CS223996B2 - Herbicide means - Google Patents

Abstract

N-alkyl-2-haloacetanilide compounds, herbicidal compositions containing said compounds as the active ingredient and herbicidal method of use in various crops, particularly, soybeans, cotton, peanuts, rape, bush beans, etc. The herbicides herein are particularly effective against the hard-to-kill annual weeds Texas panicum, itchgrass, wild proso millet, alexandergrass, red rice, shattercane and seedling johnsongrass.

Description

(54) Herbicidal product

The invention relates to 2-haloacecalides and their use in agrochemistry, for example as herbicides. The art of this invention includes certain 2-haloacetane data which may be unsubstituted or substituted by many different substituents on the nitrogen atom of the anilide moiety and on the anildo ring, including alkyl, alkoxy, alkoxyalkyl, halogen and other sub-substituents.

With the compounds of the invention which are characterized by a methyl or ethyl sub-substituent on the nitrogen atom of the anildd ring and an alkoxy group in one ortho position and a methyl group in the longer ortho position, the closest prior art U.S. Patents 3,268,584, 3,442,945, 3,773 U.S. Pat. Nos. 3,773,492 and 4,152,137 disclose generic formulas of herbicidally active compounds which, in a broad sense, include compounds of the invention. However, only the propachhor, i.e., N-isoproppl-2-chloroacetate and Clide, a known commercial herbicide, is mentioned of the N-alkyl-substituted-2-haloacetyls specifically mentioned in either U.S. Patent 3,773,492 or 4,152,137. none of the patents discloses propachlor herbicidal activity. U.S. Pat. No. 2,863,752 (Re 26,961) discloses propachlor-related compounds (not specifically named C) and homologues and analogs thereof. Of the compounds within the scope of U.S. Patent 2,863,752, propachlor has been found to have the greatest herbicidal activity and has therefore been established as a commercial herbicide. The aforementioned U.S. Patent 2,863,752 discloses that the compounds therein may be used as low as possible, such as 1.12 kg / ha; however, as shown in Example IV, the experimental data limit application rates from 5.6 kg / ha and even to 28 kg / ha. In addition, N-ethyl-2-chloroacetane chloride in said U.S. Patent 2,863,752 is a particular feature; U.S. Pat. No. 4,137,070 discloses that the compound (Example 406 in U.S. Pat. No. 4,137,070) is an antidote to the EPTC herbicide. In contrast to the foregoing compounds disclosed in U.S. Patent 2,863,752, the compounds of the present invention are highly potent selective herbicides for difficult-to-control weed species at application rates well below 1.12 kg / ha, for example in the range below 0.07 kg / ha.

Other compounds which are structurally supported by the compounds of the invention, other than propachlor and its related compounds, are probably those listed in the aforementioned U.S. Patents 3,268,584 and 3,442,945. In particular, Example 13 of the aforementioned U.S. Patent 3,268,584 discloses N-t-butyl. -2-octoxy-2-chloroacetalide and Example 67 of U.S. Pat. No. 3,442,945 discloses 2'-methoxy-6'-tert-butyl-2-chloroeaallide. Thus, propachlor differs from the compounds of the invention in the kind of sub-substituents at two positions, i.e. in both ortho-positions of the molecule, as well as in the alkyl group attached to the nitrogen atom.

Example 13 in FIG. the above-cited U.S. Patent 3,268,584 differs in the type of sub-substituent in one ortho-position, in an alkoxy group in another ortho-position, in an alkyl group attached to a nitrogen atom; Example 67 in the cited U.S. Patent 3,442,945 differs from the compounds of the invention in the type of sub-substituent attached to the nitrogen atom and in the alkyl and alcohol groups attached at the ortho positions of the anildd residue.

U.S. Pat. No. 4,146,387 discloses 2-haloaliphatic anilide compounds which may be substituted with alkyloxy groups having nitrogen atoms and in both ortho positions. Polle U.S. Pat. Nos. 4,146,387 are described as known herbicides of the type disclosed, for example, in the aforementioned U.S. Patents 3,442,945 and 2,863,752, including propachlor.

The above-mentioned U.S. Patent 3,268,584 discloses some data relating to the herbicidal activity of the above-mentioned substances having a chemical structure very close to the compounds of the invention and some other data relating to the minerals and analogues of the less pale substances of the invention. While these data closest to the compounds of the invention show herbicidal activity against various weeds, they do not disclose any data on any compound in the additional and / or continuous control of difficult-to-control annual weeds such as Texas panic, R < tb > Extracts and panic moths, toryma ruřipogu, Sorghi bLcHor, and Halep weed seedlings while destroying or altering the growth of other harmful perennial and annual weeds such as the polygons (Polygon hydrooipee). , white moth, furrow, peri, bloody dew and hedgehog.

A very advantageous and no property of herbicides is their ability to maintain herbicidal activity over a longer period of time (the longer the more preferably) during the growing season of the crop. Many herbicides known in the art have the ability to sufficiently control weeds for only 2 or 3 weeks, or in some more preferred cases, perhaps up to 4 to 6 weeks, until the substance loses its effective phytotoxic property. One of the disadvantages of most prior art herbicides is their relatively short soil life.

Another disadvantage of some of the prior art herbicides, somewhat related to the soil life of herbicides in normal soil, is their susceptibility to leaching into the soil, resulting in a loss of herbicidal effects in high rainfall, detecting many herbicides.

A further disadvantage of many of the heretofore known herbicides is the sweeping of their ingestion on certain types of soil, i.e. while certain herbicides are effective in soils containing small amounts of soil. organic substances are ineffective in soils with a high organic content. substances or vice versa. It is therefore preferred that the herbicide be effective in all soil types within the range of light organic soil to heavy clay soil and fertilized soil. . ’

Another day. the disadvantage of many of the prior art herbicides is that they are confined to a certain effective method of application, i.e. irkemeegent topical application or, for example, a method of applying the herbicide before sowing by incorporation into the soil. It is highly desirable that the herbicide be applied. in each way, by topical application or by incorporation into the soil before sowing.

Finally, a certain disadvantage of some herbicides is the necessity of adhering to special handling with them due to their toxicity. Thus, a further requirement is that the herbicide be safe in miaiipuacc.

It is therefore an object of the present invention to provide a group of compounds with herbicidal activity which outperforms the abovementioned compounds and their advantages are multiplied.

It is an object of the present invention to provide herbicides that selectively control hard-to-control annual weeds such as Texas panic, Rootbush exaCtctc, Panic millium, Brachharic plcntaginec, Oryza rufipogon, Sorghum bicolor, and sorghum seedlings. , and non-growing crops that will crush many crops such as soybeans, cows, peanuts, rapeseed, bush beans, alfalfa and / or vegetables.

It is a further object of the present invention to provide an extension of the herbicidal activity time in the soil up to at least 12 weeks.

A further object of the present invention is to provide herbicides that are resistant to leaching and dilution caused by extreme humidity, for example in high water precipitation.

It is a further object of the present invention to provide herbicides which are effective in a wide range of soil types, for example from light-medium organic soils of heavy clay and fertilized.

Another advantage of the herbicides according to the invention is the availability of various methods of application, i.e., topical application and application by incorporation into the soil before sowing.

Finally, the advantage of the herbicides according to the invention is that they are safe and do not result in particular madipacification.

The foregoing and other objects of the invention will become more apparent from the detailed description set forth below.

The present invention relates to herbicidally active compounds, to herbicidal compositions containing them as an active ingredient and to a method of controlling said preparations in various crops.

It has now been found that a selected group of 2-halo-ethyl-acetyls having a particular β-α-β-α-β-β-α-β-β-β-α-β-β-β 2 -propyl chloride. Cyclic groups on nitrogen atoms and in one position of the ortho-cyclic radical and certain alkoxy groups in another ortho-pulse, has unexpected and outstanding herbicidal properties against herbicides known to date, including compounds very close to these compounds.

An essential feature of the herbicidal formulations of the present invention is their ability to control many weed species, including weed fungi with conventional herbicides, and in addition many weed species which have unequivocally and / or collectively escaped control using only one group of known herbicides. This is due to many crops including soybeans, cows, peanuts, rapeseed, bush beans, alfalfa and others. While the known herbicides are effective in controlling various weed species which sometimes contain weeds, however, the unique herbicides of the present invention have been shown to be effective in controlling or significantly controlling many resistant weeds, particularly annual weeds such as Texas panic. Panicum miliaceum, Brachharic plcntcginec, Oryza rufppogon, Sorghum bcolor, alternatively hippopotamus dumbbell, concurrent control and / or crop of other less resistant perennial and annual weeds.

