DE3110525A1 - 2-HALOGEN ACETANILIDES AND THEIR USE AS HERBICIDES - Google Patents

Description

DR. BERG DIPL.-ENb * STAPE- *: DIPL.-ING. SCHWABE ". - ^: DiLDl

PATENT LAWYERS

P.O. Box 860245 8000 Munich

Attorney's file: 31

March 18, 198Ϊ

MONSANTO COMPANY ST. LOUIS, MISSOURI / USA

2-rialogenacetanilides and their use as herbicides

* (089) 98S272 . 98 * 273

983310

Telegrams:

BERQSTAPFPATENT Munich TELEX: 0524560 BERG d Bank accounts: Hypo-Bank Munich 441Ο12285Ο (BLZ 70020011) Swift Code: HYPO DE MM Bjyet Vereinsbank Munich 453100 (BLZ 70020270) Postscheck Munich 65343-808 (BLZ 70010080)

description

The invention relates to 2-haloacetanilides and their use in agriculture, e.g. as herbicides.

Among the publications related to this invention there are numerous descriptions of 2-haloacetanilides that are unsubstituted or with a A large number of substituents on the anilide nitrogen atom or on the anilide ring can be substituted, e.g. with alkyl, alkoxy, Alkoxyalkyl, halogen or other radicals.

The compounds according to the invention, which are characterized by an alkoxymethyl radical on the anilide nitrogen, an alkoxy radical in one ortho position and a specific alkyl radical in the other ortho position, correspond most closely, as far as they are known, to those of US Patents 3,442 and 3,547 620, notably, the compounds 2 ^f -tert-butyl-2-chloro-N-methoxymethyl-6'-methoxyacetanilide and their Bromanalog (see FIG. Examples 18 and 34 in U.S. Patent No. 3,547,620 and Examples 18 and 36 in U.S. Patent 3,442,945).

In U.S. Patents 4,070,389 and 4,152,137 a general formula is set forth which compounds of the kind such as are described in U.S. Patents 3,442,945 and 3,547,620;

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includes. The only example connection described, the an alkyl radical in the one ortho position and an alkoxy radical in the other ortho position, but has an alkoxyethyl radical on the anilide nitrogen atom; links of this type are discussed in detail below.

Other less relevant publications are BE-PS 810 76 3 and German application 2 402 9 83; to the Compounds described therein include compounds of the type described in U.S. Patents 4,070,389 and 4,152,137 and those through an alkoxyalkyl radical 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 the BE-PS 810 763 and the German application 2 402 983 are compounds that have an ethoxyethyl radical on the anilide nitrogen atom, a methoxy or ethoxy radical in an ortho position and have a methyl or ethyl radical in the other ortho position (cf. 810 76 3, compounds no. 7, 13 and 18); it other less relevant homologues of these compounds are also described, e.g. compounds No. 6, 9, 16 and 17, the methoxyethyl or methoxypropyl radicals am Nitrogen atom, a methoxy or ethoxy radical in one ortho position and a methyl radical in the other ortho position have substituted.

U.S. Patent 3,442,945 contains some herbicide data

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- «r-ΛΗ

which relate to the above-mentioned compounds, the chemical configuration of which corresponds to the compounds according to the invention is closest related; some data are also in the other patents for others analogous and homologous Compounds indicated that are less closely related in their chemical structure, e.g. compounds 6 and 9 of BE-PS 810 76 3. In particular, although these references describe herbicidal activity against a large number of weeds, however, they do not provide any data for compounds that additionally and / or simultaneously include the perennial that are difficult to kill Weeds such as couch grass and yellow sedge, as well as a wide range of annual weeds, including those that are difficult to kill annual broad-leaved weeds such as thorny sida, Kanf sesbania, thorn apple, etc., and annual weeds such as Sorghum halepense seedlings, Sorghum bicolor, Brachiaria, Panicum species, red rice and Raoul grass under Maintain control while also controlling other harmful annual or perennial weeds such as knotweed, Melde, Amaranthus, Foxtails, Digitaria sanguinalis and check Echinochloa crus-galli.

An extremely useful and desirable property of herbicides is the ability to control weeds for an extended period of time Keeping it under control, the longer during each growing season, the better. With many known herbicides sufficient weed control is only achieved for 2-3 weeks,

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- ι * -45

in some very good cases maybe up to M up to 6 weeks, before the chemical loses its phytotoxic effectiveness. A disadvantage of most known herbicides is that is, their relatively short lifespan in the soil.

Another disadvantage of some known herbicides, to some extent related to the lifespan in the soil below normal weather conditions, is lack of continuity of weed control during heavy rains that inactivate many herbicides.

Another disadvantage of many known herbicides is the limitation their applicability to certain types of soil, i.e., while some herbicides are found in soils with little organic Proportion are effective, they are ineffective in other soils with high organic proportions, or vice versa. It is therefore an advantage if a herbicide can be used in all types of soil from light organic to heavy clays and loams is.

Another disadvantage of many known herbicides is the restriction to a particularly effective mode of application, i. Apply to the surface before emergence or work into the soil. The possibility of a herbicide on each It is very desirable to be able to apply it in a manner by applying it to the surface or working it into the ground. Finally, there is a disadvantage of some herbicides

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the need to take special precautions for their handling due to their toxicity. A Herbicide should also be safe to use.

The invention therefore relates to a group of herbicidal compounds which have the above-mentioned disadvantages of known herbicides avoid and offer a variety of benefits to date were not combined in a single herbicide group.

The invention provides herbicides that are difficult to kill Check perennial and annual weeds, e.g. couch grass, yellow sedge, sorghum halepense seedlings, Sida spinosa, hemp sesbania, Sorghum bicolor, Brachiaria, Panicum species, red rice and Raoul grass, also a broad one Range of other harmful weeds, such as knotweed, melde, amaranthus, thorn apple, foxtails, Echinochloa and Digitaria. In addition, they enable more resistant weeds such as Ambrosiaceae to be pushed back, Abutilon, bindweed and xanthium, while used for many crops such as soybeans, cotton, peanuts, and / or canola French beans remain harmless.

j
Another object of the invention is to maintain the herbicidal activity in the soil for periods of up to 18 weeks.

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The invention also relates to herbicides that are effective against leaching or dilution at high humidity, e.g. Rains, are persistent.

The invention also relates to herbicides, which in a broad Range of soils are effective, so from light to medium organic soils to heavy clay or loam.

Another advantage of the herbicides according to the invention is that they can be used flexibly, for example by application on the surface before emergence or by working into the soil.

Finally, the herbicides according to the invention have the advantage that they are harmless and do not require any special handling Make precautionary measures necessary.

These and other objects of the invention will become more apparent from the following detailed description.

The invention relates to herbicidally active compounds, herbicidal preparations which these compounds as active ingredients contain, and methods of using these herbicidal preparations in certain crops.

It has now been found that a selective group of 2-haloacetanilides which are activated by specific hydrocarbyloxymethyl radicals on the anilide nitrogen atom, specific alkoxy

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radicals in an ortho position and hydrogen or a Methyl or ethyl radical in the other ortho position are, unexpectedly superior and excellent herbicidal properties compared to known herbicides, including related and known homologous compounds.

An essential property of the herbicide preparations according to the invention is their ability to control a wide range of weeds. These include weeds, which can be controlled by common herbicides, as well as a large number of weeds, individually or collectively so far escaped control by a single class of known herbicides. At the same time they are harmless for crops of one or more crops, including in particular soybeans, cotton, peanuts, rapeseed, kidney beans and others belong. While the known herbicides used to control a number of weeds and occasionally Certain resistant weeds have also been shown to be useful The unique herbicides of the invention are found to be able to cure a wide variety of resistant perennials and annuals To control weeds or to push them back to a large extent, so 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, as well as annual grasses such as Shattercane,

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Brachiaria, Sorghum halepense seedlings, Panicum species, red rice, raoul grass, and other harmful weeds such as autumn panicum, foxtail, barnyard grass, and digitaria. An improved weed reduction was also found in resistant weeds such as Airibrosiaceae, Abutilon, bindweed and xanthium achieved.

The compounds of the invention are represented by the formula

ClCH-C CH ^ OR

marked in which

R ethyl, n-propyl, isopropyl, isobutyl, sec - butyl,

Is cyclopropyliriethyl, allyl or propargyl; R. means methyl, ethyl, n-propyl or isopropyl, and R ₂ means hydrogen, methyl or ethyl, with the proviso that, if

R "is hydrogen, R- is ethyl and R is allyl, if

R ₂ is ethyl, R ₁ is methyl and R is isopropyl ₅ when
R ₁ denotes methyl, R denotes ethyl, isopropyl, isobutyl, sec-butyl or cyelopropylmethyI, if

R ₁ denotes ethyl, R represents sec-butyl, allyl or propargyl

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90

poses when

R ₁ denotes n-propyl, R denotes ethyl and if

R. is isopropyl, R is ethyl or n-propyl.

The preferred compound of the invention is 2'-methoxy-6-methyl ^l-N- (isopropoxymethyl) -2-chloroacetanilide.

Further compounds according to the invention are:

2 ¹ -Methoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2'-methoxy-6'-methy1-N- (l-sec-butoxymethyl) -2-chloroacet-

anilide,

2'-ethoxy-6'-methyl-N- (allyloxymethyl) -2-chloroacetanilide, 2'-ethoxy-6'-methyl-N- (propargyloxymethyl) -2-chloroacetani-

2'-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide,

2 «-Methoxy-6 ^f -ethyl-N- (isopropoxymethyl) -2-chloroacetanilide, 2'-ethoxy-6'-methy1-N- (1-methylpropoxymethyl) -2-chloroacet-

anilide,

2'-n-Propoxy-6 ^I -methyl-N- (ethoxymethyl) -2-chloroacetanilide _i 2'-Isopropoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide

2'-Isopropoxy-6'-methy1-N- (n-propoxymethyl) -2-chloroacetani-

The usefulness of the compounds according to the invention as Active ingredients in the herbicide preparations produced therewith, as well as the application method, are described below.

