CS227326B2 - Herbicide - Google Patents

Abstract

A group of N- hydrocarbyloxymethyl-2- haloacetanilide compounds, herbicidal compositions containing said compounds as the active ingredient and herbicidal method of use in various crops, particularly, corn and soybeans and other crops including cotton, peanuts, rape, bush beans, wheat and sorghum. The herbicides herein are particularly effective against hard-to-kill perennial weeds such as quackgrass and nutsedges and are also effective against annual weeds.

Description

The present invention relates to 2-haloaccewiilides and their use in agricultural production as herbicides.

Prior art relevant to the present invention encompasses a variety of 2-haloacetanilides discovered which may be unsubstituted or are substituted by substantially different substituents on the anilide nitrogen atom and / or on the anildd ring and include alkyl, alkoxy, alkoxyalkyl, haloalkyl, halogen and the like groups.

The compounds of the present invention are characterized by having (hydrocarbyl) oxymethyl. . a group on the anilide nitrogen, a methyl group in one ortho position and a methyl group or, in particular, ethyl or hydrogen in another ortho position. The earliest prior publication known to the author is probably Belgian Patent No. 810,763. The most important in this Patent No. 810,763 are the generally described N-O-cycloalkyl or alkyl-substituted alkoxy ethers. The radicals which may be substituted on the anilide ring in the ortho- and meea position by at least one group selected from the group consisting of halogen, alkyl, alkoxy and the like; In particular, the overview of the compounds in Table II shows the derivatives substituted with a triLUdoraethyl group in one ortho position, where the other ortho position is not substituted (compounds Nos. 37 to 48) and compounds with trHu-orlyl substitution in the meta position with one. ortho-position without substituent and with the other. an ortho-position substituted by methoxy (compounds Nos. 22 to 25) or a chlorine atom (compounds Nos. 33 to 36).

However, Belgian Patent No. 810,763 does not individually disclose or exemplify derivatives of 2-halomethylcetalilide substituted with a trifluoromethyl group in one ortho position and a methyl or ethyl group in the other ortho position as the compounds of the present invention. 810 763 are further characterized in that they are substituted on the nitrogen atom of the enilide by an alkoxyalkyl group, wherein the alkenyl moiety must contain no less than two carbon atoms between the nitrogen atom and the oxygen atom of the alkoxy moiety. The significance of the above difference between the compounds of Belgian Patent No. 810,763 and the compounds of the present invention will be demonstrated by comparing the herbicidal data, which clearly shows the superiority of the compounds of the present invention. chain on unit effect, selectivity, weed control spectrum and crop safety ·

Other related earlier publications, less yellow than the aforementioned Belgian Patent No. 810,763, include US Patents Nos. 3,966,811 and 4,152,137, German Patent Publication Nos. 24,098,983, British Patent Nos. 2-13,188, and South Africa. While these publications provide a general description of 2-haloacetylilides, which may include, but are not limited to, trifluoroethyl aluminosubstituted as sulfide ring precipitation, only a description of certain derivatives of such compounds can only be found in US Patent No. 3,960,067. No. 966,811 and South African Patent No. 6,774,767, all of which disclose neither US Patent No. 3,966,811 nor South African Patent No. 74/0767 disclose certain derivatives of the ortho-position of the trifVoo: riethyl group that would be given generally or singly, and such compounds would be further substituted in another ortho position by a methyl or a stylish group; The trifluoromethyl substituted derivatives mentioned in these patents are only compounds containing the trifluoromethyl group in the meta position. In addition, similarly to Belgian Patent No. 810,763, as well as US Patent No. 3,966,811 and South African Patent No. 74/0767 no less than two carbon atoms are required between the nitrogen of the anilide and the oxygen of the alkoxy moiety. In all of the aforementioned prior publications, with the exception of U.S. Pat. No. 4,152,137 mentioned above, there are described derivatives substituted with triethylethyl. ·

Of the most important earlier publications mentioned above, only Belgian Patent No. 810,763 and South African Patent No. 74/0767 disclose a herbicidal data relating to N-alkoxy-4-haloacetamides containing a tertiarytyl substitution on the solid ring. the description is unclear, indeterminate and incomplete · For example, in Belgian Patent No. 801 763, the description is limited to the herbicidal data of a compound substituted with only one trifluoromethyl group (see Compound No. 37γ which is identical to Compound No. 2), i.e. to 2-trifluoromethyl- N- (2 * -mejotyejyle-2-meta.orajcenilid) · Table 3 of this Belgian Patent No. 810,763 states for Compound No. 37 that it destroys the sky seriously damaging certain unidentified species of Báchor, Shine, Dew and Hedgehog, somewhat harms the weeds of deaf and ieidentified rye genera in some useful plants · Compound No. 37 lacks specific identity in five of the six important weeds tested in assessing herbicidal efficacy ·

Similarly, South African Patent No. 74/0767 provides limited herbicidal data only for a compound substituted with one trifluoroethyl group (see Compound No. 78), i.e. 2,6-dimethyl-3-trifluoromethyl-N- (2'-meettyeyyl) - N-2-e-oxalcetalide. Heebicidal data for Compound No. 78 is given in Example 5, where Compound No. 78 is said to cause a very strong inhibition of the growth of four grass weed species. However, South African Patent No. 74/0767 does not disclose laboratory or field data concerning The efficacy of Compound # 78 on some useful plants, nor is it indicated whether the compound selectively suppresses some weeds in the useful plants, and thus an important evaluation of the compound based on such limited data is impossible. The aforementioned description of the effect on various weeds does not disclose any data for some of the N-glycol-substituted phenyl group that exhibits additional and / or concomitant control or damage in at least one usefully hard-to-control plant. weeds, creeping wheatgrass, yellow nutsedge, purple nutsedge, and a wide range of individual weeds, including those difficult to control. miliaceum), Malaysian rice and Rottbocelia exaltata, while also suppressing the sky damaging other harmful perennial skies of one-year weeds such as millet (Panic dicho, tonno-peper), pepper, white amaranth, moth, for example giant foxtail and foxtail , hedgehog k such as leg, lamb, abutilon, beet, purslane, hemp, sida (prickly sida) and the like.

A very desirable and desirable property of herbicides is the ability to achieve weed control over extended periods of time, the longer the ability, the better. With much wilder herbicides, adequate weed control is only achieved for 2 or 3 weeks, or in some better cases perhaps up to 4 to 6 weeks, before the chunikkalae loses its effect of phytotoxic properties. Therefore, one of the disadvantages of most previous herbicides is their relatively short soil life.

Another disadvantage of some of the earlier herbicides in terms of soil life under normal weather conditions is the inadequate suppression of resistant algae in heavy rainfall, which ineffectiveness for many herbicides.

A further disadvantage of many of the earlier herbicides is that they are not suitable for specific soil types, i.e., when certain herbicides are effective in soils with low organic content, they are ineffective in other soils with high organic content and vice versa. It is therefore advantageous if the herbicide is applicable in all types of soil, soil with a low proportion of organic substances into heavy clay and soil similar to mud.

Yet another disadvantage of many of the prior art herbicides is the sweeping of the individual effective methods of post-treatment, i.e. for prleiergent topical application or for incorporation into the soil, the method of use before and / or after cultivation. plant. It is highly desirable to be able to use the herbicide in various ways, either by topical application or by incorporation into the soil.

Finally, a disadvantage of some herbicides is the need to maintain and maintain a particular way of working due to the toxic nature of the herbicide. Therefore, another requirement is that the herbicide be handled safely.

It is therefore an object of the present invention to provide a set of herbicidal compounds which overcome the above-mentioned disadvantages of the previous products and have a number of advantages which have not yet been achieved in individual herbicide groups.

It is an object of the present invention to provide herbicides which control and / or damage hard-to-control perennial and annual weeds as described above, while providing safe crop plants in a number of cases, particularly in slug and soybean. grassland and other plants including cotton, peanuts, rape, bush beans, wheat and / or sorghum.

It is another feature of the present invention to provide herbicidal effects on the soil for up to 12 weeks.

Yet another feature of the present invention is the preparation of leaching and dilution-resistant herbicides due to very high humidity, for example during heavy rain.

Another feature of the present invention is the preparation of herbicides that are effective in a wide variety of soils, for example from low organic soils to heavy clay and mud-like soils.

A further advantage of the herbicides according to the invention is their adaptability to the method of use, i.e. to the post-surface use and incorporation into the soil.

Finally, the advantage of the herbicides of the present invention is that they are safe and do not require any special handling methods.

The foregoing features of the invention will be apparent from the detailed description hereinafter. This invention relates to herbicidally active compounds, herbicidal compositions containing them as active ingredients, and herbicidal methods of using such compositions in individual crops.

It has now been discovered that a particular group of 2-hydroxyacetylilides characterized by a specific combination (hydrocarbon residue) of an oxymethyl group on the nitrogen atom of an olilide, a trifluoroacetyl group of formula -CF3 in one ortho position and a methyl or ethyl group or a hydrogen atom in another ortho position - has unexpectedly superior and superior herbieid properties over earlier herbicides, including homogeneous compounds of the most important of the foregoing species.