The compounds of the invention have the general formula

О

SMELL. С R ir

where it means

R methyl ethyl ·,

R 1, C 1-6 alkyl, allyl groups,

R 1 is methyl, ethyl or tert-butyl, carbide methyl, and R is or meta-polize methyl, pyridine, with the proviso that when R is ethyl, R is n-bityl, R 8 is methyl, and R 3 is oid when R3 is methyl, R and Rg are also methyl and R is iipinyl or n-bityl when R3 is an O and R and Rg are only methyl, R1 is ethyl, n-propyl, iipinyl, n-bityl, isibxtyl, sec. tatyl, n-pennyl, isipennyl, 2-methyl-1-thityl, 1-meetlpenyl, 2-ethylpeniyl or 1,3-aminoethyltatyl, when R 8 is ethyl, R is methyl and R 1 isipripyl, and when R 8 is tert-butyl. and Rj will only mention meeyl.

The advantages of the invention are as follows:

N meetl- ^{2'--i8opnntyllKy} б * -eenyl 2-chllΓjceeajilid,

N-methyl-2'-n-pentyl-6'-methyl-2-chloroacetate,

Mmtyl- ^N-2 ' -N-o-butixy '-eeeyl ^2-chllr, jcntjIi.lid, -mey ^ ^{1-2' to} sn. ^b ltl:) qг-6'-ee ^{e- l} - ^2- chllcejce ^e tji ⁱ id,

N-Eeyl-2'-n-butyloxy-6'-methyl-2-chloroacetate,

N-methyl-2'-18-chloro-16'-4'-ethyl-2-thietylethyllide,

N-Methyl-2'-isopropylbutyl-6'-ethyl-2-chloroacetate, N-methyl-2'-chloro-1'-ethyl-2-ethyl-2-chloroacetate.

The use of the compounds according to the invention is to be found in the formulations of the active slags of the herbicidal compositions and to make them useful as pipsans.

The substances according to the invention can be prepared in many ways. For example, this may be accomplished by N-alkylation involving the addition of 2-halo-2-halogenoacetate with an alkaline alkalinizing agent. The N-alkali piston is described in Examples 1 and 2.

Example 1

Ex popistjp přípravt one of výhidných-slivCen-N-2-nmtyl * -i-butlxy-6 ^from 2--eetyl chiiracetam ϋάυ · When the piston pouteje jaki jlkyljCní přípraoě agent to N-alkyl-2-chlir aceetiadlidt of idpoiídeaícíhi sectamethylsulfate.

4.9 ^g (0.02 Mo ^{i) 2} -i- ^b u ^t l ^χy -б'-eetyl- -chllrjcctaailidu ^2, 2.6 ^g (0.02 moi) dimmeyleuLfV * ·· 2 rg trietybbenzyjmmlιni \ The mixture was mixed with 250 ml of methyl chloride. At a temperature of 10%, one milliliter of 50% 50% rhizhydroxide is added (100 ml) and the mixture is stirred at room temperature for 100 minutes and added to the organic layer. sees oystli magnesium hiřeCnatým and detStlujt of límcioé bank. a clear Cams ° ilinj and pulse ^ t ¹ Vart ¹³⁵ ° ^C at ⁰ ° 7 mmHg oe ^one above-t ^ kt 78% ^(4, 2 g) tterré with him ^ fc-hundred-ц; П of bezbarvit .átkt Warmify ¹ ttoí 41 to 42.5 ° C.

Analysis for C ^^ qCClCíí:

H, 7.44; Cl, 13.14. Found: C, 62.34; H, 7.49; Cl, 13.16. ‘

The product was oven as identification ^of N-methyl ^E-yl 2 '-n-butoxy-6'-mexyl - ^ - chloraaeteailid.

Example 2

To ehlszené mixture ⁽¹ 5 ° ^C), 2'-i- yloxy ^b u ^y - 6 * -Met ^yl -2- hloracetaa ^{e d i} ll u, ^{5.6 g (0} ° 22 mol), 4,0 g (0.024 mol) of diethyl sulfate and 2.2 g in 250 ml triyУblbenzylílinžmlbroeidu ^y Mee chloride was added in one portion 50 ml of 50% sodium hydroxide solution and the mixture is held for 5 min У Mie. 150 ml of water are added and the layers are separated. The organic layer was washed with water, dried over magnesium sulphate and then evaporated in a collar flask to give 4.1 g (66% yield) of a clear, ¹ ° C boiling point at ^0.05 mm Hg.

Analysis for CjHH CNNONO:

C, 63.48; H, 7.81; Cl, 12.44. Found: C, 63.50; H, 7.85; Cl, 12.48.

Product B iěentifi ^{yl about} b ^s i j and ^k of ^{the N} -yУ ^{yl-2'-6'-bžУlXl íaУ-yl-2-ehllracaУan and} l ^ie.

Example 1 to d 3 to 19 '

Basically stejrými manner as in Examples 1 and 2, under the same general conditions as poožití same reactants but substituting přisutým sek.anilědeí ldppl0ílějíeíhl allowing the obtaining of N-alkyd-alkylated end product is prepared by further N-meetl.-2-Hall ^g enrceУyniliěy of the above formula. These substances are listed in Table I.

Taauiuk I

Example Compound Empprický M.p. Analysis δ. vzortc (oo Hg) Element Calculated Loaded 3 N-meth ^{yl-2'-6-isopentoxr} 120 (0.05) C 63.48 63.38. -ethyl-2-chloroacetaailid ⁱⁿ 15 ^η 22 ^ΌΧΛν 2 H 7.81 7.80 Cl 12.49 12.44 4 N-meth ^{yl-2-n-propoxy y} i6 * -eetyl 2-chloracetaailid Ctą ° ₂ 130 (0.15) C H 61.05 7.09 60.88 7.12 C- 13.86 13.70 5 N-methyl-2'-3tk. buto ^ ló * - 0 H C1NO C 62.33 62.16 ethyl-2-chloroacctardide ^υ 14 _П 20 ““ 2 H 7.47 7.50 C- 13.14 13.10 6 N-methyl-2'-isopropoxy-6-ethyl-2-chloroacetaailide _{c) 3} h, ₈ Cino ₈ 127 (0.03) C H 61.05 7.09 61.05 7.09 C- 13.86 13.83 7 N-Methyl-2'-isopropoxy-6'- C _U H ₂₀ C1NO ₂ 105 (0.01) C 62.33 62.40 -lll-2-chlorocetanilide H 7.47 7.52 C- 13.14 13.03 8 N-methyl ^y -2 * -18obutox ^y l6 * - yy 14 ^ ¹ ¾ 115 (0.03) C 62.33 62.32 -et У ^у 1-2-с hlné t УаП. -id H 7.47 7.49 Cl 13.14 13.12 9 N-meth ^yl-2'-6'-yl meeox Уero.- C ₁₄ H ₂ oC1KO ₂ 99 to 100 C 62.33 62.25 buy ^γ -2-chloroacetimilide (У. У.) H 7.47 7.51 C- 13.14 13.14 10 Ν-eeУу1-2 * -yyoxl-6 * -eet ^y l- C _{2 H) 6 2} ciK0 57 to 58 C 59.63 59.63 -2-chloroacetylilide (У. У.) H 6.67 6.71 C- 14.67 14.67

continuation of Table

Example no.

Compound

N-Getyl-2- (1-methylpentoxy) -6-methyl-2-chloroacetanilide

^{N-methyl-2'-n-pentyloxy-6-methyl-2} * -chloracetánilid

N-Getyl-2'-n-propoxymethyl-6-methyl-2-chloroacetanilide

N-methyl-2 * -isopropoxy-5 *, 6 * -dimethyl-2-chloroacetanilide

N-methyl-2 * -n-butoxy-6 *, 6'-dimethyl-2-chloroacetanilide

N-methyl-2'-butoxy-5,6'-dimethyl-2-chloroacetanilide

N-Ethyl-2 * - (2-methylpentoxy) -6-methyl-2-chloroacetenilide

N-qetyl-2 * - (2-methylbutoxy) -6-methyl-2-chloroacetanilide

N-Igethyl-2 '- (1,3-dimethylbutoxy) -6-methyl-2-chloroacetanilide

Empirical formula T. v. ° C (from Hg) Analysis * Element Calculated Found c, ₆ hrs ₂₄ cino ₂ 120 (0.08) C H 64.53 8.12 64.42 8.15 Cl 11.90 11.89 (c _{) 5} hours ₂₂ hours ₂ 125 (0.12) c H 63.48 7.81 63.36 7.81 Cl 12.49 12.50 c _u h ₂₀ cino ₂ 120 to 160 (0.05 to 0, C 1) H 62.33 7.47 61.59. 7.51 N 5.19 - C ₁₄ ^h ₂₀ C1NO ₂ 121 (0.01) c H 62.33 7, '47 62.65 6.84 Cl 13.14 13.17 106 C 63.48 63.54 ^ъ 15 22 ^{п ихли} 2 (0,07) H 7.81 7.80 Cl 12.49 12.48 C15 ^ 22 ^ 10NOj 46 to 47 C 63.48 63.56 (i.e.) H 7.81 7.82 Cl 12.49 12.52 C C1NO ~ 116 C 64.53 64.59 1 6 24 ^VJJ ^ ^U 2 (0,03) H 8.12 8.11 Cl 11.90 11.96 120 C 63.48 63.53 ^u 15 ^η 22 ^υχαυ 2 (0,06) H 7.81 7.85 Cl 12.49 12.45 ^C 16 ^H 23 ^C1KO 2 128 (0.15) c H 64.53 8.12 64.49 8.14 Cl 11.90 11.89