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The compounds according to the invention can be different Way to be made. For example, they can be produced by the azomethine route, which is described in the above-mentioned U.S. Patents 3,442,945 and 3,547,620. In this azomethine process, the appropriate primary becomes aniline reacted with formaldehyde to the corresponding methylene aniline (substituted phenylazomethine), which is then reacted with a Halogenacetylating agents such as chloroacetyl chloride or Chloracetyl anhydride is implemented. Then the appropriate alcohol is used to give the corresponding N-alkoxymethyl-2-chloroacetanilide implemented as an end product.

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

Yet another method for the production of the invention Do you see connections? N-alkylation of the Ainon: - (! Er; suitable secondary 2-haloacetanilide with a. Alkylating agents under basic conditions. The N-alkylation process is described in more detail in Examples 11-14.

example 1

In this example, the preparation of a preferred embodiment, namely 2 '~ methoxy-6'-methyl-N- (isopropoxy-

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methyl) -2-chloroacetanilide.

0.025 mol of 2 ^l -methoxy-6 ^l -methyl-N- (methoxymethyl) -2-chloroacetanilide in 100-150 ml of isopropanol, which contained about 0.02 mol of methanesulfonic acid, was refluxed in a Soxhlet extraction apparatus, the thimble 25 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 dissolved in ether or chloroform. The solution was washed with 5% sodium carbonate solution, dried (MgjSO ^ and evaporated The product was purified by Kugelrohr distillation yield 55%;.. Pale amber solid, mp 40-41 ⁰ C..
Elemental analysis calculated for C. _ü H " _{r .ClN0 Q} (%):

C: 58.84; H: 7.05; N: 4.90; Cl: 12.41

Found: C: 58.55; H: 7.08; N: 4.89; Cl: 12.45 The product was identified as the initially mentioned compound.

Examples 2 to 9

Virtually the same procedures, amounts of reactant, and general conditions described in Example 1 were used used, but for the transetherification to the end product the appropriate alcohol was substituted to others, the

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N-Hydrocarbyloxymethyl-2-haloacetanilide corresponding to the above formula to manufacture; these compounds are listed in Table I.

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σ> ca «ο

Link; Table I. Bp. ⁰ C
(mm Hg) Ele
ment analysis Found ι
ι at
game
No. 2 -Methoxy-6'-methyl-N-
(ethoxymethyl) -2-
chloroacetanilide Empirical
formula 170
(0.1) C.
H
N Calculated 57.19
6.70
5.11 2 2'-methoxy-6'-methyl-
N- (1-methylpropoxy-
methyl) -2-chloroacet-
anilide ^C 13 ^H 18 ^C1N0 3 C.
H
. N
Cl 57.46
6.67
5.16 59.90
7.36
4.62
11.97 3 2'-ethoxy-6'-me thy1-
N- (allyloxymethy1) -
2-chloroacetanilide 15 22 3 110
(0.07) C.
H
N
Cl 60.10
7.40
4.67
11.83 60.30
6.80
4.64
11.69 CaJ 4th 2'-ethoxy-6'-methyl-
N- (propargyloxymethy1) -
2-chloroacetanilide C _1O H _2O C _1N O ₃ 140
(0.1) C.
H
N
Cl 60.50
6.77
4.70
11.91 60.98
6.14
4.74
11.94 CD
CJl
K)
CJl 5 2'-ethoxy-6-methyl-
N- (1-methylpropoxy-
methyl) -2-chloroacet
anilide ^C 15 ^H 18 ^C1N0 3 135
(0.09) C.
H
N
Cl 60.91
6.13
4.74
11.99 60.98
7.69
4.42
11.22 6th 2'-methoxy-6'-methyl-
N- (is obutoxyme thy1) - 2-
chloroacetanilide ^C 16 ^H 24 ^C1N0 3 140
(0.1) C.
H
N
Cl 61.24
7.71
4.46
11.30 59.88
7.41
4.62
11.82 7th C ₁₅ H ₂₂ ClNO ₃ 60.10
7.40
4.67
11.83

Table I - continued

analysis

link

Empirical
formula

Bp. ⁰ C (mm Hg)

2'-methoxy-6'-methyl-N- (cyclopropylmethoxymethyl) -2-chloroacetanilide

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

^C 15 ^H 2O ^C1NO 3

Element Calculated Found

145 C. (0.1) H N Cl oil C. H N Cl

60.50
6.77
4.70

11.91

60.10
7.40
4.67

11.83

60.26 6.77 4.66

11.80

59.81 7.46 4.61

11.71

Example 10

Preparation of the tertiary N- (methoxymethyl) -anilide starting materials used to produce the end products of Examples 1 to 9.

The N-methylene ether-substituted ones used in Examples 1 to 9 2-Chloroacetanilide precursors were obtained by alkylating the appropriate secondary 2-haloacetanilide produced by the above-mentioned N-alkylation process. In this example, this procedure is described with respect to the preparation of the starting material of Example 1.

0.025 mol of 2'-methoxy-6'-methyl-2-chloroacetanilide, 0.05 mol of bromomethyl methyl ether and 2 g of benzyltrieth3'-ammonium bromide were dissolved in 70 ml of methylene chloride. 40 ml of 50% Katriuirhydroxidlösung was then added in portions with stirring and cooling, thereby maintaining the temperature between 20 and 2 5 ⁰ C. After the addition was complete, the mixture was stirred for a further 1.5 hours. 100 ml of water was 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-SO ₄ ) and evaporated. The residue was crystallized out or distilled in vacuo, giving a yellow liquid, boiling point 140 ^° C. at 1.2 mm Hg.

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Elemental analysis; Calculated for C ₁₂ H ₁₅₃

C: 55.92; H: 6.26; N: 5, HU Found: C: 56.15; H: 6.33; N: 5.36

The product was found to be 2'-methoxy-6'-methyl-N-C (methoxymethyl) -2-chloroacetanilide identified.

Similarly, the N-methylene ether were substituted 2-chloroacetanilide starting materials of Examples 2 to 9 Alkylation of the corresponding secondary anilide with bromomethyl methyl ether manufactured; The analogous chloromethyl and iodomethyl methyl ethers can also be used.

That in this example for the preparation of the tertiary N-Methoxyir.ethylverbindungen The secondary anilide starting material used was obtained by chloroacetylation of the corresponding primary Amines made as follows:

0.03 mol of 2-kethoxy-6-methylaniline in 30 ml of methylene chloride was stirred vigorously with 0.05 mol of 10% sodium hydroxide solution, while a solution of 0.033 mol of chloroacetyl chloride in 20 ml of methylene chloride was added; the temperature was kept ^{between 15 to 25 °} C. with the aid of external cooling. After the addition was complete, the reaction mixture was stirred for a further 30 minutes, the layers separated and the methylene chloride layer washed with water, dried and evaporated in vacuo. The product was crystallized from a suitable solvent, leaving white needles,

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Mp. 130-131 ⁰ C, received.

Elemental analysis: Calculated for C ₁₀ H _{12 ClNO 2} (%):

C: 56.21; H: 5.66; N: 6.56; Cl: 16.59

Found: C: 56.16; H: 5.66; N: 6.57; Cl: 16.55

The product was found to be 2'-methoxy-6'-methyl-2-chloroacetanilide identified.

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 prepared by known methods can be produced, e.g. by catalytic reduction of the corresponding substituted nitrobenzene in ethanol under Use of a platinum oxide catalyst.

As already mentioned, the products according to the invention can also directly from the secondary anilide using the mentioned N-alkylation process can be obtained without first the N-hydrocarbyloxymethyl intermediate described in Example 10 is produced, which is then transetherified to the end product described in Example 1. In the Examples 11 to IU describe the preparation of compounds according to the invention using the N-alkylation process.

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Example 11

4.35 g of 2'-n-propoxy-6 ^l -methyl-2-chloroacetanilide, 3.4 g of chloromethyl ethyl ether, 1.5 g of benzyltriethylammonium chloride were mixed in 250 ml of methylene chloride and cooled. To the mixture, 50 ml of 50% NaOH was added at 15 C and 2 hours
stirred, because 100 ml of water were added. The layers were separated, washed with water, then over MgSO ^
dried and evaporated. The product was purified with Kugelrohr distillation and U.8 g (89% yield) of clear liquid, boiling point 130 ^° C. at 0.07 mm Hg, were obtained.
Elemental analysis: Calculated for C rH _{22 ClNO 3} (%):

C: 60.10; H: 7.40; Cl: 11.83 Found: C: 59.95; H: 7.39; Cl: 11.79

The product was found to be 2'-n-propoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide identified.

Example 12

5.55 g of 2'-isopropoxy-6'-methyl-2-chloroacetanilide, 4.4 g
Chloromethyl ethyl ether, 2.5 g of benzyltriethylammonium chloride in 2 50 ir.l methylene chloride were mixed and cooled to 0 ⁰ C. To the mixture 50 ml of 50% igesNa0H were added all at once, while the temperature was kept below 15 ⁰ C. The mixture was stirred for 2 hours, cooled, then 100 ml of water was added. The layers were separated, washed with water, _{dried over MgSO u} and evaporated, giving 4.7 g

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(69% yield) gave product as a yellow

Elemental analysis: Calculated for C ₁₅ H _{22 ClNO 3} (I):

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 ^f -methyl-N- (ethoxymethyl) -2-chloroacetanilide.

Example 13

Practically the same procedure as described in Examples 11 and 12 was followed, except that chloromethyl propyl ether was used as the alkylating agent. 5.0 g (88% yield) of a yellow oil were obtained. Elemental analysis: Calculated for C ₁₅ H _{24 ClNO 3} ^):

C: 61.24; H: 7.71; N: 4.46; Cl: 11.30 Found: C: 61.18; H: 7.76; N: 4.43; Cl: 11.31

The product was found to be 2'-isopropoxy-B-methyl-N-yne-propoxymethyl) -2-chloroacetanilide identified.

Example 14

The same procedure as described in Examples 11-13 was followed, except that the appropriate secondary anilide and halomethyl allyl ether were substituted. A yellow oil was obtained, boiling point 134 ^° C. at 0.08 mm Hg (Kugelrohr).

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Elemental analysis; Calculated for CH ₁₈ ClNO ₃ (%):

C: 59.26; H: 6.39; N: 6.94; Cl; 12.49 Found: C: 59.20; H: 6.41; N: 6.95; Cl: 12.52

The product was found to be 2 '-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide identified.