A first feature of the herbicidal compositions of the present invention is the ability to control a wide range of weeds, including weed suppressed by common herbicides and an additional range of weeds that have eaten olive - and / or together have escaped control, by a single group of known herbicides. and one or more useful plants, in particular corn and soya, but also cotton, peas, rape, sorghum, and bean. Although the herbicides of the previous species are suitable for controlling various weeds and, if necessary, certain resistant weeds, it has been found that the individual herbicides of the present invention are capable of controlling or significantly damaging a number of resistant permanent or annual weeds. Examples of perennial weeds are creeping grass, yellow nutsedge and purple nutsedge, examples of annual broadleaf sida (prickly sida), hemp, chenotica, white medicate, bent-grass, and examples of annual grasses of sorghum seedlings, - sha ^ e ^ ane, Brachiaria plactagines, millet (Panic to Texas), millet (Panicum miliaceum), Maaai rice, footbboeiia exdtata and daalí'Harmful weeds such as millet to Panic diihotonriflo: Ium, copybook, hedgehog chicken and the like . Weed control is also achieved with resistant weeds. genera such as ambbooie, abu ^ lo ^ lamb, beet, abdomen and the like.

The compounds of this invention have the general formula

The present invention provides a herbicidal composition which comprises as an active ingredient a compound of the formula

(I) wherein is alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms or nyl of 2 to 5 carbon atoms or alpines; having 2 to -5 carbon atoms and elke ^R1 is hydrogen, methyl or ethyl, with the proviso that when R1 is hydrogen, R1 is isopropyl and when R1 is hydrogen; R is ethyl, n-propyl or isopropyl.

Preferred derivatives of the invention are compounds wherein R 1 in the above formula I is methyl or ethyl and R is a C 2 -C 4 alkyl group. The preferred compounds of this invention are:

N- (ethoxymethyl) - * - trifluoromethyl-6-yl-2-chloroacetamide,

N- (n-propoxyethyl) 1222-trifluoromethyl-6'-methyl-2-meta-lactylilide,

N- (isopropoxymethyl) -2-trifluoromethyl-6'-methyl-2-chloraee tanilide, N- (isobutoxymethyl) -2'-trifluoromethyl-6'-eeyl-2-chlooaccetMilide, N- (ethoxymethyl)) - 2 Z-trifluoroethyl -6 * -etml-2-clloracetailid, N- (i-propoxymeyyl) -2 * -triftooreethyl-6 * -ethyl-2-chloroacetyl) N- (isopropoxymethyl) -2 * -triftooreethyl-6 Z-ethyl clloracetailid.

Further derivatives of the invention will be described below.

The compounding of the compounds of the invention as an active ingredient in the herbicidal compositions prepared therefrom and methods of using the herbicidal compositions are described below.

The compounds of the present invention can be grafted by N-alkylation of the anion of a suitable secondary 2-haloacetamide with an alkylation agent under basic conditions, as exemplified in Example 1. A modification of said N-alkylation process involves the production of the ingenic lyophilized lyophilization in situ used as starting material in said N-alkylation process and described in Example 2 for the preparation of other derivatives of the invention.

He did

This example describes preparation of N- (etdxymíУyl) -2 * 6--triltuoreetyl ^/ -ííeyl-2- (Chldrccetamilidu.

4.02 g (0.016 mmol) of 2Z-trifluoromethyl-6Z-phenyl) 2-chloroacetylilide, 3.02 g (0.032 mol) of ethyl ether and 2.0 g of benzyltreethylene linine bromide (phase transfer catalyst) are mixed in 75 ml of ethylene chloride in a 500 ml round bottom flask, equipped with an agitator and a thermometer. 15 ml of 50% sodium hydroxide are added all at once with vigorous stirring, the temperature rising to 26 ° C as a result of the exothermic reaction. The purification of the peptides after about 5 minutes shows that the reaction is complete. After 15 minutes, ice and water are added, the layers are separated and the organic layer is washed with 2.5% sodium chloride, dried, filtered and concentrated. The residual dark color was distilled off in a collar flask and 3.4 g of a yellow oil fraction boiling at 110-115 ° C under 1 mbar were collected. This fraction was extracted with clclohexam and purified by high pressure liquid chromatography using 20% chlorosulfate in clclohexane. Further distillation of the purified fraction in a flask gave 3.2 g (65% yield) of a colorless oil, bp 100-110 ° C at 1 mm Hg, which on standing turned to a white solid, mp 41-43 ° C with crystallization.

Anal.

calculated: 50.41% C, 4.88% N, 4.52%, found: 50.02% C, 4.81% Η, 4.38% N.

Example 2

This example illustrates an improved alternative process with which the compounds of the invention can be prepared. A feature of the method of the present invention is that the alcloating agent is produced in situ so that an efficient, economical and simpler operation is achieved.

A suspension of 7.3 g (0.096 moles) of ethanolamine ether and 1.44 g (0.048 moles) of paraforealdehyde in 100 µl of ethylene chloride was cooled in an ice bath and 5.9 g (0.048 mol) of α-cyanoboride was added. After stirring for about 45 minutes, 4.03 g (0.016 mol) of 2Z-trilomethyl-6Z-methyl-2-chloro-cetalilide and 2.0 g of iynzyltriellailonium chloride were added. 50 ml of 50% sodium hydroxide are then added in one portion. After approximately 5 minutes, the reaction is complete. Ice and water are added to the mixture, the phases are effectively separated, and the organic phase is then dried, filtered and concentrated. The residue was distilled under vacuum to give 4.2 g (77% yield) of a clear colorless oil, b.p. 150-160 ° C at a pressure of 6.7 Pa.

Analysis for C ^ HHjClClF NONO ^:

calculated: 49.49% C, 5.04% H, 4.12% N, found: 49.33% C, 5.04% H, 4.08% N.

The product is identified as N - [(4-methoxypetoxy) ethyl] - (trifluoromethyl-6-methyl-4-chloroacetyl).

If the N-alkylation process is not carried out at a high or too low temperature, various impurities may be formed, for example with the N-amide, the corresponding imidate, alpha-alkoxyamine or diketopiperazines. Such impurities may be removed by washing the organic layer with dilute aqueous salt or acid solution, for example 2-3% sodium chloride solution or 5% hydrochloric acid.

Examples 3 to 13

Using a substantially sterile and reactive reagent procedure and under the same general reaction conditions as described in Examples 1 or 2, but substituting the impurity starting sec-α-anilide and alkylating agent to give the final product, additional compounds of the above are prepared. formulas are also characterized in Table I.

Table I

Example no. Compound EmePrický formula Boiling point ° C (Pa) element Ainaysis,% calculated found 3 N- (isopropoxymethyl) -2 --- Cl 3 ^H 15 ^F 3 ^ClNO 2 100 to 101 C 50.41 50.52 -tгflUooгtdtll-2-chloг- (7) H 4.88 4.89 acetanniid N 4.52 4.46 4 N- (n-propoxymethyl) - С ^ НцС ^ Од 110 to 120 C 51,94 51,80 -2 * -trffUoortdtll- (13) H 5.29 5.17 6-methyl-4-chloro N 4.33 4.28 acdtanniid • 5 N- (isopropoxymethyl) - C ^ HH ^ClF ^ 110 to 120 C 51,94 51,69 -2 * -trffUoortdtll- (13) H 5.29 5.23 -6- ^ 6 ^ 1-2- ^ 1 ^ - N 4.33 4.22 acetanniid 6 N- (i ^^ me ^) - C _{) 5} H, ₉ ClF ₃ NO ₂ 130 to 140 C 53.34 53.07 -2 * -trffUooredtll- (13) H 5.67 5.61 4 '- methyl 4-chloro- N 4.15 4.01 acetaiilid 7 N- (Inylolyl) -2 '- C ^ jClF ^ ^ oil C 48.47 49.94 - ^ f ^ uorme ty1-7 * - H 4.43 4.44 -eedyl-2-chloroacetate N 4.74 4.70

anilide continuation of Table I

Example # Compound Empirical formula Boiling point ° C (Pa) element Analysis,% calculated found 8 N- (n-butoxymethyl) - ^C 15 ^H 19 ^C1F 3 ^NO 2 135 to 138 C 53.34 53.32 -2'-trifluoromethyl- (7) H 5.67 5.68 -6'-methyl-2-chloro- N 4.15 4.14 acetanilide 9 N- (sec 5-butoxymethyl) - ^C 15 ^H 19 ^C1F 3 ^NO 2 135 to 142 C 53.34 53.23 -2'-trifluoromethyl- (7) H 5.67 5.67 -6 * -raethyl-2-chloro- N 4.15 4.13 acetanilide 10 N- (allyloxymethyl) - ^C 14 ^H 15 ^ClF 3 ^NO 2 123 to 125 C 52.27 52,11 -2'-trifluoromethyl- (13) H 4.70 4.74 -6 * -methyl-2-chloro- N 4.35 4.34 acetanilide 1 1 N- (propargyloxymethyl) - c, ₄ (h _{) 3} cif ₃ no ₂ oil C 52.59 52.44 -2 '-trifluoromethyl-6 * - H 4.10 4.14 Methyl 2-chloroacetanilide N 4.38 4.34 12 N- (isamyloxymethyl) - C ₆ H ₂ CIF ₃ NO ₂ 150 C 54.63 54.66 -2'-Trifluoromethyl-6 * - (7) H 6.02 6.03 methyl-2-chloroacetanilide N 3.98 4.00 13 N- (ethoxymethyl) -2 * - C, 4 ^H and ₇ C1F ₃ NO ₂ 133 to 135 C 51, 94 51.32 -trifluormety1-6 * - (3) H 5.29 5.26 -ethyl-2-chloroacetanilide N 4.33 4.39 14 N- (n-propoxymethyl) - c, ₅ H, ₉ cif ₃ no ₂ colorless C 53.34 53.74 -2 '-trifluoromethyl- oil H 5.67 5.77 -6 * -ethyl-2-chloro- N 4.15 4.16 acetanilide 15 Dec N- (isopropoxymethyl) - c, ₅ H, ₉ cif ₃ no ₂ 100 to 105 C 53.34 53.43 -2 * -trifluoromethyl- (13) H 5.67 5.74 -6 * -ethyl-2-chloro- N 4.15 4.18 acetanilide

The secondary anilide used as starting material in the examples above to produce the compounds of the invention is preferably produced by conventional chloroacetylation of a suitable primary amine, as shown in Example 14 below.