The secondary anilides which are used as starting materials in the above-mentioned N-alkylation process are prepared by known methods, for example, by halogenacylation of the corresponding aniline. For example, the secondary anilide used in Example 1 is prepared as follows:

27.4 g (0.0153 mol) of 2-n-butoxy-6-methylaniline in 250 ml of methylene chloride are stirred vigorously with a solution of 10% sodium hydroxide (0.25 mol) and a solution of 17.4 g is added over 30 minutes. (0.0154 mol) of chloroacetyl chloride in methylene chloride. The temperature is maintained between 15 and 25 ° C by external cooling. The reaction mixture was then stirred for an additional 60 minutes. The layers were separated, the methylene chloride layer was washed with water, dried and evaporated in vacuo to give 28.3 g of a white solid, mp 127-128 ° C.

Analysis for

C ₁₃ H ₁₈ ^C ₂ 1№ calculated: 61.05% C, 7.09% H, 13.86% Cl found: 61.04% C, 7.08% H, 13.86% Cl.

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

The secondary anilides used as starting materials in Examples 3 to 19 were prepared in a similar manner.

The primary amines used to prepare said secondary anilides can be prepared by known methods, for example by reducing the corresponding 2-alkoxy-6-alkyl-nitrobenzene in ethanol using platinum oxide as a catalyst.

As mentioned above, the compounds of the invention have proven to be potent herbicides, in particular pre-emergence herbicides, although they have also shown post-emergence activity. Preemergence tests of the compounds of the invention include both greenhouse and field tests.

In TESTEC ^h in a glass, the herbicide is applied ^{BU3 p} ovrc But watch · ^h after zaseeí seeds or vegetative propagules or by incorporation into určiéého eenoství soil, which is applied as a cover layer over the test seeds in pre-seeded pots. In field tests, the herbicide is introduced into the soil before sowing (E1.1), i.e. the herbicide is applied to the soil surface, then mixed in the soil by suitable means, and then the soil is planted with the seeds of the crop.

The method of surface application of the herbicide used in the greenhouse tests is carried out as follows:

Fill containers such as 24.13 cm x 13.34 cm x 6.99 cm aluminum troughs or 9.53 cm x 9.53 cm x 7.62 cm plastic mugs with drain holes in the bottom along Riay's dust-drenched soil, which is then packed to a distance of 1.27 cm from the top of the vessel. The flasks were then planted with seeds of the plant species to be tested and the surface was then covered with a 1.27 cm layer of test soil. The herbicide is then applied to the soil surface with a strip spreader at a rate of 187 L / ha and a pressure of 2.11 kg / cm 2. Each container is irrigated from above with 0.64 cm of water, placed in a greenhouse and watered from below as needed.

Alte] ιnatv ^<thia irrigation method can be omitted above. Evaluation of the herbicidal effects is performed about three weeks after treatment.

The herbicide trial by incorporation into the soil in greenhouse tests is performed as follows:

The oraice is put into the clay mugs and tastes of quality and packed to a depth of three eighth to one half of an inch from the top of the mug. A predetermined number of seeds or vegetative shoots are placed on the soil surface. of different weed species. The soil required to replenish the containers after planting the seeds or the shoots is weighed into the container. This soil and the known active ingredients. In the dissolved form or in the sowing powder suspension, they are intensively mixed and used to superimpose the soil in the prepared containers. The containers thus prepared are irrigated from above in a dose corresponding to 0.64 cm of precipitation, and then irrigated from below, as necessary, with sufficient moisture for germination and growth. In an easy way, the irrigation is top-down. The effect is performed about 2 to 3 weeks after sowing and herbicide treatment.

Tables II and III summarize the results of the pre-gegeetic activity tests of the compounds of the invention; in these tests, the herbicides were applied by incorporation into the soil and only bottom irrigation was performed; the (-) sign means that the plant has not been tested. The heerbididal effect was evaluated on a porn scale based on the percent damage to each cultivated species. Grades are defined as follows:

-ž-kontrolv- Stucrn 0 to 24 0 25 to 49 1 50 to 74 2 75 to 100 3

In the group of tests whose results are shown in Table II, the plants indicated in the table were used as follows:

And Cirsuma arvense

B beet

C Aiujilot kheophraski

D povíjniee

E grades

F Polygone hydropiper

G yellow flat

H reptiles

Even sorghum

J Broous lecOouon

K ježaOka

Table II

Pnioergintně

The compound of Example no. Og / ha AND (B) D C ruhy r D E os t F li n G H AND J TO 1 11.2 3 3 3 3 3 3 3 3 3 3 3 5.6 3 2 2 3 3 3 3 3 3 3 3 2 11.2 3 1 1 2 3 3 - 3 3 3 3 5.6 3 0 1 1 3 3 - 3 1 3 3 3 11.2 3 2 3 3 3 3 3 3 3 3 3 5.6 3 1 3 2 3 3 3 3 2 3 3 4 11.2 3 2 3 3 3 3 3 3 3 3 3 5.6 2 1 3 2 3 3 3 3 3 3 3 5 11.2 3 2 3 3 3 3 3 3 3 3 3 5.6 3 2 3 3 3 3 3 3 3 3 3 6 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 7 11.2 3 3 3 3 3 3 3 3 3 3 3 5.6 3 1 2 3 3 3 3 3 3 3 3 8 11.2 3 2 3 3 3 3 3 3 1 . 3 3 5.6 3 2 2 2 3 3 3 3 3 3 3 9 11.2 3 0 3 3 3 3 3 3 3 3 3 5.6 3 0 2 3 3 3 3 3 3 3 3 1.12 2 0 2 3 3 1 2 3 1 3 3 10 11.2 2 2 3 3 3 3 3 3 3 3 3 - 5.6 3 1 3 2 3 2 2 3 2 3 3 11 11.2 3 2 and 3 3 3 3 3 3 3 3 5.6 2 2 2 2 3 2 3 3 3 3 3 12 11.2 3 2 2 3 3 3 3 3 3 3 3 5.6 3 1 1 3 3 2 3 3 2 3 3 13 11.2 - 2 2 2. 3 3 3 3 - 3 3 5.6 - 1 1 1 3 3 2 3 - 3 3 14 11.2 3 1 3 3 3 2 3 3 3 3 3 5.6 0 0 2 3 3 2 3 3 1 3 3 15 Dec 11.2 1 1 2 3 3 3 3 3 3 3 3 5.6 2 0 1 2 2 1 3 2 0 3 3 16 11.2 3 1 1 2 3 3 3 3 3 3 3 5 ^, 6 2 0 0 0 3 2 3 3 3 3 3 17 11.2 3 1 1 0 2 3 3 3 3 3 3 5.6 3 0 2 2 3 2 3 3 3 3 3 18 11.2 3 2 3 3 3 3 3 3 3 3 3 5.6 3 2 2 3 3 3 3 3 3 3 3 19 Dec 11.2 3 1 2 2 3 3 3 3 2 3 3 5.6 3 0 2 2 3 3 3 3 1 3 3

These compounds have been tested for the following plant species as described above:

L

M

N

O

P

(B)

Q

D

R

E

E

C

J s

TO

T Soybeans Sugar Beet Wheat Rice Sorghum Beet Braid Morning Glory

Sesbania exaltata sorrel

Polygons hydropiper Abuttlon theophhasSi Bromus tectoum Panicum Spp. hedgehog dew

The results are shown in Table III.