It has been found that the herbicides of the invention are unexpectedly superior as pre-emergence herbicides, especially for selective control of difficult-to-kill perennial and annual weeds; this includes perennial weeds such as couch grass and yellow sedge, annual broad-leaved weeds such as thorny sida, hemp sesbania, thorn apple, Knotweed plants, melde plants, 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 compared to known acetanilides an improved reduction of the weed population of other resistant species such as e.g. Ambrosiaceae, Abutilon, Bindweed and Xanthium scored.

Selective control and improved suppression of the mentioned weeds with the herbicides according to the invention was made observed in a variety of crops including soybeans, cotton, peanuts, canola, and French beans. selectivity was also shown in some tests for sugar beet, field maize, sweet maize, wheat, barley and sorghum; this KuI-

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Doors are generally opposite to those according to the invention Herbicides less tolerant than the above crops. It will be apparent to those skilled in the art that not all of the above-listed weeds selectively by all compounds according to the invention under all conditions what Climate, soil type, humidity and / or application method are controlled.

To the unexpectedly superior properties of the compounds according to the invention on both absolute and relative To represent the basis, comparative greenhouse and field tests were carried out with:

1. Known compounds which are most closely related in their chemical structure to the compounds according to the invention are;

2. other homologues from the field of the known compounds mentioned, which have outstanding herbicidal properties;

3. Commercially available herbicide compounds whose chemical structure is generally similar to that of the compounds according to the invention Is related. All of the compounds in the comparative tests listed below are generally considered to be substituted Phenyl-N-alkoxyalkyl-2-haloacetanilxde defined. In the tables, the compared known compounds are identified as follows:

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A. 2'-Methoxy-6'-tert-butyl-N- (methoxymethyl) -2-chloroacetanilide (Example 18, U.S. Patents 3,442,945 and 3,547,620).

B. 2'-Methoxy-6'-tert-butyl-N- (methoxymethyl D-2-bromoacetanilide (Example 34 of U.S. Patent 3,547,620 and Example 36 of U.S. Patent 3,442,945).

C. 2 ', 6'-Diethyl-N- (inethoxymethyl) -2-chloroacetanilide (Example 5 of U.S. Patents 3,547,620 and 3,442,945; this compound is known as "Alachlor" and represents the active ingredient in the commercially available herbicide LASSO, registered trademark of Monsanto Company).

D. 2 ^l -Methyl-6'-ethyl-N- (ethoxymethyl) -2-chloroacetani-

lid (Example 53 of U.S. Patent 3,547,620; general name "Acetochlor").

E. 2 ', 6'-Dimethyl-N- (isopropoxymethyl) -2-chloroacetanilide (Example 31 of U.S. Patent 3,547,620 and Example 33 of U.S. Patent 3,442,945).

F. 2'-Methoxy-6'-methyl-N- (methoxyethyl) -2-chloroacetanilide (Connection no. 6 of BE-PS 810 763).

G. 2'-Methoxy-6'-methyl-N- (ethoxyethyl) -2-chloroacetanilide (Connection no. 7 of BE-PS 810 763).

H. 2'-Methoxy-6'-methyl-N- (1-methoxyprop-2-yl) -2-chloroacetanilide (Connection no. 9 of BE-PS 810 76 3) and

I. 2 ^L -Methyl-6 ^L -ethyl-N- (1-methoxyprop-2-yl) -2-chloroacetanilide (U.S. Patent 3,937,730; generic name

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"Metolachlor"; this compound is the active ingredient in that commercial 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 I with regard to the control of various perennial or annual weeds, with the difficult-to-kill species being predominant such important crops as soybeans, cotton, peanuts, rapeseed and French beans are particularly affected became. The test results are summarized below.

In the following discussion of the data, reference will be made to herbicide application rates beginning with "GR _11. " and "GR _RI -" are displayed; these amounts are given in "pounds per acre" (lbs / A) which can be converted to kg per hectare (kg / ha) by multiplying by 1.12. GR ₁ ^ defines the maximum amount of herbicide at which damage occurs in 15% or less of the crops, while GR _t the necessary minimum amount

DJ

with which an 85% inhibition of weeds is achieved. The GR ₁ and GR _p , quantities are used as a measure of the possible performance of commercially available products, it being understood that suitable commercially available herbicides can cause greater or lesser damage to plants within reasonable limits.

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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 degree of harmlessness to crops and is called the ratio GR ^ _C / GR_ _C

SO OO

expressed, i.e. GR ₁ , - amount for the crop divided by GR ₀ - amount for the weed, both amounts expressed

in lbs / A or kg / ha. The tables show the selectivity factors, as far as a.e are used, in brackets after given to the weeds; "NS" means "non-selective"; insignificant or indefinite selectivity is indicated by a dash After the weed appears, a blank means that the plant species is not participating in a particular test implied that for some reason the data was not obtained or was less significant than existing data were Y then shorter-term observations are not given, for example in favor of longer-term data, or longer-term observations Data is omitted because data was definitive for a shorter period for a particular herbicidal activity.

Because crop tolerance and weed control are related to each other Relationship, a brief discussion of this relationship, expressed as a selectivity factor, is appropriate. In general it is desirable that the harmless factors for the crop are high because of one or the other Reason often higher herbicide concentrations are desired.

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3b

Conversely, the quantities for weed control should be used for economic and possibly ecological reasons be small, i.e. the herbicide should have a high unit activity. Small application rates of a herbicide are however, it may not be sufficient to control certain weeds and a greater amount will be needed. the The best herbicides are therefore those that control the greatest number of weeds with the lowest application rate and offer the greatest possible harmlessness to the crop, i.e. crop tolerance. The (defined above) Selectivity factors are thus used to determine the relationship between harmlessness to the crop and quantify control of weeds; the following applies to the selectivity factors given in the tables: the higher the numerical value, the greater the selectivity of the herbicide for weed control in a particular one Culture.

The listed pre-emergence tests include both greenhouse and Field tests. In the greenhouse tests, the herbicide is used either after seeds or cuttings are planted on the surface or it is worked into a certain amount of soil that is used as a top layer over test seeds in sown test containers should be spread. In the field tests, the herbicide is used in the soil before planting incorporated (P.P.I.) i.e. it is applied to the earth's surface

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applied, then mixed with the earth, then the cultivated plant seeds are planted.

The surface test procedure used in the greenhouse is carried out as follows: Containers, e.g. aluminum pans with about 2 4x13x7 cm, or plastic pots with about 9.5x9.5x8 cm, with drainage holes in the bottom, are to the edge with Ray Silt loam filled, which 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 with a 1.3 cm layer of the test soil. The herbicide is then applied to the surface of the soil with a belt sprayer (187 l / ha, 2.11 kgf / cm); Other spray devices, such as a DeVilbiss sprayer, are used on occasion used. Each pot is doused from above with 0.6 4 cm of water, then the pots are placed on greenhouse tables and watered from below as needed. In an alternative method, watering from above can also be omitted. Approximately The effect of the herbicide is determined 3 weeks after the treatment.

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

Good topsoil is placed in aluminum pans and up to Tapped 1 to 1.3 cm below the edge. Onto the earth becomes a number of seeds or offshoots of various types of plants

- / 37

distributed. The soil required to completely fill the pans after sowing or planting is poured into a Pan weighed. The earth and a known amount of active ingredient in the form of a solution or suspension of wettable Powders are mixed thoroughly and used to cover the prepared pans. After the treatment, the Pans an initial watering from above, which corresponds to 0.64 cm of rainfall, then they are from as needed watered below so there is adequate moisture for germination and growth. The irrigation of above can also be omitted. Assessment takes place about 3 weeks after sowing and treatment.

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

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Amount for ^GR 85 Table II (NS) Quantity for GR ₁₅ Corn (NS)
(NS) (2)
(1.5) (NS)
(NS)
(NS)
(NS) (kg / ha (NS)
(NS) (kg / ha) 0.17
0.28 0.034 (NS)
0.07 (NS) (1)
(1) Cyperus Couch grass (4)
(2) cotton 0.78
0.84 (NS) link > 2.2 1.6 (1.5)
(2) > 2.2 (-) 0.22
0.22 (NS)
(NS) A. 0.69 2.8 (1) > 2.2 (> 2.0) 0.09 (NS)
(NS) β 0.45 0.56 (NS)
(NS) <O, 22
<O, 22 <1.5 (NS)
1.25 (3.5) C. 0.2 0.18 Soy off (NS)
(NS) 0.25 (1) <0.07
<0.07 <0 ^ 9
<0.07
<0.07 D. 0.17 3.1
0.28 (1.5)
(6) 0.48 (3) E. 0.34 0.27 0.56
1.1 (NS)
(1.5)
(3)
(1.5) 0.21 (NS) F. 0.25 0.20 1.7
1.1 0.39 (1.5) G 1.5 0.36 0.39
0.39 2.9 (2)
2.7 (7.5) H 1.7
0.10 0.9
0.20 0.21 <1.7 (NS)
1.3 (1.5)
0.28 (3) Example 1 0.21
0.21 <0.07
<0.07 2.2
2.2 1 »* 3
0.28
0.28

Table II - continued

2 Amount for
(kg / ha ^GR 85 Soybeans Quantity for GR ₁₅
(kß / ha) Corn (NS)
(NS) Sr
■ 0 • CO 3 Cy perus Couch grass 0.17 (1)
0.13 (2) cotton <0.17
<0.07 (NS)
(NS) CD
CJl link 4th
5 0.17 0.07 0.77 (3)
0.81 (6) 0.17 (1)
0.07 (1) <O, 26
<0.13 (NS)
(NS)
(NS)
(NS) Ex. 6th 0.26 0.13 1.0 (3.0)
1.0 (4.5)
3.4 (12.0)
3.4 (12.0) 0.77 (3) <O, 34
<O, 22
<O, 28
<O, 28 (NS)
(NS) Ex. 7th 0.34
0.28 0.22
0.28 2.0 (8.0)
2.2 (8.0) 1.0 (3.0)
2.8 (10.0) <O, 26
<O, 28 (NS)
(NS) Ex.
Ex. 8th 0.26 0.28 0.90 (4.0)
0.90 (1.6) 2.5 (10.0) <0.15
<0.15 (NS)
(NS) Ex. 9 0.22 0.56 0.56 (1.5)
0.56 (3.3) 1.5 (6.5) <0.13
<0.13 (NS)
(NS) Ex. 0.37 0.17 5.6 (10.0)
5.6 (11.9) 0.72 (1.9) <O, 28
<O, 28 Ex. 0.56 0.47 1.7 (3.0) Ex.
I. ■ ^.
-P
O

