CS226730B2 - Herbicide - Google Patents

Abstract

N-hydrocarbyloxymethyl-2- haloacetanilide compounds, herbicidal compositions containing said compounds as the active ingredient and herbicidal method of use in various crops, particularly sugarbeets. The herbicides herein are particularly effective against annual grasses, including hard-to-kill narrowleaf weeds such as blackgrass, wild oats, and downy brome and other prevalent grasses such as yellow foxtail; barnyardgrass, crabgrass, annual rye, etc.

Description

The invention also relates to herbicidal compositions containing 2-halohaleailides as active ingredient.

OF . Numerous prior art 2-haloacetylilides are herbicidal compositions according to the invention which are closest to the active ingredient and which contain 2-halogenated alcohols optionally substituted with various compounds. sub on the nitrogen atom of the an-people and on the ring of the ring; as such substituents are suitable, for example. alkyd groups, alkoxy groups, alkoxyalkyl groups, halogen atoms -and similar groups.

In the prior art, the closest active compounds according to the invention, which are selected from alkoxymethyl or allynyloxymethyl on the .alpha.,........ Nitrogen atom, the ortho-alkoxy group and the specified ortho-alkyl group, No. 3,442,945 and 3,547,620. The closest compounds of these two patents are 2 ^of tert. -bttyl22-chlcr-- ^τ · thoxymeehyl -ice-6 '-niethoxy · aceCaailii and its bromo analog - / Examples 18 and an in-3Ί eeřekem Patent No. 3,547,620 and Examples. 18 and 36 of U.S. Patent 3,442,945].

The U.S. Patent Nos. 4,070,389 and 4,152,137 protect compounds of the general formula which include those protected in the aforementioned U.S. Patents. - 3 442 - 945 and 3 - '547 620. However, only protected types

226,730 compounds having an alkyl group in the ortho position and an alkoxy group in the second ortho field have an alkoxyethyl group on the anilide nitrogen atom; compounds of this type are described in detail below »

Other, less close compounds are protected in the Belgian patent. No. 810 763 and German Patent Application No. 2 402 98.3; the compounds of the present invention include compounds of the type disclosed in U.S. Patent Nos. 4,070,389 and 4,152,137 and are characterized by an alkoxyalkyl group having 2 or more carbon atoms between the anilide nitrogen atom and the oxygen atom of the alkoxyodil as the closest active ingredient. According to the invention, it appears in the aforementioned Belgian loan file and in the aforementioned German patent application. compounds of the κοάί (ϊϊ - ethoytythyloo group on the anilide nitrogen atom, meehoxysine or erhoxy group in the ortho position and the methyl, ethyl or isopropyl group in the second ortho position »Concerning Belgian Patent No. 810 763, Reference is made to compounds Nos. 7, 13, 18 to 20 and 26. Other less related homologues of these compounds are also protected, see, for example, compounds Nos. 6, 9, 16 and 17, wherein these compounds have an ethoxyethyl or methoxyl group as a substituent. on a nitrogen atom and a methoxy or ethoxy group in one ortho position and a methyl group in a second ortho position »

The aforementioned U.S. Pat. No. 3,442,945 includes some herbicidal data relating to the aforementioned

- 4,226,730 compounds having a chemical configuration closest to the active ingredients. according to the invention and some values are given for other homologues and analogous compounds of less related chemical structure; as, for example, compounds 6 and 9 in the Belgian patent specification: 810,763. In particular, the closest values with respect to herbicidal activity on various weed plants do not contain any data for any compounds which show an additive and / or simultaneous action on the hardly destructive species. such as copybook, annual rye, hedgehog corns and bloody dew, however the aforementioned Belgian patent. It has been shown to have a good destructive effect on deaf oats and on undefined species of various other plant species. 'in diabetes. The compositions of the present invention have unexpectedly more advantageous properties as selective herbicides for the cultivation of diabetes with respect to hleological compounds known in the art.