Table III

Preemergent

Example compound kg / ha

No L

Second

Μ N O P B Q D of the plant

R EFCJSKT

5,6 33

1,12 23

0,28 02

0,06 01

0,01 00

0,006 00

5,6 12

1,12 02

0,28 01

0,06 00

0,01 00

5.6 23

1,12 13

0,28 12

0,06 01

0,01 00

0,006 00

5.6 2.3 ', 12 02

0,28 02

0,06 01

0,01 00

5,6 33

1,12 23

0,28 02

3 3 33

3 3 12

312

11312 o 0 01 o o o -0

3 3 11

3 3 01

2 2 0o

2 0 0o

1 0 0o

3 3 23

3 3 22

3 3 01

110 0 0 0 0 3. 01 o o 0 0o

3 3 33

3 3 13

3 3-1

113-0

0 0 0o

3 3 23

3 3 i3

2 311

3 33

3 33

33

122

0111

0110

3 33

3 33 o 3 o 3 o * o o oo

3 33

O 2 33

0 33

0 31 o 0 oo o 0 11

3 33

3 32

3 31

1 O'o

- 00 00

3 33

3 33

33

3 3 33

3 3 33

3 3 33 o 3 3 33

0 133

0 2 32

3 3 3-

3 3 30 3 3 301130 0 0 13 3 3 33

3 3 33

3 3 33

0 3 33

2 3 33

0 0 11

3 3 33

3 3 33

3 3 33

3 3 33

0 12 3

3 3 33

3 3 33

3 3 33 continued Table III

The compound of Example no. kg / ha L M N 0 P 0 r u h y r R o s tli n J with TO T (B) Q D E F C 0.06 0 1 1 2 2 0 0 0 3 3 3 1 2 3 3 3 0.01 0 0 0 0 0 0 0 0 1 1 1 0 0 1 3 3 0.006 0 1 0 0 0 0 0 0 2 1 1 0 0 0 1 2 6 5.6 3 3 3 3 3 2 3 2 3 3 3 3 3 3 3 - 1.12 2 3 3 3 3 1 2 2 2 3 3 2 3 3 3 - 0.28 0 2 1 3 3 0 1 1 2 3 2 2 3 3 3 - 0.06 0 1 0 0 0 0 0 0 1 3 1 0 3 3 3 - 0.01 0 0 0 1 0 0 1 0 1 1 0 0 2 0 3 - 7 5.6 1 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1.12 0 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3 0.28 0 2 3 2 2 0 2 2 2 3 2 1 3 3 3 3 0.06 0 2 1 1 1 1 0 3 2 2 1 1 1 3 3 3 0.01 1 1 0 1 0 0 0 1 1 0 0 0 1 0 2 3 0.006 0 0 0 0 0 0 0 1 2 0 0 0 1 0 2 2 8 5.6 2 3 3 3 3 1 2 3 3 3 3 3 3 3 3 3 1.12 0 2 2 3 3 0 2, 2 2 3 2 1 3 3 3 3 0.28 0 2 2 3 3 0 1 0 2 3 2 0 3 3 3 3 0.06 0 1 0 2 3 0 1 0 0 1 0 0 1 2 3 3 0.01 0 1 0 0 0 0 0 0 1 3 2 0 0 1 3 3 9 5.6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1.12 1 2 3 3 3 1 2 2 2 3 1 1 3 3 3 3 0.28 0 1 2 2 2 0 1 3 2 3 2 1 2 2 3 3 0.06 0 1 2 1 1 0 0 0 2 0 2 0 0 2 3 3 0.01 0 1 2 0 0 0 0 0 2 1 1 0 0 0 2 3 10 5.6 2 2 3 3 3 0 3 3 3 3 2 3 3 3 3 3 1.12 0 2 2 3 3 1 1 2 3 3 2 2 3 3 3 3 0.28 0 2 1 3 3 0 2 2 2 3 0 2 3 3 3 3 0.06 0 1 0 1 2 0 0 0 3 2 0 2 3 3 3 3 0.01 0 1 0 0 0 0 0 0 1 0 0 1 0 0 0 3 11 5.6 1 3 3 3 3 1 3 3 3 3 3 1 3 3 3 3 1.12 0 1 2 3 3 0 2 2 2 3 3 0 3 3 3 3 0.28 0 1 2 3 3 - 0 1 1 3 3 0 3 3 3 3 0.06 0 0 1 2 1 0 0 0 2 3 2 0 2 2 3 3 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 3 12 5.6 2 2 3 3 3 1 3 1 3 3 3 1 3 3 3 3 1.12 0 2 3 3 3 1. 3 2 3 3 3 1 3 3 3 3 0.28 0 2 3 3 3 0 0 0 1 .3 2 0 3 3 3 3 0.06 0 0 2 3 3 0 2 0 0 1 2 0 3 3 3 3 0.01 0 0 0 0 0 0 0 0 2 0 0 0 1 0 3 3 13 5.6. 1 2 3 2 '3 2 3 3 3 3 3 2 3 3 3 - 1.12 0 2 2 3 3 1 2 2 3 3 3 1 3 3 3 - 0.28 0 2 2 3 0 0 1 1 2 3 2 0 2 3 3 - 0.06 0 1 1 1 0 0 0 0 1 2 1 0 0 3 3 - 0.01 0 0 0 0 0 0 0 0 0 0 1 0 1 0 1 -

Continuing Table III

The compound of Example no. : kg / ha L M N 0 P Dr (B) u h Q y D ro R o S 1 E t i F n C J WITH TO T 14 5.6 3 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 1.12 2 3 2 3 3 0 2 4 4 4 4 2 3 3 3 3 0.28 2 2 2 2 3 0 2 3 2 2 2 1 3 3 3 3 0.06 0 2 1 2 1 0 1 2 1 2 2 0 2 2 3 3 0.01 0 1 1 1 0 0 1 1 1 1 0 0 0 0 2 3 0.006 0 1 0 1 0 0 1 1 1 1 0 0 0 0 1 3 15 Dec 5.6 2 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 1.12 .0 2 3 3 3 1 2 1 1 3 2 0 3 3 3 3 0.28 0 1 1 1 1 0 1 0 0 1 1 0 3 3 3 3 0.06 0 1 0 0 0 0 0 0 0 1 0 0 0 2 3 3 0.01 0 0 0 0 0 0 0 0 0 1 1 0 0 0 2 2 16 5.6 1 3 3 3 3 1 2 2 . 3 3 3 1 3 3 3 - 1.12 0 2 2 3 3 0 2 1 2 2 3 0 3 3 3 - 0.28 0 2 1 3 3 0 0 0 1 3 3 0 2 3 3 - 0.06 0 1 0 1 0 0 0 0 3 1 0 0 3 2 3 - 0.01 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 - 17 5.6 0 3 3 3 3 0 1 1 3 3 3 1 3 3 3 - 1.12 0 2 2 3 3 0 1 0 2 2 2 0 3 3 3 - 0.28 0 2 1 3 2 0 0 0 1 0 1 0 3 3 3 - 0.06 0 0 0 1 0 0 0 0 1 1 0 0 1 1 3 - 0.01 0 0 0 0 0 - 0 0 0 0 0 0 0 0 1 - 18 5.6 3 3 3 3 3 3 3 3 3 3 3 2 3 3 3 3 1.12 0 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3 0.28 0 2 2 3 3 0 2 0 2 3 2 1 3 3 3 3 0.06 0 2 0 0 2 0 2 0 0 2 3 0 3 3 3 3 0.01 0 2 0 0 0 0 0 0 0 0 - 0 0 0 3 3

The herbicides according to the invention have unexpectedly advantageous properties as pre-emergence herbicides, in particular in the selective control of difficult-to-control annual weeds, such as Texas panic, sorghum sorghum seedlings, Sorghum bicolor, Brachharia plantaginea less resistant perennial and annual weeds.

It has been found in various crops including soybeans, cotton, peanuts, rapeseed and bush beans that we have been able to control and increase the growth control of the above weeds by the substances according to the invention. In some tests, at different application rates, the herbicidal effect of sugar beet and pea cultivation is improved. However, certain crops, especially grass crops, are usually less tolerant to the herbicide of the invention than the above crops.

To illustrate the unexpectedly advantageous properties of the compounds of the invention, both absolute and relative, comparative tests were carried out in the greenhouse with substances having the closest chemical structure and known in the art. These substances are labeled as follows:

A. N-tert-Butyl-2-met (oχ-2-choor is detail) (Example 13, U.S. Patent 3,268,584).

B. 2'-terc.l: uιtyl.6 mnetoχy * 2-c ^{and h} lorjcetaaili. Example ^67, U.S. Pat. No. 3,442,945.

C. N-isopropyl-2-chloroacetanilide (common name propachlor). U.S. Patent 2,863,752 (Re Patent 26,961); Propachlor is disclosed in the above-cited US patents 3,773,492 n

n 4.152 137 n is an active ingredient of the commercial herbicide Ramrod, a trademark of Monsnnto Compacny.