Example 16

This example illustrates the production of a secondary rilide used as a starting material to produce the compound of Example 13.

6.0 g (0.03174 mol) of 2-trifluoromethyl-6-ethylanilide are dissolved in 75 ml of toluene and 3.77 g (0.033 mol) of chloroacetyl chloride are carefully added. The resulting suspension was heated to boiling and held for 4 hours. The mixture was then diluted with an equal volume of hexane and allowed to stand. The product crystallized and the resulting solid was filtered off and air dried to give 5.8 g (69% yield) of the product. The filtrate was concentrated to give an additional 2.7 g of white

mp 121 to 124 ° C (sealed tube). Aialysis for СцН ^ CIF ^ NO: calculated: 49.73% C, 4.17 % H, N, 5.27 found: 49.36% C, 4.09 % - H, 5.38% N.

The product is identified as 2-trifluoromethyl-6'-ethyl-2-chloroacetyl.

The primary amines of the type used for the production of the secondary anilides of halogenated acyl as described above are known from the literature, see for example the aforementioned US Patent No. 3,966,811 and GB Patent No. 2,013,188.

As mentioned above, the compounds of the present invention are effective as herbicides, especially as preemegaenic herbicides, although postemergence activity has also been found. Pre-emergent tests reported herein include both greenhouse and field tests. In greenhouse tests, the herbicide is used either for topical application after planting the seeds or vegetative shoots or for incorporation into the soil, which is used as an overlay over the test seeds in the pots before seed emergence. In field trials, the herbicide can be used to incorporate the soil prior to planting (PPI), i.e. the herbicide is applied to the soil surface and then mixed into it after mixing, after planting the crops, or the herbicide can be applied to the surface ЗД.) After planting the seeds of the useful plants.

The surface test method (S.A.) used in the greenhouse is carried out as follows:

Containers - for example aluminum pots usually 24.13 x 13.34 x 6.99 cm or 9.53 x 9.53 x 7.62 cm plastic pots with drainage holes in the bottom are filled with dust Ray silt loam sooi, which is compressed to a level of 1.27 cm from the top of the pot. Plants of the species to be tested are then sown in the pot and then covered with a layer of test soil 1.27 cm high. The heebicide is then applied to the soil surface by a transferring sprayer at a rate of 187 liters per hectare at a pressure of 211 kPa. 0.64 cm of water are introduced into each pot from above, and the pots are then placed on greenhouse workbenches, where the watering is carried out as required from below. In an alternative procedure, top irrigation may be omitted. Observation of the herbicidal effects is made about three weeks after treatment.

The treatment of the soil into which the herbicide (S.I. ”) is applied, used in greenhouse tests, is as follows:

The topsoil of good quality is introduced into aluminum pots and compressed to a depth of 0.9 to 1.27 cm from the top of the pot. A specified number of seeds or vegetative shoots of different plant species are placed on the soil surface. The soil needed to fill to the rim of the pot after sowing or placing the vegetative shoots is weighed into the pot. The soil and known amounts of active ingredient used in the solvent or as a wettable powder suspension are thoroughly mixed and used to coat the prepared container. After treatment, the pots are first surface-moistened with water at a rate of 0.64 cm of rainfall and then irrigated from below as necessary to obtain suitable moisture for germination and growth. In an alternative procedure, irrigation from above may be omitted. Observations are made about two to three weeks after sowing and treatment.

Tables II and III summarize the results of the tests performed to determine the pre-emergence herbicidal effect of the compounds of the invention. In these tests, the herbicides are added to the soil and irrigated only from below. Heebicidal evaluation is obtained using a fixed scale based on the percentage of damage to each plant species. The values are defined as follows:

% suppression Evaluation 0 to 24 0 25 to 49 1 50 to 74 2 75 to 100 3 not identified 5

The plant species used in one set of tests, the results of which are given in Table II, are marked with the letters as follows:

A thistle G B rhubarb H C abutionn I D whipgrass J E white goosefoot K F rdenno pepper shrew pecker creeping sorghum seedlings (Downy Brome) hedgehog corns foot

Table II

Compound kg / ha of the product of Example no

Type of plant

D E F G I

11.25

5.65

11.22

5.63

11.23

5.62

11.25

5.65

11.25

5.65

11.25

5.65

3 33

2 33

113 2

132

33

2 33

2 33

1 23

2 33

0 33

133

013

3 3 3 3 3 3 3 3 2 3 3 3 3 0 2 2 3 3 3 2 2 3 3 1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1 3 3 3 3 3 3 3 3

0 continuation of Table II

Example compound no kg / ha AND в C D Species E plants F G H AND J к 7 11.2 3 1 2 2 3 0 2 3 1 3 3 5.6 1 0 1 1 3 0 1 3 1 3 3 8 11.2 3 2 0 2 3 3 3 3 3 3 3 5.6 3 1 0 3 3 3 3 3 3 3 3 9 11.2 3 2 2 3 3 3 3 3 3 3. 3 5.6 3 2 1 2 2 3 3 3 1 3 3 10 11.2 3 2 1 3 3 3 3 3 3 3 3 5.6 3 1 1 2 3 3 3 3 0 3 3 11 1 ', 2 3 1 1 3 3 3 3 3 0 3 3 5.6 3 1 1 2 3 3 1 3 1 3 3 1 2 11.2 3 2 0 2 3 3 3 3 0 3 3 5.6 3 1 0 2 1 2 3 3 3 3 3 13 11.2 3 2 2 3 3 3 3 3 3 3 3 5.6 3 2 2 3 3 3 3 3 2 3 3

The compounds are further tested using the above procedure on the following plants:

L soya leguminous

M diabetes

N wheat rice

P sorghum

В řepen

Q buckwheat

D povijnice

R hemp

E goosefoot white

F rdeeno pepper

C abutilon

J sveřep

К hedgehog corns T rosacea bloody

S рГО80

The results are shown in Table III.

Table III

Pre-emergence test

Compound of Example No. kg / ha L M N 0 P в Q 1 5.6 1 2 3 3 3 0 3 1.12 0 1 1 2 3 0 1 0.28 0 1 0 2 1 0 1 0,056 0 0 0 0 0 0 0 0.0112 0 0 0 0 0 0 0

D R E F C J with к T 3 3 3 3 2 3 3 3 3 2 2 3 2 0 3 3 3 3 0 3 3 3 0 2 3 3 3 0 1 1 1 0 0 2 2 3 0 0 1 1 0 0 1 2 2