Table Xl -

link 12th Quantity for GR _g5 Couch grass Soybeans (2,
(2, 5)
5) Amount for GF 0) Corn (NS)
(NS) Ex. 13th (kg / ha) 0.11 0.28
0.28 (2,
(2, 0)
0) (kg / ha) 0) <0.12
<0, ll (NS)
(NS) Ex. 14th Cyperus 0.28 0.45
0.56 :> i5 , 6) cotton ) <O, 22
<O, 28 (15.6)
(11.1) Ex. 0.12 0.50 > 5.6 (
> 5.6 ( 0.25 (2, 5.6
5.6 0.22 2.7 (12, O
O
σ>
"_". 0.36 1.4 (3.9 " ¹ N,
O
430
Cn »
«Ο

From Table II it can be seen that in general the invention Compounds as a class are significantly more active, i.e., a higher unit activity against Cyperus esculentus and couch grass, and are more harmless to soybeans and cotton than the reference compounds.

Regarding the control of Cyperus esculentus, it should be noted that each tested compound of the invention was remarkably more active than compounds A and B, which are structurally most closely related by the reference compounds, and also as compound H, which is less related than A and B, which in certain respects can be regarded as more closely related to the compounds according to the invention than the compounds C, D, E and I. It should be noted in particular that the compound of Example 1 with a GR _{R [} . 10 kg / ha was about twice as active as the most active reference _{compound E (GR g} t 0.17 kf./ha), while it had a harmless factor 3 times as high as 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 unit activity than compound E against Cyperus esculentus. The reference compounds F and G, while having fairly high unit activity, none of the compounds was selective against Cyperus

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in soybeans, nor was Compound F selective in cotton. Compound G controlled Cyperus in cotton that However, harmlessness was lower than that of all of the invention Compounds, with the exception of Example 2, and noticeably lower than those of Examples 5, 6 and 13. The selectivity factors the compounds of Examples 9 and 14 versus Cyperus in soybeans were particularly excellent.

With regard to the couch potato control, the compound of Example 2 was almost 3 times as active as the most active reference chemical, Compound D, while equivalent harmlessness to soybeans was achieved. The compound according to the invention from 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 tested compound according to the invention had an outstandingly superior unit activity against couch grass compared to compounds A and B, which the air. next related tested reference compounds. The unit activity of compound H against couch grass was slightly higher than that of the compounds of Examples 9 and IU _{5, but} the selectivity factors of these latter compounds for couch grass in soybeans were about twice as great as those of compound H, the closest related reference compound · Im otherwise the reference compounds A, B, F and G were not selective towards couch grass in soybeans.

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Table II also shows that of all the compounds tested, the compounds of Examples 5, 6, 9 and 14 possessed by far the highest safety factors for soybeans relative to Cyperus and couch grass. The compounds of Examples 5, 6 and 13 had by far the highest safety factors for cotton, relative to Cyperus esculentus. It can also be stated that the extremely good harmlessness factors of the compounds of Examples 5, 6, 9, 13 and IU were associated with very low GR _fit amounts, which indicates a high unit activity against Cyperus and couch grass. In these tests, most of the compounds of the invention were not selective in quays, the same is true for all but three reference compounds. However, the compound of Example 14 showed extraordinarily superior selectivity relative to couch grass and Cyperus in maize.

In further comparative tests, the herbicidal pre-emergence activity of the reference compounds C and D and the compound of Example 1 in various annual broadleaf Weeds tested with an application rate of 3.35 kg / ha. The assessment was carried out 6 to 7 after the boil Treatment (WAT) and percent control of weed growth was recorded. The data from this test are shown in Table III.

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Table III

Control annual broad-leaved weeds

Pre-emergence test, 6 to 7 WAT

weed % Control at
link 3, C. 36 kg / ha example 1 35 D. Sida spinosa 93 0 73 Sesbania exaltata 100 62 69 Amaranthus 83 64 88 Polygonum 88 61 76 Report 75 53 81 Aii.brosiaceae 72 68 43 Thorn apple 98 9 8

It can be seen from Table III that the compound of Example 1 has excellent activity superior to that of the compound C to each broadleaf weed tested. Similarly, the compound of Example 1 shows markedly superior activity compared to Compound D towards Sida spinosa, Sesbania exaltata, Polygonum and Ambrosiaceae, while having equivalent activity towards thorn apple, and slightly less activity towards Amaranthus and Melde.

For further comparisons, field tests were carried out to determine the relative pre-emergence activity and selectivity of the compound

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of Example 1 in comparison 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 2 80.6 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 (GRq ₅ ) was achieved at only 1.96 kg / ha, while GR _{05 was} 5.6 kg / ha for each of compounds C, E and I and 5.0 kg / ha for compound D. GR _1c 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 GR ₀₁ value, about three times the amount of the compound from 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. 4.2 kg / ha of compound I and 2.8 kg / ha of compound E were used to achieve GR_ ₅ and 1,1 or. 1.5-fold selectivity factors are required. With the compound of Example 1, however, GR _fin . with 0.8 kg / ha and a 4.7-fold selectivity factor in

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130061/0833

MT-

Reached soybeans.

Compounds C, D and E were opposite at 7 WAT
Echinochloa in soybeans non-selective. Compound I.
and compound of 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 comparable Control of Echinochloa by compound I, the compound of Example 1, the reference compounds C, D, E and I. significant in the selective control of all three annual weeds in soybeans 7 weeks after treatment was superior.

Further tests to determine the relative herbicidal activities and selectivities over even longer periods of time found the same herbicides as the previous ones
Tests examined again in field tests, this time in individual plots from silty clay to silty clay lehir,
with 3.0 to 3.5% share of organic substances. In parallel tests, for pre-emergence control, emulsifiable concentrates of the respective herbicides were applied to the surface or worked into the soil before planting, again at 280.5 l / ha, which contained the appropriate herbicide concentration as active ingredient. In these tests, the herbicides were used in the control of perennial couch grass and

- / 1 + 7

130061/063 9

uft

Annual broad-leaved weeds Ambrosiaceae, Amaranthus and Polygonum in soybeans compared. These tests were exposed to heavy precipitation, 4.45 cm am fifth day after treatment ("DAT"), and 2.2 9 cm, 1.52 cm, 1.27 cm on the following days. The data are compiled in Table IV.

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Table IV

ο σ> ο » co

Pre-emergence activity

Incorporation before planting GRgg amount (kg / ha)

GR ₁₅ amount (kg / ha)

link 1 WAT Couch grass Ambrosiaceae Amaranthus polygonum 4.5
3.4 2.5
3.4 Soybeans Ex. 3
6th
9.5 2.2
2.2
2.5 5.6
> 6.7 2.2 4, 5
5.0 > 6.7
> 6.7 1.7
. 2.5
> 3.4 C. 3
6th
9.5 > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 > 6.7 5.6
> 6.7 > 4.5
> 4.5
> 4.5 D. 3
6th
9.5 5.6
> 6.7
6.7 > 6.7
> 6.7 > 6.7 4.5
4.5 3.9
4.2
4.5 E. 3
6th
9.5 > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 4.2 > 6.7
5.9 2.2
2.8
4.2 I. 3
6th
9.5 > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 > 6.7 1.7
3.9
5.0 1 Surface treatment 3.4
4.8 Ex. 3
6th
9.5 2.5
2.5
4.5 4.5
5.0 > 6.7
5.9 1.5
3.4
4.2 C. 3
6th
9.5 5.9
> 6.7
> 6.7 > 6.7
> 6.7 3.9
2.2
> 4.5

O <jri

Table IV - Pre-Emergence Activity Continuation

Incorporation before planting GR ₈₅ -Henge (kg / ha)

GR ₁₅ amount (kg / ha)

link WAT 5 Couch grass Ambrosiaceae- Amaranthus Polygonum Soybeans D. 3
6th
9, 5 > 6.7
> 6.7
> 6, 7 > 6.7
> 6.7 6.7
5, 0 7.0
6.7 0.34 '
3.9
5.3 E. 3
6th
9, 5 5.6
> 6.7
> 6.7 > 6.7
> 6.7 5.6
5.0 4.5
5.6 2.5
2.0
4.8 I. 3
6th
9, > 6.7
> 6.7
> 6.7 > 6.7
> 6.7 > 6.7
> 6.7 > 6.7
> 6.7 4.5
4.5
4.5

'Vl

cn O

OT

It can be seen from Table IV that when incorporated prior to planting, none of the reference compounds 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 ₁₅ / GR _fi5 , which gives a value% on 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 connection 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.

Also in the surface application tests of the herbicides, none of the reference chemicals controlled any of the weeds in soybeans selectively at application rates of 6.7 kg / ha at 6 or 9.5 ViAT, with the exception of compound D in Amaranthus at 9.5 WAT. In these tests, selective weed control was used for the compound of Example 1 on couch grass and poly-

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gonuiJi observed at 6 WAT j and in Amaranthus at 9.5 WAT; the harmlessness factor here was slightly greater than that for compound D, i.e. 1.3-fold versus 1.1-fold. In these tests, too, the compound from Example 1 showed a much higher herbicidal activity than the reference compounds.

The table shows that on the basis of the following criteria, namely the unitary activity against the weeds, the tolerance of the soybeans to the herbicides, the harmless factors and the methods of application, the compound of Example 1 had significantly superior properties as a pre-emergence herbicide than the compared reference compounds.