In the following, the application rates of herbicides are referred to as GR? N GRg, these rates are expressed in kg / ha. GR4 defines a minimum herbicide dose by debarking 15% or less crop loss. GR4 defines a minimum herbicide dose resulting in 85% weed inhibition. The doses expressed as GR ^ and GRgj are used as a measure of possible commercial use. It will be appreciated, however, that suitable carbohydrate herbicides may exhibit a greater or lesser degree of plant damage, in measured meel.

Another criterion for the efficacy of a compound as a selective Hebricide is the selectivity factor (SF) for a herbicide in a given crop or weed. The factor sc1 is a measure of the ratio of resistance to one another. crop and weed damage, and is expressed by the ratios of GR GR / GRg, i.e. the dose of GR j refers to the crop being divided by the dose of qG5 relating to the weeds, both being in kg / ha. In the tables below, the teivativity factors are given in parentheses after the GR value for each weed; the term NS means teecionion. The marginal or problematic s ^ ^ ^! ^ Is indicated by the sign (-); an empty space indicates that the plant has not been tested in the test or that the plant is non-vermin.

Since the resistance of the crop to be grown and the ability to control weeds are mutually dependent, a brief discussion of these relationships, included in selective factors, is warranted. Generally, it is desirable that the crop resistance factors, i.e., tolerated amounts of herbicides, are high, as it is often desirable for various reasons, due to higher herbicide concetrations. On the contrary, it is desirable that the doses of herbicides that adequately control the weeds are mell, i.e. the herbicide has a high unit efficiency for economic and possibly ecological reasons. However, the small application rates of herbicides may not be sufficient to control certain weed species and they are sufficient. higher doses desirable. Thus, the best herbicides are those which control most weed species with not only the herbicide carrier and produce the highest degree of crop resistance, i.e. its tolerance. Thus, according to the above, selectivity factors express the quatitatiotic relationship between odoonosic crops and ppevel control. Regarding the sektion factors listed in the tables, the higher the numme value, the higher the herbicide selectivity for a given weed in the crop.

In the first comparative test, the results of which are shown in Table IV, the primary greenhouse potency of the compound of Example 1, a precursor compound of the invention, with important compounds known in the art - see compounds A, B and C, of selective herbicides for eating weeds commonly accompanying eoj beans. The data shown in Table IV were obtained for all compounds under the same conditions, ie by incorporation into the soil and initial irrigation from above; the data presented represent the averages of two replicate experiments for each compound. The compound of Example 1 was used in the form of two different samples. The weed species included in the test are indicated in the table by the following abbreviations: Texas panic (TR), Downy sorghum seedlings (SJG),. So hum hum bico T T (SCC, θγθοΙΊθγ ^ plantaginea (AG), Panic (W? M), Panic Dicstiflon (FP), Oryza, rufipogsn (RR) and RoStbosiic e ^ ltata (IG).

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Based on the data in Table IV, it can be found that it did not show any weed control. from the previously known substances, the herbicidal effect against any of the weeds in soybeans at a maximum application rate of 1.12 kg / ha, with the sole exception of the effect of compound C on panitomifloum. Here, too, the selection factor was one unit lower than that of the compound of Example 1. In contrast, the compound of Example I selectively destroyed every weed included in the test at extremely low application rates, while soybeans were resistant up to 0, 71 kg / ha. Of particular significance is the fact that the compound of Example 1 killed Halle sorghum seedlings, Sorghum bLcHor, Brachiaria plantaginea, Panic dichotomiflorum and Kottboeeia exaatata at doses of 0.07 kg / ha (minimum applied dose) or less, and also weed-controlling fungi, i.e. Texas. Panicas, Panicas miiaaeetm and Oryza rufipogon at doses of only 0.10, 1.14 and 0.18 kg / ha. Further greenhouse tests were performed to compare the mutual herbicidal activity of known A-C compounds with the compounds of Examples 1, 3-5 and 6-17, pre-surviving compounds of the invention. These tests were carried out as described above by incorporating the herbicide into the soil at application rates ranging from 0.07 to 1.12 kg / ha and initial irrigation from above followed by lower irrigation as needed. Vyhodnocen! was done 19 days after the US. The results of these additional tests are shown in Table V. The weed names are truncated similarly to Table IV and the selectivity factors are shown in parentheses after the indicated doses of GRqc for each weed.

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The data in Table V shows that, within the application rates of these tests, Compound A did not show a selective herbicidal effect against any tested soybean weed, Compound В showed only a partial selective herbicidal effect against Panic Dichotomiflores (not significantly resistant weeds) and Compound C it selectively killed only Panic dichotomlflorum and showed a partial herbicidal effect against Texas panic, Brachiaria plantaginea and Oryza rufipogon. With few exceptions - effects of substance C on Panic Dichotomlflorum (^ 35 0.28 kg / ha) and В on Brachiaria plantaginea and Panic Dichotomlflorum (UR ^^ 1.00 kg / ha) - none of the previously known substances tested from weeds under test at less than 1,12 kg / ha.

Except for isolated cases of action against certain weed species, this contrasts sharply with the effects of all the compounds according to the invention, which have shown unexpectedly suitable selective herbicidal effects against all weeds in soybeans. Only a few herbicidal activity was shown, for example in the effects of the compounds of Examples 8 and 17 against Oryza rufipogon, the compounds of Example 9 against Panic millium and Oryza rufipogon, the compounds of Example 14 against Panic mileacum and the compounds of Example 15 against Sorghum bicolor . Moreover, unlike the substances known to date (with the above exceptions), all the compounds according to the invention have killed all weeds at extremely low application rates ranging from no more than 0.56 kg / ha to less than 0.07 kg / ha, thus proving remarkable efficacy both in absolute terms with respect to highly resistant weed species (excluding Panic Dichotomlflorum) and in particular due to the inability of the closest known compounds in the art to control any of the weeds tested except the above exceptions.

Preferred compounds of the invention were further tested in the field to determine their selective pre-emergence herbicidal potency and soil life against annual weeds such as Texas panic, Aeanthospermum hispidum, and Richardie scebra in peanut cultivation (Florunner). The evaluation was carried out 4, 8 and 12 weeks after treatment (1 LAT) by topical application of the herbicides. The soil type was Dethan's sandy loam containing 1.3% organic matter, the results are shown in Table VI.

Table VI

Percent inhibition *

Weight kg / ha 4 WAT 8 WAT 12 WAT 4 WAT 8 WAT 12 WAT 4 WAT β WAT 12 WAT 8 WAT 12 WAT

Ex. 1 1.12 0 0 0 85 60 52 - 80 85 - 95 - 2.24 12 5 0 93 83 83 - 90 95 95 90 95 3.36 22nd 13 0 95 97 87 - 97 95 98 98 4.48 40 27 Mar: 21 100 ALIGN! 95 98 95 100 ALIGN! 98 100 ALIGN! 98 98 Ex. 2 1.12 0 0 0 82 58 62 - 80 80 - 90 - 2.24 3 3 0 90 88 87 95 95 90 95 95 100 ALIGN! 3.36 8 10 0 95 95 92 - 90 95 - 97 95 4.48 15 Dec 15 Dec 15 Dec 98 100 ALIGN! 100 ALIGN! - 100 ALIGN! 100 ALIGN! 98 95 Ex. 3 1.12 10 0 0 78 78 43 - 85 - - 85 70 2.24 15 Dec 10 0 92 87 70 - 88 - - 98 - 3.36 27 Mar: 13 0 95 93 88 - 95 95 - 98 95 4.48 37 27 Mar: 13 100 ALIGN! 97 90 - 97 95 - 98 100 ALIGN!

* through three attempts

The data in Table VI show that the compound of Example 2 selectively kills all three weed species in peanuts at doses ranging from 2.24 to 4.48 kg / ha up to 12 weeks after treatment. The compounds of Examples 1 and 3 also showed selective control of one or more of the weed species tested for up to 12 weeks at smaller application rates, which means that of the three test compounds, the compound of Example 2 had the highest level of safety in peanuts under this test. .

Further assays were performed to determine the relative potency of the compounds of Examples 1, 3, and 4 to Panic millium in soybeans up to 12 weeks after cell treatment by surface application (SA) or by incorporation of the herbicide into the soil prior to sowing (PPI). The soil used was a sand-aluminum type containing 1.7% organic matter. 6.35 cm rainfall occurred two days after treatment. The results of this test are shown in Table VII.