continuation of Table III

Compound

from the example number kg / ha L M N 0 P (B) Q D R E F C J with TO T 2 5.6 1 3 2 3 3 1 2 3 3 3 3 0 3 3 3 5 1.12 0 3 2 3 2 0 1 3 1 2 2 0 3 3 3 5 0.28 0 2 0 1 1 0 0 1 1 1 0 0 3 3 3 5 0,056 0 1 0 0 0 0 0 0 0 0 0 0 1 1 3 5 0.0112 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 5 3 5.6 0 3 3 3 3 1 3 3 3 3 3 1 3 3 3 3 1.12 0 1 1 3 3 1 0 3 1 3 0 0 3 3 3 3 0.28 0 0 0 2 2 0 0 0 0 3 0 0 1 3 3 3 0,056 0 0 0 1 0 0 0 0 0 2 3 0 0 3 3 3 0.0112 0 0 0 0 0 0 0 0 0 1 0 0 O 3 3 3 0.0056 0 0 0 0 0 0 0 0 0 3 0 0 0 1 0 1 4 5.6 2 3 3 3 3 2 3 3 3 3 3 1 3 3 3 3 1.12 1 3 2 3 3 1 3 2 3 3 3 1 3 3 . 3 3 0.28 0 1 2 2 1 0 1 0 1 3 3 0 2 3 3 3 0,056 0 1 1 1 2 2 1 0 2 1 1 0 0 2 2 3 0.0112 0 1 0 0 0 0 0 0 0 1 0 0 0 3 3 3 5 5.6 1 2 3 3 3 1 3 3 3 3 3 1 3 3 3 3 1.12 0 2 2 3 3 0 2 0 2 3 3 0 3 3 3 3 0.28 0 2 1 3 3 2 2 3 2 3 3 0 3 3 3 3 0,056 0 1 0 1 2 1 2 0 1 3 1 0 2 3 3 3 0.0112 0 1 0 0 0 1 1 0 0 3 1 0 1 2 3 3 6 5.6 1 3 3 3 3 2 3 3 3 3 3 1 3 3 3 3 1.12 0 1 0 3 3 1 3 3 1 3 3 0 3 3 3 3 0.28 0 2 0 2 2 2 2 1 3 3 3 0 3 3 3 3 0,056 0 2 0 1 2 1 2 2 2 3 1 0 2 3 3 3 0.0112 0 2 0 1 O 2 2 2 2 3 1 0 1 1 3 3 7 5.6 0 3 2 2 3 0 2 2 2 3 0 0 3 3 3 3 1.12 0 1 0 0 1 0 1 0 0 2 0 0 0 2 3 3 0.28 0 0 0 0 0 0 1 2 0 0 0 0 0 2 2 3 0,056 0 1 0 1 0 0 0 0 0 3 2 0 0 0 2 3 8 5.6 2 3 3 3 3 2 3 3 3 3 3 1 3 3 3 3 1.12 1 2 3 3 3 0 2 0 1 3 3 0 3 3 3 3 0.28 0 1 2 1 2 0 2 0 2 1 1 0 2 3 3 3 0,056 0 0 1 1 1 0 0 0 0 1 1 0 1 3 3 3 0.0112 1 0 0 0 0 1 0 0 1 0 0 0 1 0 2 3 9 5.6 2 2 3 3 3 2 3 3 3 2 3 1 3 3 3 3 1.12 1 2 3 3 1 1 3 ' 1 2 2 2 0 3 3 3 3 0.28 1 2 2 3 2 0 1 1 2 1 1 0 3 3 3 3 0,056 0 0 0 0 0 0 0 0 0 2 1 0 2 3 3 3 0.0112 0 0 0 0 0 0 0 0 0 0 0 0  0 0 3 3

continuation of Table III

Compound

from the example number kg / ha L M N 0 P (B) Q D R E F C J WITH K T 1 0 5.6 3 3 3 3 3 2 3 3 3 3 3 0 3 3 3 3 1.12 1 2 3 3 3 0 3 3 2 2 3 0 3 3 3 3 0.28 0 2 2 2 2 0 1 0 2 3 2 0 3 3 3 3 0,056 0 1 0 1 0 0 0 0 1 0 0 0 0 3 3 3 0,01 12 0 0 0 0 , 0 0 0 0 0 0 0 0 0 1 2 3 11 5.6 0 3 3 3 3 1 3 3 3 3 3 1 3 3 3 3 1.12 0 3 1 3 1 1 1 '2 1 2 2 0 3 3 3 5 0.28 0 2 1 2 1 0 0 0 1 1 1 0 3 3 3 3 0,056 0 1 0 0 0 0 0 0 5 0 0 0 1 2 3 5 0.0112 0 1 0 0 0 0 0 0 0 0 0 0 0 1 3 5 12 5.6 1 2 2 3 3 1 2 2 0 2 1 0 3 3 3 3 .1,12 1 2 1 2 3 0 2 2 1 2 2 0 3 3 3 3 0.28 0 1 0 1 0 0 1 0 0 1 0 0 1 2 3 2 0,056 0 5 0 0 0 0 5 0 0 0 0 0 . 0 0 2 0 13 5.6 2 3 3 3 3 2 3 3 3 3 3 2 3 3 3 3 1.12 1 2 3 3 3 0 2 2 3 2 3 0 3 3 3 3 0.28 2 2 3 3 1 0 1 0 3 1 3 0 3 3 3 3 0,056 0 1 1 1 0 0 1 0 0 0 0 0 2 3 3 3 0.0112 0 0 0 0 0 0 0 0 1 5 5 0 0 0 2 2

The herbicides of the invention have been found to have unexpectedly superior properties to pre-emergent herbicides, particularly to selectively control hard-to-control and annual weeds, including perennial weeds such as creeping wheatgrass and broadleaf weeds such as sida, hemp, pepper white goosefoot, bent-grass and annual grasses such as shattercane, Brachiioria plarttaginra, hallow sorghum, millet (Texas virgin and millet), Maaai rice, Rottboeelia exaltata, blackgrass (for example green, yellow and stage ^ beeti), hedgehog chicken and rosička krevavá. Weed control is also achieved in other resistant genera such as alpha-ol, abutilone, seedlings, beet, purslane and the like.

Selective control and increased weed control above by the herbicides of the invention has been found in various useful plants, including those of particular interest, such as corn, soybean, soybean, but also others such as cotton, peanut, rapeseed, bush bean, wheat and sorghum, however, wheat and sorghum are usually less tolerant to the herbicides of the invention than the other aforementioned useful plants. The reduced resistance can be improved by the use of safety means, i.e., herbicidal antidote agents. ,

In the data analysis below, reference is made to the use of the herbicide dose designated as G 1 R 2 and GR 4. These doses are expressed in kilograms per hectare (kg / ha). GIR? Is defined as the maximum herbicide dose needed for 15% or less of the damage to the crops. ^GR 85 is defined as the minimum dose required to achieve 85% weed control. The doses of GR @ + and G @ + gj are viewed as a measure of the strength of an industrial product and it is understood that suitable commercially available herbicides may cause greater or lesser damage to the plants in an adequate seed.

Another measure of the effectiveness of a chemical as a selective herbicide is the selectivity factor ”(abbreviated as“ SF ”) for the herbicide in given crops and weeds. The selectivity factor is a measure of the relative degree of crop safety and weed damage and is expressed by the ratio GR4 / GRg4, i.e. the dose GR4 for the crop weed divided by the weed dose, both of which are given in kg / ha. In the tables below, the selectivity factor is expressed in brackets for weeds. The symbol NS means non-selective. Marginal or unspecified selectivity is indicated by a dash (-).

Since the resistance of the crop and weed control are correlated, a brief analysis of this relationship with respect to the selectivity factor is important. In general, it is desirable that the safety factor for the useful plants, i.e. the herbicide resistance value, is high, because a higher concentration of the herbicide is often needed for which reason. On the contrary, it is desirable for the weed control dose to be small, i.e. the herbicide has a high unit effect for economic and possibly also ecological reasons. However, small amounts of herbicide applied may not be sufficient to control certain weed species and larger doses may be required. Therefore, the best herbicides are those which control the largest number of weeds with the least amount of herbicide and have the greatest degree of safety for the crop plant, i.e. crop plants are resistant to them. Therefore, the term selectivity factor (as defined above) is used to quantify the relationship between crop safety and weed control. In connection with the selectivity factors shown in the table, it is shown that the higher the numerical value, the greater the selectivity of the herbicide for the suppressed weed in said crop.

To illustrate the unexpectedly superior properties of the compounds of the invention on both absolute and relative basis, comparative tests were performed in the greenhouse. To this end, the compounds previously described having a similar chemical structure closest to the compounds of the invention have also been used. These former compounds are named as follows (using the same nomenclature as the compounds of the invention):

A. N- (methoxyethyl) -2'-trifluoromethyl-2-chloroacetanilide,

B. N- (ethoxyethyl) -2'-trifluoromethyl-2-chloroacetanilide.

Tables IV and V show pre-emergence herbicidal activity data to compare the relative efficacy of the compounds of the invention and the previously described compounds as selective herbicides against resistant and difficult permanent weeds of creeping grass and grass in 80% of pulses and maize. These weeds commonly grow in most useful plants such as corn and legume soy. The test data in Tables IV and V were obtained under the same conditions and represent the average of two replicate experiments (except for the compound of Example 13 where one comparative test was performed). The test procedure is the same as described for Tables II and III, except that the original overhead irrigation is adjusted to 0.64 centimeters of rainfall and then irrigated from below. NS means non-selective in the range used in the assays.

Table IV

Compound Dose GRi5 (kg / ha) soya leguminous Dose GRq ^ (kg / ha) creeping grass yellow nutsedge AND > 2.24 > 2.39 (NS) 1.13 (1.98) В 1.96 0.61 (3.21) 0.44 (4.45) Example 1 2.67 0.17 (15.6) 0.17 (15.6 Example 3 1.68 0.27 (6.22) 0.19 (8.84) Example 4 1.12 0.13 (8.62) 0.17 (6.59) Example 5 1.46 0.26 (5.62) 0.26 (5.62) Example 13 2.13 0.20 (10.65) 0.17 (12.53)

In connection with the 8 data from Table IV, it should be noted that each compound of the invention exhibits an extraordinarily high selectivity factor - (values in parentheses) against both the plasmid plains and the saxifrage in comparison to the compounds described previously. In particular, the unit efficacy (relative phytotoxicity per unit herbicide) of the compounds of the present invention is clearly higher than that of the prior art compounds, as shown in the prior art, while maintaining safety for the crop. Of particular note are the extremely high selectivity factors of the compounds of Examples 1 and 13.

