> 4.0) <0.07 (> 16.0) 0.28 (> 4.0) 0.09 (> 12.0) 0.56 (> 2.0) <0.07 (> 16.0) 0.56 (> 2.0) 0.28 (> 4.0) 0.07 (> 16.0) 0.20 (> 5.6) 0.14 (> 8.0) 0.28 (> 4.0) <0.07 (> 16.0) 0.48 (> 23) 0.28 (4.0) 0.14 (8.0) 0.28 (4.0) 0.38 (3.0) 0.28 (4.0) <0.07 (> 16.0) 0.50 (2.2) 0.14 (4.0) <0.07 (8.0) 0.14 (4.0) 0.28 (2.0) 0.56 (1.0) <0.07 (8.0) 0.07 (8.0) 0.56 (> 2.0) 0.19 (> 5.9) 1.12 (> 1.0) 0.56 (> 2.0) 0.56 (> 2.0) <0.07 (> 16.0) 0.28 (> 4.0) 0.28 (4.0) <0.07 (16.0) 0.14 (8.0) 0.09 (12.0) 0.28 (4.0) <0.07 (> 16.0) 0.28 (4.0) 0.56 (> 2.0) 0.28 (> 4.0) 0.14 (> 8.0) 0.12 (> 9.3) 0.56 (> 2.0) <0.07 (> 16.0) 0.75 (> 1.5)

From Table V it can be seen that within the limits of the herbicide levels used for the test, Compound A did not selectively control any of the tested weeds in soybeans; Compound B only barely selectively controlled autumn panicum (not a particularly resistant weed), and compound C selectively controlled autumn panicum only, and, barely, Panicum texanum, Brachiairia and Oryza sativa. With the sole exception of Compound C against Herbstpanicum (GR ₈ 5 at 0.28 kg / ha) and Compound B against Brachiaria and Herbstpanicum (GRes at 1.00 kg / ha), none of the known compounds controlled any of the weeds tested to a lesser extent than 1.12 kg / ha.

With a few exceptions for certain weeds, all of them according to the invention showed in sharp contrast Compounds provide an excellent positive selective control of all weeds in soybeans. In only In a few cases, selective control was scarce; B. in example 8 and 17 against Oryza sativa, example 9 against Panicum miliaceum and Oryza sativa, Example 14 against Panicum miliaceum, and Example 15 against Sorghum bicolor. In contrast to the known compounds, and again with the exceptions mentioned, controlled all compounds according to the invention, moreover, all weeds with extremely low application rates, from a maximum of 0.56 kg / ha to less than 0.07 kg / ha; this is a remarkable achievement both absolutely in view of the high resistance of the weeds tested (with the exception of autumn panicum), as especially also relative to the inability of most of the relevant known compounds to be tested Control weeds with the exceptions mentioned.

Preferred compounds of the invention were also field tested for their selective pre-emergence activity and duration of action in the soil against the annual weeds Panicum texanum, Acanthospermum hispidum and Richardia scabra in peanuts (Florunner). The assessments were made 4, '8 and 12 weeks after the treatment, which was carried out by applying the herbicides to the surface; in which Soil was Dothan sandy loam with 1.3% organic matter; the results are in the table VI compiled.

lot % Inhibition 8th 0 12th Panicum texanum 8th 12th Acanthospermum 12th Richardia scabra 12th kg / ha peanuts WAT WAT 5 WAT WAT WAT hispidum WAT WAT 0 13th 0 4th 60 52 4 8 85 4 8 4th 12th 27 0 WAT 83 83 WAT WAT 95 WAT WAT 95 22nd 0 0 85 97 87 - 80 95 - 95 98 1.12 40 3 21 93 95 98 - 90 98 95 90 98 2.24 0 10 0 95 58 62 - 97 80 98 3.36 3 15th 0 100 88 87 95 100 90 100 98 100 4.48 8th 0 0 82 95 92 - 80 95 - 90 95 1.12 15th 10 15th 90 100 100 95 95 100 95 95 95 2.24 10 13th 0 95 78 43 - 90 - 97 70 3.36 15th 27 0 98 87 70 - 100 - - 98 - 4.48 27 0 78 93 88 - 85 95 - 85 95 1.12 37 13th 92 97 90 - 88 95 - 98 100 2.24 95 - 95 - 98 3.36 100 - 97 - 98 4.48 Table VI link example 1 Example 2 Example 3