Continued weed control by the compound of Example 1 under heavy rainfall demonstrated that the Connection 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 were tested the herbicide both applied to the surface and incorporated into the soil prior to planting; yellow sedge was included in the pre-planting test. The soil used for the tests was silt loam with

130061/0039

1.7% organic content. Assessment took place 2, 6 and 9 weeks after treatment. The data for the application on of the surface based on 3 passes show that compound 1 has more than 2 times the unit activity against Like compounds D and E, Sida spinosa had its activity at 6 WAT and 1.5 times its activity at 9 WAT. Connection D was not selective towards Sida spinosa in cotton at 6 and 9 WAT, respectively. The selectivity factors for compound E. 6 and 9 WAT were 1.1 and 1.3, respectively, compared to 3.3 and 1.8 for the compound of Example 1. Although the unit activities of each compound tested were comparable to Digitaria at 6 WAT, that compound was of Example 1 at 9 WAT more active than Compound E, and more selective (i.e., S.F. > H, 0) as compound D, the S.F. 2.8.

When testing with incorporated herbicide before planting was the unit activity of the compound of Example J after 9 WAT compared to Cyperus about 2 times as large as that of the Reference chemicals, compared to Digitaria slightly less than 2 times as large, and compared to Sida spinosa more than 1 1/3 times as large. In this field test checked the connection of Example 1 Cyperus in cotton selectively up to 6 VJAT, while the PeffcrenzchemiKalien not even with 2 WAT selectivity showed. None of the test chemicals selectively controlled Sida spinosa in this PPI test, the compound of Example 1 compared to the other compounds

130061/0639 ^{/ 53}

but much better. The compound of Example 1 and compound E controlled Digitaria at just under 2 WAT, waim thereafter, however, non-selective; connection D was closed selective to Digitaria at no point in time.

The most important conclusions from the above field tests in cotton are thus that the compound of Example 1 is compared the weeds Cyperus and Sida spinosa was significantly more active than the reference compounds, with this activity was maintained over a longer period, and that the compound of Example 1 against these weeds possessed superior selectivity factors. Moreover, the compound of Example 1 compared with Compound E is superior unit activity, and when compared to compound D is superior in selectivity to Digitaria in cotton at 9 WAT.

Further comparative tests were carried out with the compound of Example 1 and the compounds D and E, about their relative herbicidal effectiveness and the duration of action in the soil against the perennial weeds Cyperus exculentus and couch grass to determine. The compounds D and E are among the most active selective herbicides of the known 2-haloacetanilides, and they were considered for this class as Standards for testing other herbicides against cyperus and couch grass and other weeds. With the ones discussed here

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Tests were planted for 2 rounds of each treatment 25 Cyperus tubers and 25 pieces of mercury rhizomes. the
Herbicides were incorporated into the soil cover layer in _{amounts sufficient to determine the GR 50 amount}
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, replanted, then for the
placed in the greenhouse for the next cycle. The test results are shown in Table V, "WAT" means
"Weeks After Treatment".

Table V

Duration of action in the soil GR ₅₀ kg / ha

Compound Cyperus esculent us couch grass VJAT

Example l <1.4 <1.4 3

<1.4 · <1.4 6

1.4 1.4 12

8.4 11.2 18

D <1.4 <1.4 3

1.12 1.4 6

5.9 5.6 12

> 11.2> 11.2 18

E <1.4 <1.4 3

1.4 1.7 6

7.8 11.2 12

> 11.2> 11.2 18

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The data for the control of Cyperus in Table V shows that at 3 WAT the GRgQ amount of each compound is below 1.4 kg / ha was, while at 6 WAT there were some decisive differences occurred. In 12 WAT, significant differences in the 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 was needed of Compound D and 7.8 kg / ha of Compound E to achieve the same level of control over Cyperus esculentus. at 18 WAT, only 8.4 kg / ha of the compound of Example 1 was required for the 50% control of Cyperus with a mean value above 11.2 kg / ha (the maximum amount used) of compounds D and E.

Similarly, the data on couch grass in Table V shows that at 6 WAT the compound of Example 1 and the compound D showed slightly superior activity to compound E. At 12 WAT, however, the extraordinary superiority of the compound of example 1 in that only 1.4 kg / ha are required to produce the same To achieve control over couch grass, which requires 5.6 kg / ha for compound D and 11.2 kg / ha for compound E. 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 to act in a variety of soil types. Accordingly

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are summarized in Table VI data showing the herbicidal Effect of the compound of Example 1 on Cyperus in cotton and soybeans in a variety of soil types show the different proportions of organic matter and clay. The herbicides were in the soil incorporated, the seeds planted 0.9 5 cm deep, from above it was watered with 0.6 4 cm. The assessment took place 18 days after treatment.

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Table VI Organi
sch
Shares,% Ray silt loam 1.0 Sarpy clay loam 2.3 Georgeville
silty clay loam 2.9 Wabash clay 4.3 Drummer
silty clay loam 6.0 Florida sand 6.8

^GR 85 ^GR 15

υ γ, κ-ηΗ _{n R} ,, Dune (kg / ha) (kg / ha)

verpxnaung poqenarx proportions,% clay,% Cyperus cotton soybeans

Example 1 ^Ra y silt loam 1.0 9.6 0.22 0.73 0.56

0.07 0.95 0.95

37.0 0.12 0.47 0.56

O Wabash clay 4.3 33.0 0.22 1.12 0.95

37.0 0.22 0.95 0.87

1.8 0.27 0.56 0.48 (U)

cn ro cn

From Table VI it can be seen that the compound of Example 1 is fairly insensitive to soil type and organic content Fabrics seems to be; it shows selective control of Cyperus in both cotton and soybeans in Soils with 1.0 to 6.8% organic matter and 1.8 to 9.6% clay, the selectivity factors were greatest in Sarpy Clay.

Further tests were carried out to determine the herbicidal performance of the compound of Example 1 in soils rich in organic matter. In three repeated field tests, the activity of the compound of Example 1 against Amaranthus and Melde was tested in soybeans planted in black peat soil. 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 application to the surface, they were carried out in black peat soil containing 2-3% organic matter. In these tests, the compound of Example 1 showed the highest unit activity against reporting in H WAT both in the PPI and in the SA method and, in the PPI method, the highest selectivity factor in soybeans, ie greater than 2.7 against 1, 1 for each of compounds C and D; compounds E and I were non-selective at 4 WAT. All compounds were nonselective to reporting at 7 WATs in either method of application;

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Compound E was slightly more active than the compound of Example 1 at 7 WAT in both application methods. Compared to Amaranthus, compound D had the highest unit activity and the highest selectivity factor (1.9) 7 WAT in both application methods; in the method of application to the surface, the selectivity factor of Compound D was almost twice that of Compound of Example 1 and Compound E; no other compounds were selectively controlled by Amaranthus at 7 V7AT in either method of application. The compound of Example 1 (SF 2.0) and compounds C and E (SF 1.0 each), Amaranthus selectively controlled U WAT using the PPI method.

The above tests thus show that when the compound of Example 1 is incorporated into the soil, the best selective control of reporting in soybeans is obtained when compared with the reference compounds in black peat soil; this compound had the highest unit activity and the highest selectivity factor at 4 VJAT of any compound tested. In addition, the compound of Example 1 selectively controlled Amaranthus up to 7 WAT with the surface method, and up to H WAT with the PP! Method. Compound D gave the best control of Amaranthus at 7 WAT with both application methods. The relative performance of the compound of Example 1 and compound D in

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black peat should be further compared to that relative performance of these two compounds in soils that contained less organics, e.g., 3.0-3.5%, in which the compound of Example 1 had superior unit activity and lifespan in soil along with selectivity in soybeans in both application methods shows how this can be seen in Table IV ".

The above description emphasized the excellent herbicidal activity of the compounds according to the invention in the control perennial weeds and annual broadleaf weeds in soybeans and cotton. Furthermore, was mentioned above and occasionally also shown, e.g. in the tests with Echinochloa and Digitaria, that the inventive Compounds also have excellent herbicidal activity against annual narrow-leaved weeds, i. Grasses, own. In fact, compounds according to the invention show as will be presented below in relation to certain annual grasses, distinct superiority over the most herbicidally effective and / or commercially available known 2-haloacetanilides. From the test data cases can be seen in which a related known 2-haloacetanilide is compared with compounds according to the invention superior herbicidal effectiveness with respect to certain annual weeds under comparable conditions shows. However, from the comparative tests presented here can also be seen that compounds according to the invention as a whole

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the best 2-haloacetanilides as selective herbicides for the control of annual and perennial narrow-leaved weeds in soybeans, cotton, peanuts and others Cultures are at least comparable and often superior, sometimes in excellent ways.

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

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Table VII

GR ₁₅ ~ quantity (kg / ha) (kg / ha)

Pani- Rottboellia

Sorghum h. Sorghum cum milia- Oryza exaltata
Compound seedlings bicolor Braohiaria ceum sativa soybeans

0.84 0.28 0.56 0.95 0.84 *> 1.1

0.28 0.14 0.56 1.1 0.28> 1.1

0.28 0.28 0.56 1.1 1.1> 1.1

O I 1.1 1.1 0.56> 1.1> 1.1> 1.1> 1.1

Ex. 1 0.14 Ex. 11 0.28 C. 0.56 I. 1.1

cn

CD cn ro cn

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 each weed tested, and showed no selectivity in soybeans in relation to Panicum miliaceum, Oryza sativa or Rottboellia;

2) Compound C was as active as the more active of the compounds of Examples 1 and 11 versus Sorghum bicolor and Panicum miliaceum;

3) the compounds of Examples 1 and 11 were both the known compounds in Sorghum halepense seedlings and Rottboellia superior and

4) the compound of Example 11 was more active against Brachiaria pl. ₉ and the compound of Example i was more active against Oryza s than the known compounds.

From the comparative data of Table VII, it can be said that one or the other or both of the present invention Connections to two annual narrow-leaved weeds (Sorghum bicolor and P'anicum ir.iliaceum) herbicidally as effective as the best known reference compounds, and clearly better against four narrow-leaved ones Weeds (Halepense sorghum seedlings, Brachiaria plantaginea, Oryza sativa and Rottboellia exaltata). Particularly noteworthy is the excellent unit activity of the compound of Example 1 on sorghum

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halepense seedlings (GRg ₅ = 0.14 kg / ha) giving an excellent selectivity factor of about 8.0 in soybeans compared to a selectivity factor of> 2.0 for compound C, which is 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 and> 1.0 for compound C.