The comparative data showing the relative potency of the compounds of the invention in comparison with the earlier compounds in the cuvette and calyx in the cuvette provided in Table V,

Table V

šoučenina Dose GR. . (kg / ha) ¹⁵ KuNice Dose GRj (kg / ha) plush yellow nutsedge AND > 2.24 > 2.39 (Nš) 1.13 (1.98) (B) 0.81 0.61 (1.33) 0.44 (1.94) Example 1 0.76 0.17 (4.47) 0.17 (4.47) Example 3 1.94 0.27 (7.19) 0.19 (10.2) Example 4 0.75 0.13 (5.85) 0.17 (4.47) Example 5 1, 83 0.26 (7.04) 0.26 (7.04) example'13 2.24 0.20 (11.2) 0.17 (13.18)

With reference to Table V, it should be noted that each compound of the present invention exhibits an extremely high selectivity factor (values in parentheses) against both creeping grass and churn in smoke, compared to the compounds described previously, the thyme being desirable. It should be noted that the unit activities of the compounds of the invention are clearly superior to creeping wheatgrass than to the previously known compounds, while maintaining safety for the crop. Of particular note are the extremely high selectivity factors of the compounds of Examples 3, 5 and 13, especially when compared to the factors previously described.

It is apparent from the comparative data in Tables IV and V that the compounds according to the invention have an excellent higher and unexpectedly better herbicide. action against herbicidal resistance to permanent weed-like weeds and grasses in the two main use roets, i.e., soybean and taukuiui, than compounds A and B, which are most closely related to the compounds of the prior art.

In addition, from the pre-emergence herbicidal data in other teets, it has been found that the compounds of the invention also selectively suppress creeping wheat and / or diol. weeds in at least one crop plant selected from cotton, sapling, shrub phazoo, foaming, sorghum and / or canola. For example, Table VI provides data showing the herbicidal selectivity of the compounds of Examples 1 and 3 against the creeping plant, rape, bush phazoo, dumbbell and wheat. Unless otherwise stated, greenhouse. the tests in Table VI and Tables nV81 and above in soil treatment by incorporating the herbicide in the initial irrigation from above and then in the irrigation from below as described above.

Table VI

Compound rape Dose GR ₁ groundnut ₍₅ (kg / ha) Sorghum wheat Dose GR ₈ g (kg / ha) ⁸⁵ creeping grass Example 1 0.86 0.12 (7.2) - 0.90 - - 0.12 (7.5) - - 0.24 - 0.12 (2.0) - - - 0.21 0.12 (1, 8) Example 3 1 »9 - 0.28 (6.8) - 2.24 - - 0.26 (8.0) - - 0.84 - . 0.28 (3,0) 0.28 0.28 (1,0)

The compound of Example 1 was also tested under field conditions to determine pre-emergence selectivity against fox-tail, hedgehog, corn and millet in several useful plants. Data (representing the average of three experiments) are shown in Table VII for both the topical application of the herbicide (S.A.) and the incorporation of the herbicide into the soil (P.P.I.). The seeds were planted in a fine, hot soil of medium humidity, to a depth of 5.08 cm. The first rainfall (0.51 cm) did not occur the day after treatment, the second rain (0.64 cm) two days after treatment. Total rainfall during 22 days after treatment was 4.57 cm water. Observations were made 6 weeks after treatment.

Table VII

Compound

Example 1

Method of Administration S.A. P.P.I.

Rate (kg / ha) 0.56 '2 2.24 4.48 0.56 1.12 2.24 4.48 Override percentage: field corn 0 0 0 15 Dec 0 0 5 32 sweet corn 0 0 7 37 0 3 27 Mar: 40 soya leguminous 0 5 0 13 5 7 20 May 40 peanuts 0 0 8 22nd 17 13 15 Dec 28 cotton 0 13 20 May 25 13 32 37 82 sorghum 0 3 17 77 32 53 92 98 bush beans 0 8 20 May 32 23 10 37 43 rape 0 0 5 33 0 0 15 Dec 40 psárka (Foxtail spp.) 62 92 93 98 75 90 98 100 ALIGN! hedgehog corns the leg 63 93 93 98 75 93 98 100 ALIGN! millet 63 83 95 97 23 58 60 85

The data in Table VII show that, in general, the compound of Example 1 acted better as a selective herbicide when applied topically than when incorporated into soil. Especially in topical application tests, the herbicide selectively suppresses three weeds at the applied rate above 0.58 kg / ha while maintaining crop safety (maximum damage of 15%) for field corn and soybean at doses up to 4.48 kg / ha, while maintaining safety in sweet corn, groundnut and rape at a rate of more than 2.24 kg / ha and in cotton, sorghum and bush beans at a rate of just under 2.24 kg / ha. The compound of Example 1 in P.P.I. Tests selectively suppresses various species of blackgrass and hedgehog corns in a dose less than

1.12 kg / ha, while maintaining the safety for a crop plant of kilki uici, underground and rapeseed at a rate of up to 2.24 kg / ha and weak below 2.24 kg / ha for soybean grass.

Further field test data for the compound of Example 1 shows pre-emergence selective control of other weeds such as purple nutsedge, setmia uberli, yellow foxtaH, white medic, whitefly, iepe, ab ^ tlm, peppermint (Р < ^ го ^ о5 ^ 11 ^ и ^ 01 ^ 1, sida (prickly sida), purslane, bloody dew, go ^ se ^ pig, millet (Texas panic), Rchardie scabra and / or Acanthospemzum hispddim in soybean, kiukuid, cotton Those skilled in the art will recognize that not all of the aforementioned weeds are selectively suppressed in all said crop plants under all climatic, soil and moisture conditions and / or by all herbicide application methods. weeds in useful soybean, soybean, cotton, and podzezmice plants from a number of field tests at different locations under different soil conditions, humidity, etc. are summarized in the tables ch VIII to XI.

The term WAT in the tables and the following refers to the number of weeks after herbicide treatment of the plants used either for topical application (S.A.) or for incorporation into the soil prior to planting (P.P.I.). Dose data used for each crop and weed combination is given as the ratio GR4 and GR4 (as defined above). From the ratio GR ^ / GRg ^ results in a selectivity factor (SP), 'NS is a designation for noelectivity, and the theorem - (-) indicates marginal or non-determinable selectivity, for example because the actual ratio GR ^ to GRg is higher or lower than in said test. In Tables VIII to XI, the blank indicates that the plant species were absent from the special test area or that - no data were obtained or less important than the other data reported; for example, observation of 3 WAT is omitted because 6 WAT is favorable or 6 WAT * is omitted because 3 WAT is final.

Table VIII

Compound Κ ^ ηα ^ crop / weed Method of application WAT ^GR 15 ^ ^gr 85 SF Example 1 soya S.A. 3 f ^ edi 5 > 4.48 / 0.12 4.0) P.P.I. 3 5 > 4.48 / <1.12 4.0) 8 > 4.48 / <1.12 4.0) soybeans roaring S.A. 6 2.52 / 2.8 (NS) Yellow foxtail P.P.I. 6 1.4 / <1.12 (> 1,3) arya / goosefoot S.A. 6 2.52 / 2.52 (1,0) White ... p.p.i. 6 1.4 / 2.8 (NS) soybean (Pexrnsylvanla) P.P.I. 8 4.48 / 2.52 (1.8)

srnwtweed)

Data shown in Table VIII that the compound of Example 1 selectively suppresses foxtail (Satuta fedi and yellow foil), a white medication and a pepper tree in a soybean from 6 to 8 weeks after treatment with the S.A. and P.P.I.

Table IX

Compound In addition to weed crops Method of application WAT GR ₅ and / «8 ₅ SF Example i ku] kljiic / Setaria S.A. 6 4.48 / < 1.12 (4.0) faberii S.A. 6.5 > 7.84 / 8.4 (NS) P.P.I. 6 4.76 / 1.96 (2.5) P.P.I. 6.5 > 6.72 / 4.48 (1.5) whine o / string S.A. 3 > 4.48 /> 4.48 (-) S.A. 6 > 4.48 /> 4.48 (-) 3 4.76 /> 4.48 (-) P.P.I. 6 4.76 /> 4.48 (-) ice / ice bath S.A. 3 > 4.48 /> 4.48 (-) S.A. 6 > 4.48 /> 4.48 (-) P.P.I. 3 4.76 /> 4.48 (-) P.P.I. 6 4.76 /> 4.48 (-)

Data in Table IX that the compound of Example 1 selectively suppresses Setaria faberii in kiUkUici from 6 to 6.5 weeks after treatment with the S.A. or P.P.I. Pseudopathic selectivity at the doses tested was not determined but showed weed damage.