a. Average of 3 runs

The data in Table VI show that the compound of Example 2 was found to have all three weeds in peanuts Selectively controlled application rates of 2.24 to 4.48 kg / ha up to 12 WAT. Selective control of one or more of the weeds tested were also carried out by the combination of Examples 1 and 3 in the case of lesser ones Amounts up to 12 WAT, indicating that of the three test compounds, the compound of Example 2 had the highest peanut safety factor under the test conditions.

Additional field tests were conducted to determine the relative effectiveness of the compounds of the Examples 1, 3 and 4 to determine against Panicum miliaceum in soybeans for periods up to 12 WAT, if that Herbicide either applied to the surface (SA) or incorporated into the soil before planting became (PPI). The soil was sandy loam with 1.7% organic matter; 2 days after treatment 635 cm of precipitation recorded; the results of this test are shown in Table VII

lot % Inhibition PPI 31 10 8WAT PPI 452 PPI Panicum miliaceun PPI 1 PPI 12 WAT PPI Table VII kg / ha Soybeans 32 SA 22nd 0 3WAT 82 8WAT 43 SA 18th link 3WAT 33 0 33 0 SA 78 SA 48 25th 50 SA 32 0 32 10 85 85 40 60 77 60 1.12 15th 50 13th 30th 23 92 92 78 78 85 70 2.24 15th 27 20th 8th 0 95 73 90 57 78 20th example 1 3.36 15th 37 0 25th 5 98 75 85 53 25th 43 4.48 33 40 0 27 12 WAT 0 85 87 60 70 72 63 1.12 0 60 7th 47 SA 8th 92 88 68 70 85 62 2.24 15th 15th 13th 10 0 0 95 85 88 55 83 10 Example 2 3.36 22nd 22nd 5 18th 0 0 92 85 88 67 63 47 4.48 30th 25th 7th 18th 0 0 95 80 68 50 58 42 1.12 8th 43 10 33 8th 30th 95 90 80 78 82 58 2.24 15th 15th 0 , 95 82 85 Example 3 3.36 22nd 0 95 90 4.48 22nd 0 7th 0 0 0 0

a. Average of 3 runs

The data from Table VII shows that at 336 kg / ha each compound Panicum miliaceum selectively 3.8 and 12 weeks after treatment, checked to see if the herbicide was applied to the surface. Certain treatments of the culture with the compounds of the invention thus resulted in control of Panicum miliaceum for the entire season, as this weed species germinates and emerges progressively with the season The greater harmfulness for soybeans in the PPI treatments is due to too deep and uneven working in with the disc harrow and on the precipitation 2 days after treatment In this test, treatment by application to the surface gave superior weed control and harmless to culture.

In a further field test, the compounds of Examples 1, 3 and 4 were tested for their herbicidal activity tested against the very resistant annual weed Sorghum halepense, both by Apply to the surface as well as work into the soil before planting. This field test was carried out in Clay (58% clay and 3.1% organics). The assessments took place for 4 and 8 weeks after treatment; the results are summarized in Table VIII.