A further disadvantage of the numerous herbicides known in the prior art is their limited application to a particular type of soil, for example, while some herbicides are effective in soils that have a low organic content, are ineffective in early soils having a high soil content. organic substances. It is therefore preferred that Zyly herbicides be applicable in all soil types from. light organic soils over heavy clay soils and baiui ··

A further drawback of the prior art herbicides is the lack of stability of efficacy in heavy rains, resulting in soil leaching.

226 730

Finally, an even longer deficiency of some herbicides known in the art is the need to introduce and maintain special precautions for their toxic nature. It is therefore desirable that the herbicides be safe to handle.

It is therefore an object of the present invention to provide a group of herbicidal compounds which do not have the above. The aforementioned drawbacks of the prior art herbicides and which illustrate the advantages of a particular group of herbicides.

The present invention is directed to herbicides selectively infecting certain weed species, in particular annual grass, including hard-to-eat weed species such as field foxes, deaf oats and swine, and other weeds such as foxtail, hedgehog corns, bloody and annual rye in diabetes, yet effective in a wide variety of soil types ranging from light to medium organic soils to heavy clays and bahnp '® · leach resistant in strong cases. destů. The advantage of the herbicides according to the invention is that they are safe in use and do not require any in-use precautions.

^The invention therefore relates to herbicides which. . they contain, as active ingredient, a selective group of S-haloaneaniides, characterized by a specific combination of alkoxybutyl, or alkenyloxymethyl groups on a low nitrogen atom, having three alkoxy groups in one ortho position and an alkyl group. C 1 -C 3, such as methyl, ethyl

226 730 or an isopropyl group in a second ortho position having unexpectedly higher and excellent selective herbicidal properties as herbicides for the cultivation of diabetes with respect to the known herbicides, including homologous compounds most related to the known art.

The primary property of the herbicides according to the invention is their ability to control narrow-leaved weed plants in sugar crops, particularly hard-to-control species such as deaf oats and fowl. field species, as well as less resistant species such as typists, hedgehog corns, bloody dew and other harmful weeds.

. sulfur «А ел (Л \ У

The active compounds according to the invention are characterized by the general formula 1

O

II

where it means

R. ethyl, n-propyl, isopropyl, isobutyl, allyo or butenyl;

R 1 is methyl, n-propyl, isopropyl, n-butyl, isobutyl or isoamyl; and

22B 730

R ₂ is methyl, ethyl or isopropyl, with the proviso that.

in the case where R 8 represents an isopropyl group, then R represents an ethyl group R < n >n-butyl;

if Rg means. ethyl, then R is ethyl, n-propyl or allyl and R is n-butyl or butyl;

R when R is n-propyl or .j. isopropyl-1-skun-butyl or pin, is R-, isobutyl;

if. R is isopropyl. R is isobutyl, when R is isobutyl, R is n-propyl, isopropyl, isobutyl or isoamyl, and when R is butenyl is R. metal band.

Of particular interest are compounds of formula I wherein R is C 2 -C 4 alkyl. or an allyl group, R is a C 3 or C 4 alkyl group, in particular an n-butyl or isobutyl group, and R 8 is a methyl or ethyl group.

Of the active ingredients according to the Invention This invention particularly resemble N- / isobutpxymeehhy / 2'-O-soopropoxy -eeehyУ ^of 2-chllrace.eanήlid ',. N / islbutlxymeehyУ / -2 -Sloamlo ^of: χy-6 '-meeihy -chlorac eetnnlid ^, N / n-prlplxymethyУ / -2'-O -soobutoxy -eethyУ ^of 2-ehllrnce.eaniiliď ,. N / ethl: χymtl · χyl / -2 ^from N-б Zutlxy ^of -isc> prlpyl 2-ehllrccettnnlid ,. N / islbu · toxyeethyУ / Z -2-isobutoxy-o -eethhУ ^of 2-chllraceetnnlid,

22В 730

- 8 N / isopropoxymathyl / -2 ^from -isobutoxy-6 ^from methyl-2-chloroacetanilide, N / isobutoxymethyl / -2'-n-propoxy-6'-methyl-2-chloroacetanilide ,. N- (2-buten-lyloxymethyl) -2 ^z -methoxy-6'-methyl-2-chloroacetanilide, N- (n-propoxymethyl) -2 ^z- n-butoxy-6 ^z- ethyl-2-chloroacetanilide _r N- (allyloxymethyl) -2 ^from -n-butoxy-6 ^from -ethyl-2-chloroacetanilide, N- (ethoxymethyl) -2 ^from -ixobuthoxy-6 ^from -ethyl-2-chloroacetanilide and N- (allyloxymethyl-2 ^from -isobutoxy-) 6 ^from -ethyl-2-chloroacetanilide.