Table VII

Percentage inhibition ^a

Compound Rate kg / ha Soybeans beans Panicům miliaceum 3 VAT 8 ШТ 12 VAT 3 VAT 8  VAT 12 VAT SA PPI SA PPI SA PPI SA PPI SA PPI SA PPI Ex. 1 1.12 15 Dec 32 0 ’22 0 22nd 85 82 40 43 25 18 2.24 15 Dec 33 0 33 0 0 92 78 78 48 77 50 3.36 15 Dec 32 13 32 0 10 95 85 90 60 85 60 4,4S 33 50 20 May 30 8 23 98 92 85 78 78 70 Ex. 2 1.12 0 27 Mar: 0 8 0 0 85 73 60 57 25 20 May 2.24 15 Dec 37 0 25 0 5 92 75 68 53 72 43 3.36 22nd 40 7 27 Mar: 0 0 ’ 95 87 88 70 85 63 4.48 30 60 13 47 7 8 92 88 88 70 83 62 Ex. 3 1.12 8 15 Dec 5 10 0 0 95 85 68 55 63 10 2.24 15 Dec 22nd 7 18 0 0 95 85 80 67 58 47 3.36 22nd 25 10 18 0 0 95 80 82 50 82 42 4.48 22nd 43 15 Dec 33 0 30 95 90 90 78 85 58

^{and the} average of three replicates

The data in Table VII show that the dose of 3.36 kg / ha of each compound selectively kills Panic millium in soybeans at 3, β and 12 weeks after topical treatment. It follows that treatment of the crop with the compounds of the invention can provide long-term protection against Panicum millium, as it is a species whose germination and emergence increases progressively throughout the growth period. The greater degree of soybean damage when applied to the soil before sowing (PPI) by the herbicide is attributed to too deep and uneven insertion through the disc harrows and rainfall that occurred 2 days after treatment. In this test, more suitable herbicidal effects and crop resistance were obtained by topical application of the herbicide.

In another field test, the compounds of Examples 1, 3 and 4 were tested for herbicidal activity against particularly resistant annual weeds, sorghum seedlings both by topical application and by incorporation of the herbicide into the soil before sowing. This field test was performed on clay soil (58% clay and 3.1% organic matter). Evaluation was performed 4 and 8 weeks after treatment, the results are shown in Table VIII.

Table VIII

Percentage inhibition ^a

Soybean Sorghum seedlings

Compound Rate kg / ha 4 WAT 8 WAT 4 WAT 8 WAT PPI SA PPI SA PPI SA PPI SA Ex. 1 1.12 5 3 12 3 7 23 10 2.24 13 12 28 10 75 67 85 80 3.36 23 15 Dec 22nd 17 78 85 87 60 4.48 30 18 38 22nd 80 85 93 78 Ex. 2 1.12 10 3 13 5 17 25 0 23 2.24 22nd 13 13 7 47 67 70 60 3.36 28 18 22nd 15 Dec 70 82 85 78 4.48 32 22nd 32 23 78 78 90 68 Ex. 4 1.12 10 0 8 0 7 23 33 8 2.24 13 13 8 12 60 68 85 78 3.36 23 12 20 May 13 73 82 87 88 4.48 22nd 17 28 15 Dec 75 85 88 85

^{and the} average of three replicate trials

The compound of Example 4 selectively kills halibut sorghum seedlings in soybeans at a dose of 2.24 kg / ha for up to 8 weeks after application of the herbicide by incorporation into the soil prior to sowing and at doses of 3.36 and 4.48 kg / ha for topical application. The compound of Example 1 selectively kills Halep sorghum seedlings at a dose of 3.36 kg / ha for at least 4 weeks after topical application of the herbicide.

As indicated in the above tables, the compounds of this invention are suitable for either topical application or incorporation into the soil prior to sowing. The preferred method of application depends on various factors such as soil type, weather, etc. In general, topical application of these herbicides is preferable to application by incorporation into the soil.

For laboratory evaluation of herbicide resistance to soil leaches and the resulting herbicidal activity, the compound of Example 1 was transferred to acetone and sprayed at various concentrations onto Ray's dusty soil placed in mugs whose drainage holes at the bottom were covered with filter paper. These pots containing treated soil were subjected to leaching by placing them on a turntable that rotated under two water tank nozzles calibrated to a rate of 2.5 cm water per hour as a simulation of water precipitation. Leach doses were measured by varying residence times on the turntable below the nozzles. The water supplied to the soil in the mugs was soaked and passed through filter paper and drainage holes. The cups were then allowed to stand for three days at room temperature. The soil thus treated was then removed, ground and superimposed as a surface layer of soil onto the surface of other mugs containing Ray's dusty soil with a piglet. The mugs were then placed in greenhouses, irrigated from below, and the seedlings were allowed to vegetate for 2-3 weeks. Visual inhibition in percent relative to control (untreated) and piglets in fresh soil was performed 18 days after treatment. The data of three identical experiments of this test are shown in Table IX.

Table IX

Ježatka

Evx Compound Precipitation eg 1 kg / ha cm

Inhibition New sample% (mean of three determinations)% control sample

2.24 0 100 ALIGN! 0 0 0.64 100 ALIGN! 0 0 1,27 100 ALIGN! 0 0 2.54 100 ALIGN! 0 0 5.08 100 ALIGN! 0 0 10.16 95 0 0 0.56 0 100 ALIGN! 0 0 0.64 100 ALIGN! 0 0 1,27 100 ALIGN! 0 0 2.54 100 ALIGN! 0 0 5.08 95 0 0 10.16 95 0 0 0.14 0 100 ALIGN! 0 0 0.64 100 ALIGN! 0 0 1,27 100 ALIGN! 0 0 2.54 95 0 0 5.08 95 0.20 3.3 10.16 90 0.83 14.1

The data presented in Table IX indicate that the compound of Example 1, as a representative of the compounds of the invention, was completely resistant to leaching into the soil under considerable precipitation and showed at least 90% hedgehog control at application rates as low as 0.14 kg / ha at 10.16 cm precipitation.

The obvious advantage of herbicides is their ability to work in different types of soil. The data in Table X show the herbicidal effects of the compounds of Examples 1 and 3 on Brachiaria plantaginea (AG) and Hedgehog (BXG) in soybeans in various soil types and amounts of organic matter contained. Herbicides were applied topically with top dressing as described above. Selective factors for these weeds are shown in parentheses after the doses of GRo ₅ for these weeds.

Table

X

Soil type compound Org. substances % Clay % ®, ₅ ⁸ 0 ^ 85 ⁸ (kg / ha) (kg / ha) Soybeans AG BYG. R ^-dusty 1.0 9.6 Example 1 1.12 <0.14 08.0) 0.14 (8.0) Example 3 1.12 <0.14 08.0) <0.14 08.0) Se ^ p-clay ^ it- j -aluminous 2.3 Example 1 <2.24 0.28 (> 8.0) 0.96 (> 2.3) Example 3 <2.24 0.21 (> 10.7) 0.42 05.3) Drummerrjíi ovi 6.0 37.0 Example 1 2.24 <0.14 (> 15.0) 0,24 09,3) Example 3 <2.24 <0.14 (> 16.0) 0.28 08.0) Florida-sand 6.8 1,8 Example 1 1.12 <0.14 (> 8.0) 1.12 (1.0) Example 3 1.12 0.28 (4.0) 2.24 (NS) Florida — pers 22.1 - Example 1 2.24 1.12 (2.0) 2.24 (1.0) Example '3 2.24 2.24 (1.0) <2.24. (NS) Brazilian (Sao Paulo sandy-clayey 17.6 20.0 Example 1 1.12 <0.14 08.0) 0.14 (8.0) Example 3 1.12 0.14 (8.0) 0.14 (8.0)

and

Data shown are the average of two experiments. Evaluation was performed 13 days after treatment.

It can be seen from the data in Table X that the compounds of the invention were largely unaffected by soil type. In particular, the compound of Example 1 showed a pooidal herbicidal effect on Brachiaria plantaginea and soybean hedgehog in all test soils with an organic content ranging from 1.0% in Ray-Transit soil to 22.1% in Florida deposit soil. Similarly, the compound of Example 3 showed a positive selective herbicidal effect on the weeds tested in soybeans and in all soil types except for the effect on hedgehogs in Florida sand (6.8% organic matter) and F1 soil. Because the compound of Example 3 selectively has both Brachharla plantaginea and a hedgehog in Drumee-clayey soil with about the same organic content as Florida-sand, but with much higher clay content (37%) and in soils with higher organic content a. content of clay, such as Brazilian - 18-Sito-clay soil. It is believed that a low clay content (1.8%) contributes to the selective herbicidal effect on the hedgehog in Florida sand.