Another test was carried out in soybeans, using Texas and Autumn Panicum seeds in addition to the other annual grasses mentioned in your previous test. In this test, the compounds of Examples 1 and 12 were compared with the known compounds C, D and I with regard to their herbicidal pre-emergence activity. The herbicides were worked into the soil and watered from below as needed. The maximum amount of herbicide used in this test was 1.2 kg / ha, the exact GRg ₅ "and GR.g amounts above 1.2 kg / ha are therefore somewhat indeterminate. Assessment took place two weeks after the Treatment, the data from this test are summarized in Table VIII.

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Table VIII

GRgr quantity GR ₁₅ ~ quantity

. (kg / ha) (kg / ha)

Panicum Sorghum Sorghum Bracha- Panicum Autumn- Oryza Rott-

Connection tex. H_. bicolor ria pl »m. panicum sativa boellia e. Soybeans

Example 1 1.1 <0.07 0.14 0.56 0.56 <0.07 0.28 0.56> 1.1

ßisp. 12 0.28 <0.07 0.14 0.14 0.56 <0.07 0.21 0.07 > 1.1

C 0.56 0.07 0.28 0.56 1.1 <0.07 0.28> 1.1> 1.1

2 D 0.14 0.07 0.28 0.07 0.56 <0.07 <0.07 0.56 1.1

O I> 1.1 0.28 0.50 0.50 1.1 <0.07 0.56 0.84> 1.1

ω ta co

CD cn

CD

ro cn

Analysis of Table VIII shows that the invention Compounds of Examples 1 and 12 have the highest Exnhexts and selectivities of all against sorghum halepense and sorghum bicolor compounds tested; the compound of Example 12 had the highest Activity and selectivity towards Rottboellia, and the compounds of Examples 1 and 12 had the highest Activities towards Panicum miliaceum along with connection D, and against Herbstpanicum together with each of the known compounds, the compounds according to the invention however, were more selective in soybeans than Compound D for Panicum miliaceum. The connection of example was also the second most active compound against Panicum texanum and Oryza sativa, and the compound of Example 1 together with Compound D, had the second highest activity against Rottboellia. Compound D was the most active test compound against Panicum texanum, Erachiaria p. and oryza sativa.

From the foregoing comparative data on herbicidal activity against other grasses, therefore, it appears that the compounds according to the invention have a herbicidal activity superior to that of the leading related known compounds over certain annual grasses is, e.g. towards Echinochloa, Digitaria (S.I.), Sorghum bicolor and Rottboellia, and that they are püeichwerti ^ r or J-Hi dJ! gen *: J Jitin Verblei ehbatv li *: rbi. & ide Wxrk.bdfnkei L

130061/0639

against other weeds, e.g. against Digitaria (S.A.), Panicum species, Brachiaria and Oryza sativa.

Other greenhouse and / or field tests found selective control by the compounds of the invention from others Weed species in soybeans, cotton and / or other crops. For example, the compound of Example 1 showed selective Control of 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 an improvement Repulsion of such resistant weeds as Ambrosiaceae, Ipomoea and xanthium. Further weeds against which the compounds according to the invention are used as herbicidal Proven to be active, include field thistle, bindweed, downy bristle, knotweed, etc.

As already mentioned, the compounds according to the invention have proven themselves as effective herbicides in a wide variety of crops. The above discussion and test data were correct focus mainly on weed control in soybeans and cotton, crops of particular interest here are. 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 effectiveness the compounds of Example 11 and 12 tested,

130061/0639

namely, worked into the ground, against couch grass in rapeseed, French beans, sorghum and wheat. Both compounds tested selectively controlled 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. Were at this test both compounds are not selective against couch grass in sorghum and wheat.

In separate greenhouse tests, the compound of Example 1 was also tested for its herbicidal activity against yellow Sedge and couch grass tested in rapeseed, peanuts, sugar beet, sorghum, wheat and barley; the herbicide was found in incorporated the floor. In these tests, compound D was used as the reference compound against couch grass, and compound E used as a reference compound against yellow sedge. The assessment was carried out in the test with couch grass 19 days after treatment (DAT), in the test with yellow Sedge 18 DAT; the test data are summarized in Table IX; the selection factors for the herbicides are in brackets after the GR. ^ Quantities for the respective cultures specified.

130061/0639

Table IX

Weeds ■ culture

^GR 85 ^GR 15
(kg / ha) (kg / ha)

Compound couch grass peanuts rapeseed sugar beet sorghum v / wheat barley
Ex. 1 0 045 ° ^{'28 (6} ' ⁰⁾ ° ^{'13 (3} > ⁰⁾ °' ^{28 (6} ' ⁰⁾ <O, O34 (NS) 0.06 (1.0) 0.07 (1, 5) D 0.034 0.034 (1.0) 0.06 (1.5) 0.06 (1.5) <0.034 (NS) 0.034 (1.0) 0.11 (3.0)

Cyperus
esculen-

-

Ex. 1 0.12 0.87 (7.0) 0.48 (4.0) 0.022 (NS) 0.13 (1.0) 0.13 (1.0) 0.28 (2.0)

O »E 0.12 0.95 (8.0) 0.87 (7.0) 0.022 (NS) 0.011 (NS) 0.045 (NS) 0.13 (1.0)

ti »CO

I S

CO

O ol ro cn

From Table IX it can be seen that the compound of Example 1 and the compound D both selectively contain couch potatoes in peanuts, Oilseed rape, sugar beet, wheat and barley controlled that 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 beet, while the compound E is Cyperus not selectively kept under control in sugar beet, sorghum or wheat.

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 both from greenhouse however, as from field tests, 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 has superior selectivity in cultures for much longer periods of time. In this context reference is again made to:

1) Table IV, some comparative data from field tests up to Includes 9.5 weeks for the performance of these compounds against couch grass and other weeds in soybeans; (neither compound D nor compound E controlled couch grass

130061/0639 ~ ⁿⁱ

selective in soybeans even at 3 WAT);

2) the discussion above 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 which comparative data for the duration of action in Bottom the compound of Example 1 and the compounds D and E against Cyperus and couch grass for 3, 6, 12 and 18 weeks are included;

The compound of Example 1 showed unit activities which were higher than those of compounds D and E at 3 WAT (by several orders of magnitude in the case of observation 12 WAT) and by an indefinite value in the case of observation 18 WAT. It should also be pointed out here that the combination of superior exnstity activity, duration of action in the soil and selectivity in crops of the compound of Example 1 compared with Compounds I 'and E over Cyperus and couch grass also account for the relative performance of these compounds in many others Weeds applies »especially sorghum haiepense seedlings _} Sesbania exaltara, Sida. spinosa, Polygonum, Melde, etc.

In a multiple culture test, the preemergence activity the compound of Example 1 was further tested in the field against certain annual weeds in multiple crops.

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-TJt-

In parallel tests, the herbicides were applied either to the surface or before planting in the soil incorporated. Assessment and recording of the data takes place 33 days after the treatment in the tests with familiarization in the soil before planting, and 34 days after treatment in the herbicide application tests the surface. In both tests, the compound of Example 1 selectively controlled Echinochloa and Setaria viridia in Corn, soybeans, cotton, French beans, and peanuts; Report was also checked in soybeans. In the P. P. I. tests Echinochloa and Setaria were also selectively checked in sorghum and sweet maize.

From the preceding detailed description it can be seen that the compounds according to the invention are unexpected and exhibited excellently superior herbicidal properties, both absolutely and in comparison with those structurally most closely related compounds, other related homologues and analogs, and known commercial ones 2-haloacetanilides. In particular, those according to the invention showed Compounds excellent unit activity, duration of action in the soil and harmlessness of crops in the control of perennial and annual broad-leaved and narrow-leaved weeds in soybeans, cotton, peanuts, Canola, French beans and other crops. In particular, the compounds of the invention showed superior herbic

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cidal effectiveness against perennial weeds Cyperus esculentus and couch grass (Agropyrum repens); annual broad-leaved weeds such as Sesbania exaltata, Sida spinosa, Chenopodium album and Polygonum, as well annual narrow-leaved weeds such as Echinochloa crus-galli, Digitaria sanguinalis (P.P.I.), Sorghum bicolor and Rottboellia exaltata. In addition, the compounds according to the invention were found to be generally comparable with the best known compounds in the control of other annual weed grasses such as sorghum halepense seedlings, Digitaria (S.A.), The foxtails, Panicum species, Brachiaria plantaginea and Oryza sativa, as well as annual broad-leaved weeds such as Amaranthus and Datura stramonium. Finally, the compounds according to the invention showed an increased activity in the suppression of resistant annual broad-leaved weeds such as Ipomoea, Xanthium pensylvanicum, Ambrosiaceae and Abutilon theophrasti.

Toxicological studies of the compound of Example 1 indicated that the compound was fairly harmless. It was slightly toxic when taken orally (single dose oral LDr ₀ - 2600 mg / kg), slightly toxic after single dermal application (dermal LD ₁ -Q - 5010 mg / kg), it also caused slight eye and skin irritation. Special handling procedures beyond the normal precautionary measures

addition are not deemed necessary.

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The herbicidal preparations according to the invention, including the concentrates, which are diluted before use must 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. The active substance can therefore with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a Wetting agent, a dispersing agent, an emulsifying agent or a suitable combination thereof can be used.

The preparations according to the invention, in particular liquids and wettable powders, preferably contain one or more surfactants as conditioning agents in sufficient quantities to make a particular preparation to make it easily dispersible in water or oil. The inclusion of a surfactant in the preparations significantly promotes their effectiveness. The term "surfactant" includes wetting agents, dispersants, Suspending and emulsifying agents. Anionic, cationic and nonionic agents can

can be used equally.