Table X

Compound Combination crop / weed Method of application WAT ^OR 15 / ^OH 85 SF Example 1 cotton / pleat S.A. 6 3.64 / 1.68 (2,17) Piurple nutsedge S.A. 9 3.36 / 2.24 (1.5) P.P.I. 6 3.36 / 4.2 (NS) cotton / sida S.A. 6 3.64 / 3.08 (1,18) S.A. 9 3.36 / 4.76 (NS) P.P.I. 6 3.36 / 4.76 (NS) cotton / shiicha S.A. 9 3.36 / 1.96 (1,7) cotton ^ rosička S.A. 7 1.4 / <1.12 (> 1.25) bloody (Crabgrass / imooth and hriiry /) P.P.I. 7 0.84 / 1.12 (NS) cotton / Goose grass P.P.I. 7 0.84 / <1.12 (-)

The data in Table 'X' shows that the compound of Example 1 selectively suppresses the vesicles and up to 9 weeks after treatment, the sidu up to 6 weeks after treatment and the rosacea to 7 weeks after treatment. - Grosegrass suppression is marginal or not determined.

Table XI gives data on the pre-emergence activity of the compound of Example 1 against three-year-old weeds, i.e., millet (Texas panic), Acanthospermic Hispanium, and WchmrUa scabra in the pith for up to 12 weeks after treatment. - The data in Table XI represents the average of three replicate experiments in sandy loam soil containing 1.3% organic matter, 79.2% sand and 10% clay. H ^ 2 is used surface-wise

Table XI

Compound Rate (kg / ha) podzemiice WAT Percent suppression Richardie Acabra WAT millet (Texas virgins) WAT Acantho spermm hispddvm WAT 4 8 12 4 8 12 4 8 12 4 8 12 Example 1 2.24 5 0 0 50 57 40 78 40 0 90 3.36 10 0 0 68 63 55 85 60 0 4.48 17 7 0 85 88 78 95 100 ALIGN! 0 95 95

In conjunction with the data in Table XI, it appears that the compound of Example 1 selectively suppresses millet in the ground even. 8 weeks and provides a high degree of suppression up to 12 weeks after treatment at a dose of about 4.48 kg / ha · Selective suppression of Aciaathosperarun hispidum is achieved at a dose of 3.36 kg / ha for 8 weeks and complete suppression for 12 weeks after treatment at a dose of 4.48 kg / ha · Selective suppression of R.chardia scabra * e achieves and less than 2.24 kg / ha at 8 weeks after treatment and at a dose of '4.48 kg / ha, 95% suppression is achieved at 12 weeks after treatment·

In other greenhouse tests, the compounds of the invention show selective control of various annual and perennial weeds in a variety of useful plants. GR ^ / GRg ^ (expressed in kg / ha) for crops and weeds is 0.67 / 0.25 (SF 2,7 2.7) · in corn and 1.12 / 0.25 (SF 4 4), 5) in leguminous soybean · The compound of Example 11 selectively suppresses grass and corn creeping in maize and leguminous soybean · The GR ^ / ORg ^ ratio for the crop plant and the billet is> 2.24 / 0.95 (SF 2.4) in the cleavage and 2.24 / 0.5 (SF = 4.5) in leguminous soy. for corn and soybean in reptilian wheat is> 2.24 / 0.5 (SF * ^ 4.5) · In the anti-rum test · in cotton, the ratio is GR ^ / GR ^ (average of twice the treatment) 1 , 96 / 0.95. (SF = 2.1) Similarly, the compound of Example 13 selectively suppresses cotton swell and wheat creep, with the ratio GR ^ / GR ^ being 0.7 / 0.47 (SF 1.7) in cotton and 0.58 / 0.47 (SF 1,2 1.2) in · wheat ·

In one multiple test with utility. greenhouse plants were tested and the compounds of Examples 1, 13, 14 and 15 were tested against yellow nutsedge in cotton, peat, soybean, corn and rice. in cotton, soybean · leachy · and for each of the compounds · The GR ^ / GRg ^ ratios for these compounds are given in Table XII · The selectivity factors are given in brackets after each useful plant ·

T a b u 1 k and XII

Compound ° ^R 15 · · (kg / ha) GR ^ (Kg / ha) Cotton Cotton Soya Corn

Example 1 0.24 1.96 (8.2) 0.87. (3.6) 0.69 (2.9) Example 13 0.21 2.52 (12.0) 1.96 (9.3) 2.52 (12.0) Example 14 0.38 2.8 (7.4) ' 2.24 (5.9) 1.68 (4.4) 1 ¹ Example.15 0.44 2.8 (6.4) 1.96 (4.5) 1.96 (4.5)

The compounds of Examples 1 and 13 to 15 are further tested against wheat creeping grass, soybean and maize. None of the compounds were found to be selective in wheat. The data for said compounds against creeping rye in soybean and maize are given in Table XIII.

Table XIII

Compound QBgj (kg / ha) creeping grass ^gr 15 (kg / ha) soybean grass maize Example 1 0.07 0.81 (11.6) 0.69 (9.9) Example 13 0.36 1.68 (4.7) 1.68 (4.7) Example 14 0.45 1.46 (3.2) 2.52 (5.6) Example 15 0.75 1.96 (2.6) 2.24 (3.0)

In yet another greenhouse test of herbicidal activity, the compounds of Examples 1 and 3 were tested against a number of annual grasses, which include resistant weeds such as millet (Texas panic), halibut sorghum seedlings, shattercane, Brachiaria plaetaginea, millet, Malaysian rice and. Rottboellia exaltata · The results of these tests are shown in Table XIV, selectivity factors are noted in parentheses · A dash indicates marginal or unspecified selectivity ·

Table XIV

Compound Dose GR ₁₅ (kg / ha) of soybean Millet (Texas Panic) Dose GRq ₅ (kg / ha) of Halep sorghum seedlings Shattercane Brachiaria plaetaginea Example 1 > 1.12 1.12 0.14 0.28 0.56 (> 1.0) (> 8.0) (> 4.0) (> 2.0) Example 3 > 1.12 > 1.12 0.28 0.93 > 1.12 (-) (> 4.0) (> 1,2) 1,0)

Compound Dose GRg ^ (kg / ha) millet Panicum dechotonriflorum Malaysian rice Bottboallia exaltata Example 1 1.12 <0.07 0.2 ’,’ 2 (> 1.0) (> 16.0) (> 5.6) (> 1.0) Example 3 1.12 <0.07 0.14 > 1.12 (-) (> 16.0) (> 8.0) (-)

The data in Table XXV shows that the compound of Example 1 selectively suppresses all annual weeds in a soybean test. , 12 kg / ha · To determine the selectivity of the compound

227326 20 oy against these three weeds that are not selectively suppressed at the dose tested would require a bitch higher ·

The obvious advantage of a herbicide lies in its ability to operate in a wide variety of soil types. Therefore, Table XV shows the herbicidal effect of the compound of Example 1 on creeping wheatgrass in soybean grass in very diverse soil types with varying organic and clay content.

The treatment is carried out by introducing the herbicide into the soil, in which the seeds were planted to a depth of 0.95 cm, which were irrigated with 0.64 cm water in the top of the soil.

Table XV

Compound Type of soil Organic matter% Clay,% Dose GR ₁₅ (kg / ha) 3 leguminous soya Dose ORpc (kg / ha) ⁸⁵ creeping grass Example 1 Dusty Ray dirt 1 · 0 9.6 112 0.22 (5.1) clay soil from the Sherpa 2.3 30.35 > 2.24 0.28 (> 8.0) clay soil from Wwbash 4.3 33.0 • 0.28 (-) clay soil from Drummer 6.0 37.0 2.24 0.11 (20.0) sand from Florida 6.8 1,8 1.96 0.2 (9.6) bshmo from Florida 60 - > 2.24 0.58 (> 3.9)

The data in Table XV shows that the compound of Example 1 is completely insensitive to a type of soil with variable organic matter content and causes selective suppression of creeping rye in soybean grass in soil with organic matter content of 1.0 to 60% with clay content of at least 1 , 8 to about 37% · Yellow soybean data in clay soil from Wabash could not be determined in this test · Also the selectivity factors in Ssrpa clay soil with Florida mud are also minimal, since the meaima dose in the test was 2.24 kg / ha · Heebbcid is safe for soya paste at the same dose, above 2.24 kg / ha ·

In order to determine the resistance of the herbicides according to the invention to leaching to the soil with the resulting herbicidal activity, laboratory tests are carried out. In these tests, the compounds of Examples 1 to 4 are formulated in acetone and then sheared on different axes. z Ray with clay-like soil from Drummer contained in pots, in which they are filter paper .. covered with holes holes and water drain from the dma pot. The pots are leached and subjected to leaching by positioning the work bench rotating under two nozzles, which terminate the water tank calibrated for discharge.

2.5 cm of water per hour, to imitate

• The water coming in from the soil in the pots is allowed to pass through the filter paper with water outlets. The pots are then allowed to stand for three days at room temperature. as surface layer from above to other pots containing it msd - seedlings, hedgehog seeds corns · The potters are then planted on the workbenches in the greenhouse, watered from below with the seeds to grow for 2 to 3 weeks · Visually determined growth inhibition percentage is compared with control ( untreated) and record the raw weight of the hedgehog. Data for control assays are obtained from 6-fold repeats and data for test compounds from 3-fold repeats. These test data are shown in Table XVI. Raw weed hmoonooti is not determined in Drurnor clay soil tests.