The preferred application of the compounds of the invention is in the cultivation of soybeans and araeids. However, selective herbicidal activity has also been demonstrated in the cultivation of various other crops, as shown in Table III above. In further tests, the compound of Example 1 was shown to be useful in growing shrub bean and peas at doses up to 1.0 lb / a, in cotton, rapeseed, carrot and beetroot up to 0.5 lb / a or more and in growing alfalfa, flax and cabbage in the range of 0.25-0.5 lb / a.

These tests of the compounds of Examples 1, 3 and 4 have shown the following properties:

Toxicology Example compound 1 3 4 OLD ≥1 mg / kg 3 370 2 300 2 - 400 DLD, mg / kg > 2,000 > 1,000 <1,260 > 3,100 <5,010 eye irritation ^ t moderate strong medium skin irritation none sticky lepta jcí

The etching caused by the compound of Example 3 may be due to an impurity, dimethylsulfate, remaining in the sample used for the toxicological tests. It will be appreciated that the above compounds can be safely used in a conventional manner for killing toxic compounds. Reeative safety at ша ^ р ^ вс! with the compounds of the examples is in the following order:

Example 1.> Example 4> Example 3

From the foregoing detailed description, it is evident that the compounds of the invention exhibit unexpected and highly advantageous properties of both absoout and structurally closest prior art, one of which is a commercial herbicide (compound C). . The compounds of the present invention have been found to be excellent selective herbicides, especially in the control of difficult-to-eat annual grasses in soybeans, peanuts and other crops. In particular, the compounds of the present invention have shown efficacious herbicidal effects in the control of annual grasses, Texas panic, Roxal ezaatata, Panic era, Vagas plantaginea, sorghum seedlings, Sorghum ULcoLot and Oryza rufppogon, with or without fungi. suppression of other less resistant annual grasses and perennial weeds the weeds listed in Tables II and III above, and - other weeds such as Acanilium (Richard) scabtra, etc.

The herbicidal compositions of the present invention comprise concentrates which dilute before application and contain at least one active ingredient and excipient in solid or liquid form. These preparations are prepared by mixing the active ingredient with excipients which include diluents, buffers, carriers and other formulating agents in the form of fine powders, granules, suspensions, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an excipient such as a finely divided solid, a liquid of organic origin, water, a dehydrating agent, a dispersing agent, and an excipient. an agent, an agent, or any combination thereof.

The formulations of the invention, in particular liquids and wettable powders, preferably containing as an auxiliary agent in one or more surfactants in a sufficient amount to keep the formulation in dispersion in water or in the inclusion of surfactant in the formulations substantially increase their efficiency. By surfactant is meant wetting agents, dispersing agents and emulsifying agents. Anionic, cationic and non-ionic agents can be used equally preferably.

Preferred wetting agents are hydroxybenzene and glycylphthleosulfonates, sulfated fused alcohols, amines or amides of acidic acid, long-chain acid esters or sodium isothionates, sulfated or sulfonated esters of matic acid sulfates, petroleum sulfonates, other petroleum sulfonates glycols, polyoxyethylene derivatives of alkylimide (especially tert-butyl and otolpholol), and polyoxyethylene derivatives of esters of non-fatty acid (non-sorbitol). alkyl, oaphthalenolphonates, oaphthalene, and sodium polymers, and polymethyleniline sulfonates.

Wetting powders are formulations containing one or more active ingredients in an inert filler and one or more wetting and dispersing agents and are dispersible in water. Inert solid fillers are usually of mineral origin, such as natural clays, dlatomic clays and synthetic minerals derived from silica. Examples of such fillers include kaolinity, attapulgite clay and synthetic maagneiousisate. The wettable powders of the invention typically contain 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 an ammonium agent, from about 0.25 to 60 parts. 25 (preferably 1.0 to 15 parts) of a dispersing agent; and from 5 to about 95 parts (preferably 5 to 50 parts) of an inert solid filler, said parts being UmoOnoose parts. If desired, about 0.1 to 2.0 parts of the solid inert filler may be replaced by a corrosion inhibitor or a foam additive, or both. '

Other formulations will incorporate powder ends. Uraes containing from 0.1 to 60% of the mono-active ingredient with a suitable diluent; For administration, these powders may be diluted at a concentration ranging from about 0.1 to 10% by moles.

Aqueous suspensions or emulsions may be prepared by stirring the aqueous mixture in water-soluble active ingredient and emulsifier until emulsion formation and further himoiering to stabilize finely divided particles. Concentrated aqueous so formed. the suspension is characterized by a very small particle size, so that after dilution and spraying, the surface to be sprayed is very uniform. A suitable concentration of these preparations is from about 0.1 to 60%, preferably 5 to 50% of the mono-active ingredient, the upper limit being determined by the solubility of the active ingredient in the solvent.

Another form of aqueous suspensions is a dispersion of a water-soluble, microcapsulated herbicide in water phase. According to one embodiment of the invention, the capsule is ignited by combining the water phase liberating the emulsion, Η ^ οΙο ^ Ι! ouét ,. the compound in the urmisatlonone - and polyumlylropolyphenylisocyanate - by dispersing the phase in water in the aqueous phase - and then adding the polyfunctional amine. This isocyanate adds to form a solid urea derivative that surrounds the particles of substance mixed with water. and so create micripspsr. Generally, the concentration of the treated substance is semi-lubricated in the range of about 480 to 700 g / l of the formulation, preferably 480 to 600 g / l.

Concentrations are usually solutions of the active ingredient in a solvent. water-immiscible or partially miscible together with a surfactant. Suitable agents for the active ingredient of the present invention include, but are not limited to, polymers, N-propanol, hydrocarbons and water ethers. esters or ketones. However, the formulation can be prepared by dissolving the active ingredient in a solvent prior to further dilution, for example, with petroleum and spraying.

Said cercerates generally comprise from about 0.1 to 95 parts (preferably 5 to 60 parts) of active ingredient, about 0.25 to 50 parts (preferably 1 to 25 parts) of a surfactant, where desired about 4 to 50 parts. up to 94 parts by weight of solvent, all parts being parts by weight. based on the total weight of the oil.

The granules are physically stable granular formulations which are effective. or suspended in a base substance which is a finely divided binder. To facilitate leaching of the active ingredient from the particles, these preparations may contain a surfactant, such as those previously mentioned. Examples of comminuted mineral fillers are natural clays, pyrophosphate, illite, and dithromycin. Preferred surfactants are porous pores, sorbs, with pre-formed sections, which are processed and treated for a period of attapilgite, heat treated particles of vermilkuite, and finely divided clays such as ground clay, drilled attapugite, or bentosilicate. ] Uickn clays. These floats are. - Spray or mix with the active ingredient to form a grandiose. which are Uerbicidally effective.

The granular formulations of the invention may contain from 0.1 to about 30 parts, preferably from about 3 to 20 parts, of a mono-active substance and 100 parts of the monocarbon and 0 to about 5 parts of the mono-active surfactant. and 100 parts of mono-grain granules.

The compositions of the invention may also contain longer ingredients, for example, fertilizers, other herbicides, other pesticides, safety enhancers, and the like, which are used as excipients, any combination of the foregoing may also be used. Compounds preferred in combination with the active ingredients of the invention include, for example, iriazines, ureas, carbanates, acetamides, acetanides, uracils, acetic acid or phenol derivatives, thioccaibimates, thiazoles, benzoic acids, nitoils, taphenylethers and others such as:

Heterocyto-derivative containing a broader:

2-Chloro-4-ethylamino-6-isopropylpropylstrstrin,

Z-chloro-α-bis (isoproplylaainone (S-triazine ₎₎

S-Chloro-tha-bis (ethylariel) -s-thioisia,

3-amino-1,2,4-triazole, 3-amino-1,2,4-triazol-2-yl-4- (3H) -ln-2,2-dilxide,

6,7-dihydrodipprido (1,2-a): 2 *, 1 * - cis -pyrazidinium salt,

5-boom-3-isopropyl-6-reylmethyl,

1.1 4 -hipyridnnum,

- Urea:

N * - / 4-chloro-naphthyl-N, N-dimethylalkyl,

N, N-dimethyl-N * - (3-chloro-44-methylthienyl) mlvilvine,

3- / 3,4-dlchlolfennУ / -1,1-diretylr10wiea,

1,3-Dimethyl-3- (2-benzylthiazyl) / mliline,

3- (p-Chlorophthalene) 1,1-dimethylmline,

-iujyo-3- (3,4-dichlorophthalen) -1-retylroacetate,

Karbaméáy / Thil10ariamáty:

2-Chloroyl-phthylidyl okarbame,

S- (4-chlorophenyl) N, N-dittyl-thiocarbamate and isoproplyl- (3-chlorophenyl) oarianate,