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130061/0639

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 esters, sulfated or sulfonated fatty acid esters, Petroleum Ulfonates, Sulphonated Vegetable Oils, ditertiary acetylenic glycols, polyoxyethylene derivatives the alkylphenols (especially isooctylphenol and nonylphenol) and polyoxyethylene derivatives of 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 can be dispersed in water, the one or more active ingredients, an inert extender solid and one or more wetting and dispersing agents contain. The inert extender solids are usually of mineral origin, e.g. natural clays, diatomaceous earth and synthetic minerals of silica and the like. Such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable according to the invention Powders usually contain about 0.5 to 60 parts (preferably 5 to 20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1 to 15 parts) of wetting agent, about 0.25 to 2 5 parts (preferably 1.0 to

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130061/0639

15 parts) dispersant and 5 to about 95 parts (preferably 5 to 50 parts) inert extender solids, all parts being based on the weight of the total formulation are related. If necessary, »about 0.1 to 2 parts can be used of the inert expanded solid material can 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 a suitable extender; these dusts can be diluted for use with concentrations of about 0.1 to 10% by weight.

Aqueous suspensions or emulsions can be prepared by adding an aqueous mixture of a water-insoluble one Active ingredient and an emulsifying agent are stirred until it is uniform, and then it is homogenized so that you get a receives stable emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by their extremely small particle size, so that after thinning and spraying the coating is very uniform is. Suitable concentrations of these preparations contain about 0.1 to 60% by weight, preferably 5 to 50% by weight Active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent.

Another type of aqueous suspension encapsulates a water-immiscible herbicide so that an in

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130061/0639

Microcapsule phase dispersed in an aqueous phase is formed. In one embodiment, very small capsules are formed, by making an aqueous phase containing a lignosulfonate emulsifier contains, a water-immiscible chemical and polymethylene polyphenyl isocyanate that brings together water-immiscible phase is 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 are immiscible with water Chemical so that microcapsules of the same are formed. In general, the concentration of the encapsulated material will be in the range at about 480 to 700 g / liter, preferably 4 80 to 600 g / liter of the total preparation.

Concentrates are usually solutions of active ingredient in water-immiscible or only partially water-miscible solvents with a surfing agent. Suitable solvents for the active ingredient according to the invention include dimethylformide, Dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones. However, other strong liquid concentrates can also be dissolved by dissolving them of the active ingredient in a solvent and then diluted, e.g. with kerosene, to spray concentration will.

The concentrate preparations generally contain about 0.1 to 95 parts (preferably 5 to 60 parts) of active ingredient,

- / 7 8

130061/0639

about 0.25 to 50 parts (preferably 1 to 25 parts) surfactant and, if necessary, about <4 to SH parts solvent; all parts are parts by weight and based on the total weight of the emulsifiable oil.

Granules are physically stable, particulate preparations, which contain an active ingredient attached to a matrix of inert, finely divided, particulate extender is liable or distributed in the same. To support the leaching of the active ingredient from the particles, in the Prepare a surface-wetting gown like the one above are listed. Natural clays, pyrophyllites, illites, and vermiculites are examples of useful ones 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 finely divided clays such as kaolin clays, hydrogenated attapulgite or bentonite clays. These extenders are used to produce the herbicidal granules ir.it the active ingredient sprayed or mixed.

The granule preparations according to the invention can be about 0.1 to 30 parts by weight, preferably about 3 to 20 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about Contains 5 parts by weight of surfactant per 100 parts by weight of clay particles. - / 79

130061/0639

The preparations according to the invention can also contain other additives, for example fertilizers, other herbicides or Pesticides, protective substances and the like. Used as adjuvants or in combination with one of the adjuvants listed above be used. Chemicals that are useful for combination with active ingredients according to the invention are i.a. Triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, Triazoles, benzoic acids, nitriles, biphenyl ethers and the like, such as.:

Heterocyclic nitrogen / sulfur derivatives

2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine

3-Isopropyl-1H-2,1,3-benzothiadiazin-4- (3H) -one-2,2-dioxide

3-Amino-l, 2,4-triazole 6,7-Dihydrodipyrido- (1,2-a: 2 ', 1'-c) -pyrazidiinium salt S-Broir.-S-isopropyl-e-methyluracil 1,1' -Dimethyl- ¹ +, Μ · ¹ -bipyridinium

Ureas

N '- (4-chlorophenoxy) phenyl-N, N-dimethylurea N, N-Dimethy1-N • - (3-chloro-4-methylpheny1) urea 3- (3,4-dichlorophenyl) -1, 1-dimethylurea 1,3-dimethyl 1-3- (2-benzothiazoly1) urea 3- (p-Chlorophenyl) -1, 1-dimethylurea 1-butyl-3- (3, M-dichlorophenyl) -1-methylurea - / 80

T3006 i / 0639

Carbamates / thiol carbamates

2-chloroallyl diethyldithiocarbamate

S-CH-ChlorobenzyD-NjN-diethylthiolcarbamate

Isopropyl N- (3-chloropheny1) carbamate

S-2, S-dichloroallyl-NjN-diisopropylthiol carbamate

Ethyl NjN-dipropylthiol carbamate S-propyl dipropyl thiol carbamate

Acetamide / Acetanilide / Aniline / Amide

2-chloro-N, N-diallylacetamide N, N-dimethyl-2,2-diphenylacetamide

N- (2,4-Dimethyl-5-L £ (trifluoromethyl-sulfonyl) -aminojphenyl) -acetamide

N-isopropyl-2-chloroacetanilide

2 ', 6'-Diethyl-N-methoxymethyl-2-chloroacetanilide 2'-> iethyl-6 ^l -ethyl-N- (2-methoxyprop-2-yl) -2-chloroacetanilide a _s a, a-Trifluoro-2 , 6-dinitro-N, N-dipropyl-p-toluidine N- (I, l-dimethylpropynyl) -3,5-dichlorobenzamide

Acids / esters / alcohols

2,2-dichloropropionic acid, 2-methyl-H-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid

Methyl 2- [u- (2,4-dichlorophenoxy) phenoxy]] propionate

3-amino-2,5-dichlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid

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2,3,6-trichlorophenyl acetic acid N-1-naphthylphthalamic acid

Sodium 5- | j2-chloro-4- (trifluoromethyl) -phenoxy3-2-nitrobenzoate

H , 6-dinitro-o-sec-butylphenol

N- (phosphonomethyl) -glycine and its CL- monoalkylamine- and alkali metal salts and combinations thereof

Ether

2, H-dichlorophenyl-4-nitrophenyl ether

2-chloro-α, α, α-trifluoro-p-tolyl-S-ethoxy - ^ - nitrodiphenyl ether

Various

2,6-dichlorobenzonitrile Monosodium acid methanar sonate Disodium methanar sonate

Useful fertilizers in combination with the active ingredients are e.g. ammonium nitrate, urea, potash and superphosphate. Other useful additives include substances in where plant organisms take root and grow, e.g. compost, manure, humus, sand and the like.

Various exemplary embodiments are given below for herbicide preparations of the type described above specified.

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130 0617 0639

I. Emulsifiable Concentrates

Weight%

A. Compound of Example No. 1 50.0

Calciunidodecylbenzenesulfonat / Polyoxyethylene ether mixture (e.g. Atlox 3437F and Atlox 3438F) Monochlorobenzene

A. Compound of Example No. 1 xylene

B. Compound of Example No. 12 85.0

Calcium dodecyl sulfonate / alkylaryl polyether alcohol mixture M, 0

C _q aromatic hydrocarbon solvent

C. Compound of Example No. 13 5.0

CalciujTidodecylbenzenesulfonat / polyoxyethylene ether mixture (e.g. Atlox 3H37F) xylene

II. Liquid concentrates % by weight

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430061/0639

B. Compound of Example No. 2 Dimethyl sulfoxide

C. Compound of Example No. 3 N-methyl pyrrolidone

D. Compound of Example No. 4 Ethoxylated Castor Oil Rhodamine B
Dimethylformamide

Weight%

85 , 0 15th i ⁰ . 100 , 0 50 , 0 50 xQ. 100 , 0 5 , 0 20th , 0 0 , 5 74 il 100 , 0

III. Emulsions

Weight ■

A. Compound of Example # 1 40.0 polyoxyethylene / polyoxypropylene block

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

Water 56.0

100.0

B. Compound of Example No. 5 x 5.0 polyoxyethylene / polyoxypropylene-

Block copolymer with butanol 3.5

Water 91.5

100.0

IV. Wettable powders

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

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130061/0639

B. Compound of Example No. 6 sodium dioctyl sulfosuccinate
Calcium lignosulfonate
Amorphous silica (synthetic)

C. Compound of Example No. 7 Sodium Lignosulfonate
Sodium N-methyl-N-oleyl taurate kaolinite clay

Weight%

80.00

1.25

2.75

16.00

100.00

10.0 3.0 1.0

86.0 100.0

V. Dusts

A. Compound of Example No. 1 Attapulgite

B. Compound of Example No. 8 Montmorillonite

C. Compound of Example No. 9 Bentonite

D. Compound of Example No. Diatonic Earth

2.0

98.0 100.0

60.0 40.0

100.0

30.0 70.0

100.0

1.0

99.0

100.0

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13006170639

VI. Granules

Weight%

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

100.0

C. Compound of Example No. 13 0.5 Bentonite (20/40) 99.5

100.0

D. Compound of Example No. 14 5.0 Pyrophyllite (20/40) 95.0

100.0

VII. Microcapsules

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. 12

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. 13

encapsulated in polyurea shell 80.0 magnesium salt of lignosulphate

(Treax LTM) 2.0

Water . 18.0

130061/6 ⁸ 6 ⁶ 3 9 ¹⁰⁰ '°

When used according to the invention, effective amounts of Acetanilides according to the invention to those containing the plants Soil applied or appropriately absorbed in aqueous media. The application of the preparations as Liquids and solid particles on the earth can be done with conventional methods, e.g. with motorized atomizers, Tank and hand sprayers or spray atomizers. The preparations can also be used in small doses because of their effectiveness dispersed by airplanes as dust or spray. Herbicidal preparations are used in aquatic plants usually by adding the preparations to the aqueous medium in the area in which the aquatic plants are controlled it is asked for.

The application of an effective amount of the preparations according to the invention at the location of the undesired weeds is essential and critical for the application according to the invention. The exact amount of active ingredient to be used depends on various Factors such as the type of plant and its stage of development, the type and condition of the soil, the amount of rain and the specific acetanilide used. With selective pre-emergence application to plants or soil usually 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 used. In some cases larger or smaller quantities may be required. The skilled person can

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on the basis of the description, including the examples, it is easy to determine the optimum amount for each case.