Table VIII lot % Inhibition SA 8WAT SA Sorghum h. Seedlings SA 8WAT SA 40 link kg / ha Soybeans 3 PPI 3 4WAT 23 PPI 10 4WAT 12th 12th 10 PPI 67 80 PPI 15th 28 17th 7th 85 85 80 1.12 5 18th 22nd 22nd 75 85 87 78 45 example 1 2.24 13th 3 38 5 78 25th 93 23 3.36 23 13th 13th 7th 80 67 0 60 4.48 30th 18th 13th 15th 17th 82 70 78 1.12 10 22nd 22nd 23 47 78 85 68 Example 3 2.24 22nd 0 32 0 70 23 90 8th 50 3.36 28 13th 8th 12th 78 68 33 78 4.48 32 12th 8th 13th 7th 82 85 88 1.12 10 17th 20th 15th 60 85 87 85 Example 4 2.24 13th 28 73 88 55 3.36 23 75 4.48 22nd

a. Average of 3 runs

The compound of Example 4 controlled Sorghum halepense in soybeans at 2.24 kg / ha selectively up to 8 Weeks after treatment for PPI conditions, and at 3.36 and 4.48 kg / ha for SA conditions. the Compound of Example 1 controlled Sorghum halepense with the 336 kg / ha amount selectively for at least 4 Weeks after treatment under S.A. conditions.

As can be seen from the data in the tables above, the compounds according to the invention can both by applying it to the surface and by working it into the ground in a suitable manner can be used, with the preferred treatment being different factors such as soil or climate In general, however, the application of the herbicides to the surface is dependent on the incorporation into the

Floor preferred.

In laboratory tests to determine the resistance of the herbicide to leaching in the soil and thereby resulting herbicidal activity, the compound of Example 1 was dissolved in acetone and then in sprayed various concentrations on weighed amounts of Ray silt loam; this was in pots included, the drainage holes in the bottom were covered with filter paper. The pots containing the treated soil were leached by placing them on a turntable that was placed under two nozzles of a water container rotated, which were set so that they gave off 24 cm of water per hour and thus rain simulated. Leach rates were adjusted by changing the time on the turntable Water was added to the pots, then allowed to drain through the filter paper and the drainage holes. The pots were then left to stand for 3 days at room temperature. The treated soil in the pots was made then removed, crumbled and spread as a surface layer on other pots that contained Ray silt loam, which was sown with Echinochloa crus-galli seeds. The pots were then placed on greenhouse tables, by watered down and left to grow for 2 to 3 weeks. Visual evaluations of the percentage Growth inhibition in comparison to (untreated) control pots, as well as the recording of the fresh weight from Echinochloa crus-galli occurred 18 days after treatment; the data from three passes of this Tests are summarized in Table IX

Table IX Connection of amount of rain Echinochloa crus-galli Example No. (kg / ha) (cm)% inhibition% fresh weight

(Average of 3 continuous controls

1 2 ^ 4

046

0.14

0 100 0 0 0.64 100 0 0 1.27 100 0 0 244 100 0 0 5.08 100 0 0 10.16 95 0 0 0 100 0 0 0.64 100 0 0 1.27 100 0 0 244 100 0 0 5.08 95 0 0 10.16 95 0 0 0 100 0 0 0.64 100 0 0 U7 100 0 0 2.54 95 0 0 5.08 95 0.20 3.3 10.16 90 0.83 14.1

Table IX shows that the compound of Example 1, representative of the compounds according to the invention, fairly resistant to leaching in the soil under conditions prevailing in heavy rainfall and no less than 90% control of Echinochloa with application rates as low as 0.14 kg / ha 10.16 cm of precipitation.

A major benefit of a herbicide is its ability to act in a wide variety of soil types. Accordingly, in Table X, data are compiled on the herbicidal activity of the compounds of Examples 1 and 3 versus Brachiaria (AG) and Echinochloa (BYG) in soybeans in a number of Represent soil types with different proportions of organic matter. The herbicide was on the surface applied, watering was carried out as described above from above; the selectivity factors for the Weeds are indicated in brackets after the GRgs values for the weeds.