S-2,3-dichloro-N-N, N-diol for opltl! okarbarnmá, eLy ^ 1-^ NiN-di · prylpthiokariammt,

S-proppy-di prlpplthi okarbarnma,

Ac etami dy / Ac et tan i ^: dy / Annii ny / Ami dy:

2-chloro-N, N-diallycacetemide,

N, N-Dimethyl-1,2-diphenylacetamide,

N - (2,4-Dimethyl-η 5 - [(trifluoromethyl) sulfonyl ^] amino] ^phenyl- 1 H -amide ^, N-isopropyl-2-carboxylic acid ^, 6,6-parts-N -rttlχynetyУ chloraactiinУld-2, ^{2 '- t} yУ re-6'-tty ^- N / 2 ^i-rt lxyppolp22y ^y / ^2-i chУlricct ^aiУnd, I.iii, I.iii, iУfi-2-tonfjulO 6-dinitro-N, N-di-propyl-4-olefin, N- (1,1-dimethylpropyl) -3,5-trifluoromethyl,

Acids / Esttrl / nlOvhlУy:

2,2-longpooplonyl acid,

2- retyУ-4-chorotenoxllct (:) in acid,

2,4-Dichloroenoenoxy acetic acid, retyl-2- [4- (2,4-diclilphenoxy) phthaleniline],

3-amino-2,5-dichlorobenzene Olseine,

2-nitro-3,6-dichlorobenzoic acid,

2.3.6-trichloroacetic acid,

5- ^[2 'Chllr- ⁴ - / ^j tri luormelyl / fnoxxy] 2 ^- _ _n i_lriennzlni ^Adra,

4.6-dininrO10-seк _β OuiylУefte ^

N- (phefonomethyl) glycine and its monoalkylamines and alkali metal salts and combinations thereof,

Ethers:

2,4-dichlorophenyl-4-nitrophenyl ether,

2-chloro-alpha, alpha, alpha-trifluoro-p-1-olyl-3-ethoxy-4-nitrophenylene ter,

Different:

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

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

The herbicidal formulations of the types described above represent the following examples:

I. Etauls concentrates (EC * s)

Weight%

Compound of Example 135.6

Calcium dodecylbenzenesulfonate / polyoxyethylene ether (non-Atlox® 3437F) 5,0 monochlorobenzene29,7

C8 aromatic hydrocarbon29.7

100.00

B. Compound of Example 385.0

Calcium dodecylbenzenesulfonate / alkylaryl polyether alcohol mixture 4.0

C8 aromatic hydrocarbon solvent11.0

100.00

C. Example 45.0

Calcium dodecylbenzenesulfonate / polyoxyethylene ether mixture e.g. Atlox 3437F) 1.0 xylene94.0

100.00

II. Liquid concentrates

Weight%

Compound of Example 510.0 xylene * 90.0

100.00

B. Example 685.0 Dimethylsulfoxide 15.0

100.00

C. Compound of Example 1850.0

M-Ethylpyrrolidone 50.0

100.00

Weight%

D. Compound of Example 19 5.0 Ethoxylated castor oil * 20.0

Rhodamioe B 0.5 dioethyltormaoid 74.5

100.00

III. Emulsion

Weight%

A. Example compound 740.0

Polytxyethyleo / polyoxypo 'syl block ktptlyoer with butantleo (eg lee ^ trl ^ XH).

vtda56.0

100.00

B. Example compound 85.0

Folyoxyethyleo / pslyoxypropyl block · ktptlyoer with · butantleo3,5 water91,5

100.00

IV. Powdered powders

H ^ otr ^ c ^ sti ^:%

AND. Additive from additive 925.0

Ligoiosulfate standard 3.0

N-p-nyl-N-ool-tetholate (1.0) and silica (synthetic) 71.0

100.00

B. Learning from 1980.0

Litktylsuitosukcinát stdný1,25

Calcium Ligoiosulphate2,75 Amorphous Silica (ssyittic) · 16,00

100.00

G. Case compound 1110.0

Ligoiosulftoate standard 3.0

N- □ □ У N У N N N st ,0 ,0 ,0 ,0 ,0 ,0 ,0 ,0 ,0 ,0 ,0

100.00

V. Pills

HmoOnoosní%

A. Compound of Example 122.0

Attlpp0git98,0

100.00

B. Compound of Example 1360.0

MotOmuutOlorOt40,0

100.00

22399ο

C. Example 14 compound BmOooO t D. Example 15 compound Diatomic clay VI. Granule AND. Example 16 compound granulated attapulgite (20/40 meslh)

B. Compound of Example 17

Diatomaceous earth (20/40)

C. Compound of Example 18

BeeOooOt (20/39)

D. The compound of Example 19

Pyroppyllitt (20/39)

VII. Microcapsules

30.0 70.0 100.00

1,0 99,0

100.00

HmoonooSní%

15.0

85.0

100.00

30.0

70.0

100.00

0.5

99.5

100.00

5.0 95.0 100.00

Hmoonc> oSní%

A. Compound of Example 1 in Polyurea Uricrocapsules49.2

Sodium lignosulfonate (eg Rexas · C-21 ^R ) 0.9 water .49.9

100.00

B. The compound of Example 1 in microcapsules of polyurea 10.0

E

Potassium lignosulfonate (eg Rexas C-21) 0.5 water 89.5

100.00

C. Compound 4 from příkaadu microencapsulated in polymočoviny80,0 ^H steed ^No. mercaptobenzimidazole salt lignosulfonate ^(E Treaxy ^{LTM) 2.0} voda18,0

100.00

When applied according to the invention, they are applied effectively. The acetonitrile according to the invention is applied to the soil containing the plants or is introduced into the water by any suitable means. The application of liquid and divided solid formulations can be carried out by conventional means, for example by means of machine sprayers, rotary and hand sprayers and sprayers. atomizers. These formulations may also be applied by air as a dust or spray, taking into account the efficacy of the formulation at lower dosages. The application of the herbicidal formulations to the aquatic plants is usually carried out by adding the herbicidal formulations to the aquatic environment where the control of the aquatic plants is desired. ·

The application of an effective solution of the compounds according to the invention to the space undesirable. Weeds are essential to the embodiment of the invention. The exact nature of the active substance to be used is dependent on various factors, including the plant species, the stages of their growth, the type and condition of the soil, the amount of rainfall and the type of plant. Typically, doses of from 0.02 to 11.2 kg / ha, preferably at 0.04 to 5.6 kg / ha, or suitably from 0.02 to 11.2 kg / ha are used to pre-geemically apply the plants or soil. from 1.12 to 5.6 kg / ha. In some overflows a lower or higher longitudinal is desired. It is easy for a person skilled in the art to determine from the description and the example the optimum application rate in each case. ·

The term soil is used in the broader sense of the word to include all common soils ”, as defined by WeCbter New International Dictionary, Second Edit! On, Unabridged (1961). This term defines any substance or environment in which vegetation can spice and grow, and includes not only soil, but also compote, manure, silt, humus, sand and the like, adapted to plant growth.

While the present invention is described by specific electrophoresis, their disclosure does not in any way constitute a consequence of the present invention.

Claims (3)

SUBJECT MATTER 1. A compound of the formula (I) is introduced by containing at least one active ingredient as an active ingredient. O CICh'c R N in which means R is methyl or ethyl, R 1 is alkyl of 1 to 6 carbon atoms, Rg. meCyl, ethyl or ^Ί^^ΙΙ ^ R 1 is hydrogen or meCyl in the meta position, wherein R 1 is methyl, R 1 is methyl, R 2 is methyl, and R 1 is hydrogen when R 1 is methyl, R 2 and R 8 are also methyl; and R, isoprophyl or n-butyl, when R is hydrogen and R and Rg both represent methyl, R, is ethyl, t-propyl, itourouyl, n-butyl, itolyl, tert-butyl, n-pentyl, and melt. tulyl, Z-meC-linyl, 1-meCypertyl, 2-eeCyllueetyl or 1,3-dLm ^ Ct ^ ll ^ t ^ y ^ l when Rg is ethyl, Rc is methyl and R1 is itourvuyl, and when lc is t-butyl, H and R5 are both 2. A herbicidal composition according to claim 1, wherein the compound of formula (I) is an active compound of the formula (I) in which R1 is alkyl having from 3 to 5 carbon atoms and R and R8 are methyl groups. 3. A herbicide according to claim 2 urvsУředeí, belief JEC .sr by Zr contained as an active ingredient an ^N-H UJC mu ^e yl-2 * ^P -n гopovy- ^-6 -Iní ^e yll2 c ^{ih il} oraliCtaili