Table XVI

Compound Rate (kg / ha) Rain (cm) Hedgehog corns the leg Percent suppression Raw weight (g) Dirt soil from Bay clay soil from Drummer Dirt soil from Bay clay soil from Drummer Control checks 0 0 4.37 0 1,27 3.88 0 5.08 4.14 0 10.16 3.98

diameter 4,10

Example 1 2.24 0 100 ALIGN! 100 ALIGN! 0 - 1, 27 100 ALIGN! 100 ALIGN! 0 - 5.08 95 100 ALIGN! 0.20 - 10.16 35 100 ALIGN! 2.65 0.56 0 100 ALIGN! 100 ALIGN! 0 1,27 100 ALIGN! 100 ALIGN! 0 - 5.08 70 100 ALIGN! 1,21 - 10.16 33 100 ALIGN! 2.73 - 0.14 0 95 100 ALIGN! 0.20 «. 1,27 96 97 0.17 - 5.08 58 95 1.74 - 10.16 20 May 20 May 3.26 - Example 4 2.24 0 100 ALIGN! 100 ALIGN! 0 1,27 100 ALIGN! 100 ALIGN! 0 - 5.08 100 ALIGN! 100 ALIGN! 0 - 10.16 95 100 ALIGN! 0.22 - 0.56 0 100 ALIGN! 100 ALIGN! 0 - 1,27 100 ALIGN! 100 ALIGN! 0 - 5.08 94 100 ALIGN! 0.24 - 10.16 52 100 ALIGN! 1.97 - 0.14 0 99 81 0.05 1,27 95 99 0.22 - 5.08 63 94 1.53 - 10.16 .14 54 3.15 -

continuation of Table XVI

Compound Dose Déšl Ježatka corns foot (kg / ha) (cm) Percent suppression Raw weight (g) the dusty soil of Ray clay soil from Drummer dusty soil 2 Ray clay soil from Drummer Example 5 2.24 0 100 ALIGN! 100 ALIGN! 0 1,27 100 ALIGN! 100 ALIGN! 0 - 5.08 92 100 ALIGN! 0.31 - 10.16 71 100 ALIGN! 1.18 - 0.56 0 99 100 ALIGN! 0.02 - 1,27 100 ALIGN! 100 ALIGN! 0 - 5.08 89 100 ALIGN! 0.44 - 10.16 17 96 3.41 - 0.14 0 98 70 0 - 1,27 90 96 0.41 - 5.08 38 85 2.77 - 10.16 12 47 3.62 - Example 6 0.24 0 100 ALIGN! 100 ALIGN! 0 and. 1,27 100 ALIGN! 100 ALIGN! 0 - 5.08 99 100 ALIGN! 0.03 * r 10.16 84 100 ALIGN! 0.64 - 0.56 0 99 50 0.04 1,27 99 100 ALIGN! 0.02 - 5.08 90 93 0.41 - 10.16 72 84 1 »17 - 0.14 0 84 12 0.66 and. 1,27 90 26 0.43 - 5.08 58 20 May 1.72 - 10.16 29 12 2.92 -

The data in Table XVI shows that the compounds of the present invention are very resistant to leaching in the soil under various rainfall conditions. Especially at a dose of 2.24 kg / h, each of the compounds of the present invention suppresses hedgehog corn on the equivalent of 10.16 cm Ray dust and Drummer clay soil except for the compounds of Examples 1 and 5 in Ray dust, where the control determination is performed at 5.08 cm equivalent of rainfall · Also at a lower applied rate of 0.14 kg / ha the compounds of Examples 1, 4 and 5 suppress the hedgehog corn feet in Drummer clay soil equivalent to 5.08 cm of rainfall ·

Toxicological studies of the compound of Example 1 show that the compound is absolutely safe because it is slightly toxic (OLD ≥ 2,300 mg / kg, MLD ≥ q> 5,010 mg / kg), weakly irritating to the eye and does not irritate the skin. Special handling with normal caution ·

From the foregoing detailed description it can therefore be concluded that the compounds of the invention have unexpectedly and extremely good herbicidal properties, both absolutely and relative to most structurally related compounds known from prior publications. difficult to control perennial and annual weeds of grass type in soybean legumes and maize, but also in peanuts, cotton and other useful plants. (Texas panic), Rottboaaia exaltata, millet, Brachharia plaetaginea, sorghum seedlings, scattercane and / or maize rice, while also suppressing and / or damaging other less resistant annual grasses and perennial weeds.

compositions of the present invention comprising concentrates that require dilution prior to administration comprise at least one active ingredient and an excipient in liquid or solid form. The compositions are prepared by mixing the active ingredient with an adjuvant. These include diluents, fillers, carriers and auxiliaries for obtaining finely divided solids, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an excipient such as a particulate solid, an organic liquid, water, a wetting, dispersing or emulsifying agent or any suitable combination thereof.

The compositions according to the invention, in particular liquids and dispensers, preferably contain as an auxiliary agent at least one surfactant in an amount sufficient to obtain the composition readily dispersible in water or oil. . The incorporation of a surfactant into the composition greatly increases its effectiveness. Under the term surfactant are wetting, dispersing, suspending and formulating agents. Anionic, cationic and non-gelling agents can be used as easily.

Preferred formulations are the allyl benzene sulphouates and the allyl naphthyl sulphate flouates, sulphonated higher aliphatic alcohols, amines or acid amides, long-chain esters derived from ultrium sulphonate esters, sulphated or sulphonated fatty acid esters, petroleum sulphonates, petroleum sulphonates, polyoxyethylene sulphonates, petroleum sulphonates isoolylfluol and nonylphenol) and polyoxyethylene derivatives of higher moieties derived from fatty acids and textanhydrides (e.g. sours). Preferred dispersion formulations are methylcellulose, polyvinyl alcohol, ultriummagnesium sulphonate, polymeric polyvinyl alcohol sulphonates, ultrifluorosulphon sulphonate and polymethylcylisulfonate sulphonate.

Powdered powders are water dispersible compositions comprising at least one active ingredient, an inert solid carrier and at least one wetting and dispersing agent. Inert solid fillers are usually of mineral origin, such as natural clays, diatomaceous earth, synthetic derived from silica and the like. Examples of such fillers include calcium nitrate, attapulgite clays, and synthetic magnesium silicate; The compositions of the present invention in the form of wettable powders usually obtain from about 0.5 to 60 parts (preferably from 5 to 20 parts) of the active ingredient, from about 0.25 to 25 parts (preferably from 1 to 15 parts) of the wettable component. from about 0.25 to about 25 parts (preferably from about 1.0 to about 15 parts) of the dispersant and from about 5 to about 95 parts (preferably from about 5 to about 50 parts) of an inert solid filler. If desired, 0.1 to 2.0 parts of a solid inert filler may be replaced by corrosion inhibition, a foam preventive, or both.

Other formulations include dust concentrates containing from 0.1 to 60% by weight of the active ingredient in a suitable filler. These dusts may be diluted for use to a concentration in the range of about 0.1 to 10%.

Aqueous suspensions or emulsions can be prepared by mixing an aqueous salt of the water-insoluble active ingredient and emulsifying the composition until uniform distribution is achieved and then deepening to obtain a stable emulsion of very fine discrete particles. The resulting concentrated aqueous suspension is characterized by an extremely small particle size, so that when diluted and sprayed, they are covered very uniformly. Suitable concentrates of these formulations include:. about 0.1 to 60%, preferably 5 to 50%, by weight of the active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent.

In another form of aqueous suspension, the water-immiscible herbicide is encapsulated to form a microencapsulated phase dispersed in the aqueous phase. In one embodiment, small capsules are prepared by bringing together an aqueous phase comprising a lignin sulfonate emulsifier, water-insoluble chemicals, and polymethylene polyphenylisocyanate. The water-immiscible phase is dispersed in the aqueous phase and then the multifunctional amine is added. The isocyanate and amine derivative react to form a solid urea coating around the particles of water-insoluble chemical, forming microcapsules. Typically, the concentration of the microencapsulated material is in the range of 480 to 700 g per liter, preferably 480 to 600 g per liter, based on the total composition.

Concentrates are usually solutions of the active ingredient in water-immiscible or water-miscible solvents to a limited extent, together with a surfactant. Suitable solvents for the active ingredients of the invention include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible esters or ketones. Other very strong liquid concentrates may be prepared by dissolving the active ingredient in a solvent and then diluting, for example, with kerosene, to a spray concentration.

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

Granules are formulations of physically stable particles which contain the active ingredient adhered or deposited on the basis of inert finely divided filler particles. To facilitate leaching of the active ingredient from the particles, a surfactant may be present in the composition, for example some of those listed above. Natural clays, pyrophyllite, illite and vermiculite are examples of possible groups of special mineral fillers. Preferred fillers are porous, preformed particles having absorbent properties, such as preformed and pro-coated attapulgite particles or heat expanded vermiculite particles and finely divided clays such as kaolin, hydrated attapulgite or bentonite clays. These fillers are sprayed with or mixed with the active ingredients to form herbicide granules.