17th

Table X

Soil type & connection

organic substance

Volume %

GRiä quantity »)

(kg / ha)

Soybeans

GR / B quantity ")

(kg / ha)

AG

BYG

Ray silt loam 1.0 9.6

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

Example3 1.12 <0.14 (> 8.0) <0.14 (> 8.0)

Sarpy clay 23 -

Example 1 <23 0.28 (> 8.0) 0.96 (> 23)

Example3 <23 0.21 (> 10.7) 0.42 (> 5.3)

Drummer silty clay 6.0 37.0

Example 1 23 <0.14 (> 16.0) 03 (> 93)

Example3 <23 <0.14 (> 16.0) 0.28 (> 8.0)

Florida sand 6.8 1.8

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

Example 3 1.12 0.28 (4.0) 23 (NS)

Florida peat earth 22.1 -

Example 1 23 1.12 (2.0) 23 (1.0)

Example 23 23 (1.0) <23 (NS)

Brazilian 17.6 20.0

(Sao Paulo) sandy clay loam

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

Example 1.12 0.14 (8.0) 0.14 (8.0)

a) Average of 2 courses, observation 13 days after treatment

Table X shows that the compounds according to the invention are largely insensitive to the type of soil was. In particular, the compound of Example 1 showed positive selective control of Brachiaria and Echinochloa in soybeans in all tested soils, the organic matter from 1.0% in Ray silt loam up to Florida contained 22.1% peat peat. Likewise, the compound of Example 3 showed positive selective ones Control of tested weeds in soybeans in all soil types except for barnyard grass in Florida Sand (6.8% organics) and Florida peat soil. Since the compound of Example 3 is both Brachiaria and Echinochloa also selectively controlled silty clay loam in Drummer, which is about the same organic Share like Florida sand, but had a significantly higher clay share (37.0%), also in soils with higher organic components and clay components such as in Brazilian sandy silt loam, it is assumed that the low clay content of 1.8% in the Florida sand added to the non-selective control of Echinochloa in this one Soil type contributed.

The compounds of the invention find their main use in crops of soybeans and peanuts. However, selective weed control has also been demonstrated in a number of other crops, such as this shown in Table III above. In still further tests it was shown that the compound of Example 1 can also be used in French beans and garden peas with application rates of up to 1.12 kg / ha, in cotton, Canola, carrots and beets up to 0.6 kg / ha or more, and in alfalfa, flax and cabbage with around 0.3 to

50 0.6 kg / ha.

Toxicological studies of the compounds of Examples 1, 3 and 4 had the following results:

toxicology

Connection of example no.
1 3

2300 2400 > 1000 <1260 > 3100 <5010 heavy moderate corrosive corrosive

Oral LD ₅₀ , mg / kg 3370

Dermal LD, mg / kg> 2000

Eye irritation easy

No skin irritation

The corrosiveness of the compound of Example 3 can be due to an impurity, namely dimethyl sulfate, that was found in the sample with which the toxicological tests were carried out became. It is evident that the above compounds are harmless when combined with normal Care should be taken that compounds with the specified toxicological properties require. The relative harmlessness of handling the above compounds appears to be in the following order have: Example 1> Example 4> Example 3.

The compounds according to the invention show unexpectedly and outstandingly superior herbicidal properties

shafts, both in absolute terms and in comparison with the structurally closest known known ones Compounds, one of which (compound C) is a commercially available herbicide. In particular, the Compounds of the invention as excellent selective herbicides, especially difficult to control Annual grasses to be killed in soybeans, peanuts and other crops. In addition, show the invention Connections excellent control of annual grasses Panicum texanum, Rottboellia exaltata, Panicum miliaceum, Brachiaria plantaginea, Sorghum halepense, Sorghum bicolor and Oryza sativa, while controlling and driving back other annual grasses and perennial weeds, including those listed in Tables II and III above, as well as others such as e.g. B. Acanthospermum hispidum or Richardia scabra.

The herbicidal preparations according to the invention, including the concentrates, before use must be diluted, contain at least one active ingredient and one adjuvant in liquid or solid form. The preparations are made by mixing the active ingredient with an adjuvant, including diluents, Extenders, carriers and conditioning agents include, manufactured so that preparations in the form of Finely distributed solid particles, granules, pellets, solutions, dispersions or emulsions arise. Of the Active ingredient can therefore be organic with an adjuvant such as a finely divided solid, a liquid Origin, water, a wetting agent, a dispersing agent, an emulsifying agent or a appropriate combination thereof can be used.