The term "soil" is used in the broadest sense of the word used and includes all common types of soil as described under "soils" in Webster's New International Dictionary, Second Edition, Unabridged (1961). So the name refers to every substance or every one Medium in which plants can take root and grow, and includes not only soil, but also compost, manure, dung, Humus, sand and the like that support plant growth can.

End of description

130061/0639

Claims (1)

DR. BERG ^ DffL.-MWs. "STAPF DIPL.-ING. SCHWABE- "DR. Dr'Ä PATENTANWÄLTE PO Box 860245 8000 Munich Attorney's file: 31 Claims !. ^ Compounds of the formula ClCH ₂ C where R is ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, Cyclopropy! Methyl, allyl or propargyl, R _{1 is} methyl, ethyl, n-propyl or isopropyl, and R _{2 is} hydrogen, methyl or ethyl, with the Provided that, ^ 'means hydrogen, R ;. Represent ethyl and R allyl, _{2 is} ethyl, R, methyl and R is isopropyl,
^ Methyl means, R ethyl, isopropyl, isobutyl, represents sec-butyl or cyclopropylmethyl, ^ Is ethyl, R is sec-butyl, allyl or propargyl, when R _{1 is} n-propyl, R is ethyl and when R _{1 is} isopropyl, R is ethyl or n-propyl if if if if «(089) 988272 988273 988274 983310 represents. Telegrams: BERGSTAPF PATENT Some TELEX: ° "<* ° ^BERG « · 3006 1 / .063 - / 2 Bank accounts: Hypo-Btnk Munich 4410122850 (BLZ 70020011) Swin Code: HYPO DE MM Bayer Vereinsbank Munich 453100 (BLZ 70020270) Post check Munich 65343-808 (BLZ 70010080) 2. A compound according to claim 1, characterized that they are 2'-methoxy-6 '-niethyl-N- (isopropoxyinethyl) -2-chloroacetanilide is. 3. A compound according to claim 1, characterized in that it is 2i-methoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide is. 4. A compound according to claim 1, characterized that they are 2'-methoxy-6'-methyl-N-i1-methylpropoxymethyl) -2-chloroacetanilide is. 5. A compound according to claim 1, characterized in that it is 2'-ethoxy-6 ^f -methyl-N- (allyloxyir! Ethyl) -2-chloroacetanilide. 6. A compound according to claim 1, characterized in that it is 2'-ethoxy-6 '-ir.ethyl-N-CpropargyloxymethyD-2-chloroacetanilide is. 7. A compound according to claim 1, characterized in that it is 2'-ethoxy-6'-methyl-N- (1-methylpropoxymethyl) -2-chloroacetanilide is. - / 3 130061/063 $ 8. A compound according to claim X _9, characterized in that it is 2 ¹ -n-propoxy-6 ^f -methyl-N- (ethoxyir.ethyl) -2-chloroacetanilide. 9. A compound according to claim I _9, characterized in that it is 2'-isopropoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide. XO. Compound according to Claim X _9, characterized in that it is 2'-isopropoxy-6'-methyl-N- (n-propoxymethyl) -2-chloroacetanilide. 11. A compound according to claim X _9, characterized in that it is 2'-ethoxy-N-iallyloxymethyl) -2-chloroacetanilide. X2. Connection according to Claim 1, characterized that they are 2'-methoxy-6'-ethyl-N- (isopropoxymethyl) -2-chloroacetanilide is. 13, herbicide preparation, characterized that they are an adjuvant and a herbicidally effective amount of a compound of Forirel CH ₂ OR
N
K ₂ I 130061/0639 contains where R ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, Cyclopropylmethyl, allyl or propargyl, R _{1 is} methyl, ethyl, n-propyl or isopropyl, and R_ is hydrogen, methyl or ethyl, with the Provided that if
R _{2 is} hydrogen, R _{1 is} ethyl and R is allyl, if
R _{2 is} ethyl, R _{1 is} methyl and R is isopropyl, if
R ₁ denotes methyl, R denotes ethyl, isopropyl, isobutyl, sec. Butyl or cyclopropylmethyl is when R _{1 is} ethyl, R is sec-butyl, allyl or propargyl represents if R _{1 is} n-propyl, R is ethyl and when R _{1 is} isopropyl, R is ethyl or n-propyl. IN THE. Preparation according to claim 13, characterized in that that the compound 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide is. 15. Preparation according to claim 13, characterized that the compound 2'-methoxy-6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide is. 130061/0639 16. Preparation according to claim 13, characterized that the compound 2'-methoxy-6'-methyl-N- (1-methylpropoxymethyl) ~ 2-chloroacetanilide is. 17. Preparation according to claim 13, characterized in that the compound is 2'-ethoxy-6 ^l -methyl-N- (allyloxymethyl) -2-chloroacetanilide. 18. Preparation according to claim 13, characterized in that that the compound 2'-ethoxy-6'-methyl-N- (propargyloxymethyl) -2-chloroacetanilide is. 19. Preparation according to claim 13, characterized in that the compound is 2'-ethoxy-6 ^l -methyl-N- (l-methylpropoxymethyl) -2-chloroacetanilide. 20. Preparation according to claim 13, characterized in that the compound is 2'-n-propoxy-6 ^l -methyl-N- (ethoxyethyl) -2-chloroacetanilide. 21. Preparation according to claim 13, characterized in that the compound is 2'-isopropoxy-6 ¹ -methyl-N- (ethoxyniethyl) -2-chloroacetanilide. - / 6 130081/0830 22. Preparation according to claim 13, characterized that the compound 2'-isopropoxy-6'-methyl-N- (n-propoxymethyl) -2-chloroacetanilide is. 23. Preparation according to claim 13, characterized in that the compound 2'-ethoxy-N- (allyloxymethyl) -2-chloroacetanilide is. 24. Preparation according to claim 13, characterized in that that connection. 2'-methoxy-6'-ethyl-N- (isopropoxymethyl) -2-chloroacetanilide is. 25.Methods for controlling undesirable plants in crops of useful plants, thereby £. ekennzeich net that at the location of the plants a herbicidally effective Amount of a compound of the formula ClCH ₂ C CH ₂ OR N is applied, where R is ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, Cyclopropylmethyl, allyl or propargyl, R ₁ methyl, ethyl, n-propyl or isopropyl, and - / 7 130061/0639 R_ denotes hydrogen, methyl or ethyl, with the proviso that, if R _{2 is} hydrogen, R _{1 is} ethyl and R is allyl, if R _{2 is} ethyl, R _{1 is} methyl and 'R is isopropyl if
R ₁ denotes methyl, R denotes ethyl, isopropyl, isobutyl, sec. Represents butyl or cyclopropylmethyl if
R ₁ denotes ethyl, R denotes sec-butyl, allyl or propargyl represents if R _{1 is} n-propyl, R is ethyl and when R _{1 is} isopropyl, R is ethyl or n-propyl. 26. The method according to claim 25, characterized in that the compound 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide is. 27. The method according to claim 25, characterized in that the compound 2'-methoxy-6'-methyl-N- (ethoxy-methyl) -2-chloroacetanilide is. 28. The method according to claim 25, characterized in that that the compound 2'-methoxy-6'- ■ is methyl N- (1-methylpropoxymethyl) -2-chloroacetanilide. -/8th 29 »Process according to claim 25» characterized in that the compound is 2'-ethoxy-6 ^f -methyl-N- (allyloxymethyD-2-chloroacetanilide. 30. The method according to claim 25, characterized in that that the compound 2'-ethoxy-6'-methyl-N- (propargyloxymethyl) -2-chloroacetanilide is. 31. The method according to claim 25, characterized in that the compound 2'-ethoxy-6'-methyl-N- (l-methylpropoxymethyl) -2-chloroacetanilide is. 32. The method according to claim 25, characterized in that the compound 2'-n-propoxy-6'-methy1-N- (ethoxymethy1) -2-chloroacetanilide is. 33. The method according to claim 25, characterized in that the compound 2'-isopropoxy-6'-methy1-N- (ethoxymethyl) -2-chloroacetanilide is. - Process according to claim 25, characterized in that the compound 2'-ethoxy-N-callyloxymethyl) -2-chloroacetanilide is. 35. The method according to claim 25, characterized in that that the compound 2'-methoxy-6'- - / 9 130061/0639 is ethyl N- (isopropoxymethyl) -2-chloroacetanilide. 36. The method according to claim 25, characterized in that the crops soybeans, Cotton, peanuts, rapeseed, French beans, sugar beets, sorghum, wheat or barley. 37. The method according to claim 36, characterized in that the undesired plants are perennial Grasses and sedge as well as annual weeds are. 8. The method according to claim 37, characterized that the perennial weeds are couch grass (Agropyrum repens) and Cyperus esculentus. 39. The method according to claim 37, characterized in that the annual weeds are broad-leaved weeds. 40. The method according to claim 39, characterized in that the broad-leaved weeds Sida spinosa, Sesbania exaltata, Amaranthus retroflexus, Polygonum sp., Chenopodium album and Datura stramonium are. 41. The method according to claim 37, characterized that the annual weeds are grasses. 42. The method according to claim 41, characterized in that the grasses Setaria spp. , Echino - / 10 130JO61 / 06-39 chloa crus-galli, Digitaria sanguinalis, Panicum ερρ. , Are Sorghum bicolor, Brachiaria plantaginea, Oryza sativa and Rottböellia exaltata. 43. The method according to any one of claims 36 to U1 or 42, characterized in that the compound 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide is. 44. Process for the selective control of the growth of weeds in soybeans, cotton, peanuts, rapeseed, Kidney beans, sugar beet, sorghum, wheat or barley, characterized in that on Place the weeds in a herbicidally effective amount of 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide is applied. 45. Method for the suppression of the weed population on Air.brosiaceae, Ipomoea sp. , Xanthium pensylvanicum and Abutilon theophrasti, characterized in that at the same location a herbicide effective amount of 2'-methoxy-6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide is applied. - / 11 130061/0639