The granular compositions of the present invention may contain from about 0.1 to about 30 parts, preferably from about 3 to 20 parts, by weight, per 100 parts by weight of clay and 0 to about 5 parts by weight of surfactant per 100 parts by weight. clay particles.

The compositions of the present invention may also contain other ingredients such as fertilizers, other herbicides, other pesticides, preservatives and the like used as adjuvants or in combination with any of the adjuvants described above. Chemicals suitable in combination with the active ingredients of the invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like as mentioned below.

Heterocyclic nitrogen / sulfur derivatives

2-chloro-4-ethylamino-6-isopropylamino-sym-triazine

2-chloro-4,6-bis (isopropylamino) -symmetris-1-azine

2-chloro-4,6-bis (ethylamino) -sym-triazine

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

3-Amino-1,2,4-triazole

6,7-dihydrodipyrido (1,2-a: 2 ', 1'-c) pyrazidinium salt

5-Bromo-3-isopropyl-6-methyluracil

1,1'-dimethyl-4,4'-bipyridinium compound

Ureas

N * - (4-chlorophenoxy) phenyl-N, N-dimethylurea

N, N-dimethyl-N- (3-chloro-4-methylphenyl) urea

3- (3,4-dichlorophenyl) -1,1-dimethylurea

1,3-dimethyl-3- (2-benzothiazolyl) urea

3- (p-chlorophenyl) -1,1-dimethylurea

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

Carbamates / thiolcarbamates

2-chlorallyl (diethyldithiolcarbamate)

S- (4-chlorobenzyl) -N, N-diethylthiocarbamate sopropyl N- (3-chlorophenyl) carbamate

S-2,3-dichlorallyl (N, N-diisopropylthiolcarbamate / ethyl) N, N-dipropylthiolcarbamate /

S-propyl (dipropylthiolcarbamate)

Acetamides / acetanilides / anilines / amides

2-chloro-N, N-diallylacetamide

N, N-dimethyl-2,2-diphenylacetamide

N- (2,4-dimethyl-5 - [[(trifluoromethyl} sulfonyl) amino] phenyl) acetamide

N-isopropyl-2-chloroacetanilide *, 6'-diethyl-N-methoxymethyl-2-chloroacetanilide ^> -methyl-6'-ethyl-N- (2-methoxy-2-propyl) -2-chloroacetanilide alpha, alpha, alpha -trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine

N- (1,1-dimethylpropinyl) -3,5-dichlorobenzamide

Acids / esters / alcohols 2,2-dichloropropionic acid 2-methyl-4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid methyl [2- / 4- (2,4-dichlorophenoxy) phenoxy / propionate] 3-amino-2-acid 5-dichlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid 2,3,6-trichlorophenylacetic acid N-1-naphthylphthalic acid sodium-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoyl oát

4,6-dinitro-o-sec-butylphenol

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

Ethers

2,4-dichlorophenyl-4-nitrophenyl ether 2-chloro-alpha, alpha, alpha-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether

227326 Miscellaneous fabrics

2,6-dichlorobenzonitrile methanesonic acid monosodium salt methanesonic acid disodium salt

Fertilizers suitable in combination with the active ingredient are, for example, ammonium nitrate, urea, potash and superphosphate. Other suitable ingredients include materials in which the plant organism roots and grows, such as compost, manure, humus, sand, and the like.

The herbicidal compositions of the types described above are exemplified in several illustrative embodiments below.

I. Emulsifiable concentrates Percent weight A. Compound of Example 1 / 50.0 a mixture of calcium dodecylbenzenesulfonic acid and polyoxyethylene ethers (e.g. Atlox® 3437F) 4.85 calcium dodecylbenzenesulfonate (FloMo 60H) 0.15 Cg aromatic solvent 45,00 100.00 B. Compound of Example 4 85.0 mixtures of calcium dodecylsulfonic acid and alkylaryl polyether alcohol 4.0 an aromatic hydrocarbon solvent of 9 carbon atoms 11.0 100.0 C. Compound of Example 6 5.0 Mixture of calcium dodecylbenzenesulfonic acid and polyoxyethylene esters (for example, Atlox 3437F) 1.0 xylene 94.0 100.0 II. Liquid concentrates Percent weight A. Compound of Example 4 Xylene 10.0 90.0 100.0 B. Compound of Example 5 85.0 dimethylsulfoxide 15.0 100.0

II. Liquid concentrates C. Compound of Example 6 Percent weight 50.0 50.0 100.0 N-meeyypyrroli don D. Compound of Example 7 5.0 ethoxylated castor oil 20.0 Riodamine B 0.5 dieetylforeeeid 74.5 100,0 ' III. Emulsion Percentage of moisture content A. The compound of Example 12 polyoxyethylene / polyoxypropylene block 40.0 copolymer with butanol (eg Tergitol ^R XH) 4.0 water 56.0 100.0 B. Compound of Example 13 Polyoxyethylene / Polyoxypropylene Block 5.0 copolymer with butanol 3.5 water 91.5 100.0 IV. Wettable dusters Percentage of mass A. Compound of Example 1 25.0 III) sodium osulfonate 3.0 Sodium amorphous N - methyl - N - ooeyltaurate (synthetic oxide 1.0 silicon) 71.0 100.0 B. Compound of Example 12 80.00 natriiedioktylsulfosuccinate ', 25 calcium aminosulfonate amorphous (synthetic oxide) 2.75 silicon) 16.00 100.00 C. Compound of Example 13 10.0 sodium 3.0 Sodium N-methyl-N-oeyltaugate 1.0 kaolinite clay 86.0

100.0

V. Popraš

Percent weight

A. Example compound 72.0 attapulgit98.0

100.0

B. Compound of Example No. 860.0 montmorillon t40.0

100.0

C. Compound of Example 930.0 bentonite 70.0

100.0

D. Compound of Example No. 101.0 diatomaceous earth99.0

100.0

VI. Granules Percentage by weight

A. Example Compound No. 115.0 granulated attapulgite (20/40 meeh) 85.0

100.0

B. Compound of Example No. 630.0 diatomaceous earth (20/40) 70.0

100.0

C · Example compound · 120.5 bentonite (20/40) 99.5

100.0

D. Compound of Example No. 135.0 pyrophyllite (20/40) 95.0

100.0

VII. Microcapsules

Percent weight

A · Compound of Example 1 encapsulated in a polyurethane coating 49.2 sodium lignosulfonate (e.g., Reax 88 ^ B) 0.9 water49.9

100.0

B. Compound of Example 12 Encapsulated in a Polyurea Wave Coat of Potassium Lignosulfonate (e.g.

Heex ^R C-21) 0.5 water 89.5

100.0

VII. Mikr eaves βί- Percentage of hmoonoot ο. Compound of Example 13 encapsulated in a polyurea container 80.0 Magnesium sulphate (eg Treax ^R LTM) 2,0 water 18.0 100.0

When operating in accordance with the present invention, an effective amount of the acetanilides of the present invention is applied to the soil containing the plants or is introduced into the aqueous medium in any conventional manner. The application of the liquid particle to the soil can be carried out by conventional methods, for example by means of a machine sprayer, a squeegee sprayer, a hand sprayer and a sprayer. The compositions may also be used from aircraft such as dusting or spraying because of their efficacy in small doses. The application of the herbicidal compositions to the aquatic plants is usually accomplished by adding the compositions to the aquatic environment in an area where the suppression of aquatic plants is desired.

It is an effective moiety! The compounds according to the invention at the site of occurrence of undesirable plants are of fundamental importance and are critical to the practice of the invention. The exact amount of active ingredient to be used depends on various factors, including the species of plant, the stage of their development, the type of soil and its condition, the amount of rainfall and the particular species used. For selective pre-emergence application to and from a plant or soil, a dose of from 0.02 to about 11.2 kg / ha, preferably from about 0.04 to about 5.60 kg / ha - or preferably from 1.12 to - 5.6 kg / ha of acetanilide. In some cases, lower or higher doses may be required, and those skilled in the art can readily determine the optimum composition of the composition, which can be used in any particular case, based on the above description and the examples above.

The term soil is used in its broadest sense to encompass all common soils as defined in the New Iotematiooa Substance, second edition, not abbreviated (1961). Thus, the term refers to any substance or environment in which vegetation may be rooted and grow and make the soil more dense, but also compote, manure, mud, humus, sand and the like, adapted to promote plant growth.

Although the invention is described with respect to specific moodfications, the details are not intended to be limiting except for the scope encompassed by the following subject matter of the invention.

Claims (1)

OBJECT OF THE INVENTION i. A herbicidal composition comprising an adjuvant and an herbicide of an effective amount of a compound of formula (I) 5. ', C II CICH ₂ C N / CH ₂ OR ^R 1 '[O] - ^CF 3 (I) where R is alkyl of 1 to 5 carbon atoms or alkoxyalkyl of β-1 to 5 carbon atoms or alkenyl β of 2 to 5 carbon atoms or alkynyl of 2 to 5 carbon atoms, and R 1 is hydrogen, methyl or ethyl, with the proviso that when R 1 is hydrogen, R is iaopropyl and when R 1 is ethyl, R is ethyl, n-propyl or isopropyl.