The preparations according to the invention, in particular liquids and wettable powders, preferably contain one or more customary surfactants in sufficient quantities as conditioning agents Quantities to make a particular preparation easily dispersible in water or oil. The inclusion of a Surface active agent in the preparations promotes their effectiveness significantly. Under the. expression "Surfactant" includes wetting agents, dispersants, suspending agents, and emulsifying agents. Anionic, cationic and nonionic agents can equally be used.

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 sulfonates, polymeric alkyl naphthalene sulfonates, 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 from silica. Such extenders include kaolinites, attapulgite clay, and synthetic Magnesium Silicate The wettable powders of the 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) inert stretch solids, all parts by weight of the total Preparation related. If necessary, about 0.1 to 2 parts of the inert extender solids can through a Corrosion inhibitors or foam inhibitors, or both, are replaced.

Other formulations contain dust concentrates that contain 0.1 to 60% by weight of active ingredient on a suitable Contain extenders; these dusts can be used with concentrations of about 0.1 to 10 Wt .-% are 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 ingredient according to the invention are i.a. 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 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 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

ίο The granule 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 additives, e.g. B. Fertilizers, other herbicides or pesticides, and foams, used 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 include. Substances in which plant organisms take their roots and grow, e.g. B. compost, manure, dirt and sand.

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

I. Emulsifiable Concentrates

25% by weight

A. Compound of Example No. 1 35.6 Calcium Docedylbenzenesulfonate /

Polyoxyethylene ether blend (e.g. Atlox 3437F) 5.0 Monochlorobenzene 29.7

30 cg aromatic hydrocarbon 29.7

100.0

B. Compound of Example No. 3 85.0 Calcium Dodecylsulfonate / Alkylarylpoly-

35 ether alcohol mixture 4.0

C9 aromatic hydrocarbon solvent

100.0

40 C. Compound of Example No. 4 5.0

Calcium dodecylbenzenesulfonate / polyoxy-

ethylene ether mixture

(e.g. Atlox 3437F) 1.0

Xylene 94.0

45 100.0

II. Liquid concentrates

Weight

A. Compound of Example No. 5 10.0 50 Xylene 90.0

100.0

B. Compound of Example No. 6 85.0 Dimethyl sulfoxide 15.0

55 100.0

C. Compound of Example No. 18 50.0 N-methylpyrrolidone 50.0

D. Compound of Example No. 19 5.0 ClIlDAyHCl IC »I \ I1I £ U1U» U1 JJ, J

Rhodamine B 0.5

Dimethylformamide 74.5

65 100.0

20th

III. Emulsions

A. Compound of Example No. 7

Polyoxyethylene / polyoxypropylene block copolymer with butanol (e.g. Tergitol XH)
water

B. Compound of Example No. 8 Polyoxyethylene / polyoxypropylene block copolymer with Btitanol water

IV. Wettable powders

A. Compound of Example No. 9 Sodium Lignonsulfonate Sodium N-methyl-N-oleyl taurate Amorphous silica (synthetic)

B. Compound of Example No. 10 Sodium Dioctylsulfosuccinate Calcium Lignosulfonate Amorphous silica (synthetic)

C. Compound of Example No. 11 Sodium Lignosulfonate Sodium N-methyl-N-oleyl taurate kaolinite clay

V. Dusts

A. Compound of Example No. 12 Attapulgite

B. Compound of Example No. 13 Montrnorillonite

C. Compound of Example No. 14 Bentonite

D. Compound of Example No. 15 Diatomaceous Earth

VI. Granules

A. Compound of Example No. 16 Granulated Attapulgite (20/40 sieve)

B. Compound of Example No. 17 Diatomaceous Earth (20/40)

C Compound of Example No. 18 Bentonite (20/40)

D. Compound of Example No. 19 Pyrophyllite (20/40)

Wt% 40.0

4.0 56.0

100.0 5.0

3.5

91.5

100.0

Weight - ⁰ /

25.0

3.0

1.0

71.0

100.0

80.00 1.25 2.75

16.00 100.00

10.0

3.0

1.0 86.0

100.0

Wt% 2.0 98.0 100.0

60.0 40.0

100.0

30.0

70.0

100.0

1.0

99.0

100.0

Wt. ¹ 15.0 85.0

100.0

30.0

70.0

100.0

0.5

99.5

100.0

5.0

95.0

100.0 "

10

20th

30th 35 40 45 50 55 60

V ''

I!

21

VII. Microcapsules

Wt%

A. Compound of Example No. 1

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. 3

ίο encapsulated in polyurea shell 10.0

Potassium lignosulfonate (e.g. Reax® C-21) 0.5

Water 89.5

100.0

C. Compound of Example No. 4

encapsulated in polyurea shell 80.0

Magnesium salt of lignosulfate (Treax® LTM) 2.0

Water 18.0

100.0

For use, effective amounts of the acetanilides according to the invention are applied to those containing the plants Soil applied or appropriately taken up in aqueous media. Applying the Preparations as liquids and solid particles on the earth can be done using conventional methods, z. B. with motorized atomizers, tank and hand sprayers or spray atomizers. The preparations can be due to their effectiveness in small doses can also be distributed by airplanes as dust or spray. The application herbicidal preparations in aquatic plants are usually carried out by adding the preparations to 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 site of the undesired Weeds is essential and critical. The exact amount of active ingredient to be used depends on various factors such as B. on the plant species and its stage of development, type and condition of the Soil, the amount of rain and the specific acetanilide used. With selective pre-emergence application on plants or soil is usually an application rate of 0.02 to 11.2 kg / ha, preferably of about 0.04 to 5.60 kg / ha, or 1.12 to 5.6 kg / ha acetanilide is used. In some cases it can be larger or smaller Quantities are required, which on the basis of the description, including the examples, is easy to apply for each case is to determine.

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, sand and the like. that can sustain plant growth.

Claims (10)

Claims: 1.2-chloroacetanilide of the general formula OR, where mean: either R is ethyl and Ri η-butyl, R2 is methyl and R3 is hydrogen; or
R methyl and Ri isopropyl or η-butyl, R2 methyl and R3 methyl in a meta position;
or R methyl and Ri ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sea-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl or 1β-dimethylbutyl, R ₂ methyl and R ₃ hydrogen; or R methyl and Ri isopropyl, R2 ethyl and R3 hydrogen or methyl in a meta position;
or R is methyl and Ri is methyl, R2 is tert-butyl and R _{3 is} hydrogen or methyl in a meta position. 2. N-methyl ^ '- isopentyloxy-ö'-methyl ^ -chloroacetanilide. 3. N-methyl-2'-n-propoxy-6'-methyl-2-chloroacetanilide 25 4. N-methyl ^ '- n-butoxy-e'-methyl ^ -chloroacetanilide. 5. N-methyl-2'-sec-butoxy-6'-methyl-2-chloroacetanilide. 6. N-methyl-2'-isopropoxy-6'-methyl-2-chloroacetanilide. 7. N-methyl-2'-isobutoxy-6'-methyl-2-chloroacetanilide. 8. N-Ethyl ^ '- n-butoxy-ö'-methyl ^ -chloroacetanilide. 30th 9. N-methyl-2'-isopropoxy-6'-ethyl-2-chloroacetanilide. 10. Herbicide for combating unwanted plants in crops of useful plants, especially in soybean, Peanut, rapeseed, cotton, French bean, alfalfa and vegetable crops containing at least one 2-chloroacetanilide according to claims 1 to 9 in a herbicidally effective amount and at least one conventional amount Additives.