The compounds of the formula (I) active according to the invention can be prepared in a variety of ways. For example, they can be prepared by the azomethine method as described in the aforementioned U.S. Patent Nos. 3,442,945 and 3,547,620. reacting with formaldehyde to form the corresponding methylenaniline (substituted phenylazomethine) which is reacted with a haloacetylating agent such as chloroacetyl chloride or chloroacetylanhydride and then. with a suitable alcohol to give the corresponding N-alkoxymethyl-2-chloroacetanilide as the final product.

Another method of preparing a compound of formula I comprises N-alkylating the anion of a suitable secondary 2-halogenation of the tanilide with an alkylating agent under basic conditions.

In Example 1, the N-alkylation process for the preparation of compounds of Formula I is employed.

A modified N-alkylation process is described in Example 2

9,226,730 for the preparation of another type of compounds of formula (I). The modified N-alkylation processes described in Example 2 include the in situ preparation of a halomethyl alkyl ether or halomethylalkenylether as starting materials for the N-alkylation process.

He did

2 ^of -lsobutoxy ^of 6-methyl-2-chloroacetanilide 5.6 g / 0.022 mol /, chloromethyl n-propyl ether, 4.75 g / 0.44 mole / and 2.0 g of benzyltriethylammonium chloride were stirred in 250 ml of methylene and quickly cool. 50 ml of 50% sodium hydroxide solution are added at 15 ° C at once and stirred for two hours, then 100 ml of cold water are added. Layers up. The layers were separated, washed with water, dried over magnesium sulphate and a flask, and evaporated to give 6.5 g (90% yield) of a clear oil; boiling point 130 ° C at 5.32 Pa.

Anal. Calcd for C 14 H 14 ClNO 4 (%): C 62.28; H 7.99; Cl 10.81; found: C 62.27; H 8.01; Cl 10.81.

The product identified as N- (n-propyxymethyl) -2 ^from isobutoxy-6 ^from -methyl-2-chloroacetanilide.

Example 2

This example describes the modified N-alkylation method described in Example 1. In this embodiment, the alkylation is carried out

- 10 226 730 creates an in-situ reagent, making the operation more efficient, economical and simpler.

To a cooled mixture of 4.6 g (0.1 mol) of ethanol, 1.5 g (0.05 mol) of anhydrous paraformaldehyde and 100 ml of methylene chloride is added 6.1 g (0.05 mol) of acetyl bromide; the mixture was stirred until all paraformaldehyde was added. dissolve. Add to the mixture. 5.1 g (0.018 mol) of 2'-n-butoxy-6' ^- isopropyl-2'-chloroacetanilide, 2.0 g of benzyltriethylammonium chloride and 40 ml of methylene chloride are then added. The mixture is cooled to 15 ° C and added in one portion. 50 ml of 50% sodium hydroxide solution and stirred for two hours. The layers were separated, washed with water, dried in a flask of magnesium sulfate and evaporated to give 4.6 g (77% yield) of a yellow liquid, b.p. 125 DEG C. at 0.3 mm Hg. Analysis for C C ^HggClClNO ^ (%): C, 63.24; H, 8.26; Cl 10.37 found: C 63.23, H 8.29, Cl 10.37

The product identified as N- (ethoxymethyl) -2'-n-butoxy-6'-isopropyl-2-chloroacetanilide.

Example 1d. 3 to 12

In essentially the same manner and under the same conditions as described in Example 1 or 2, but using the appropriate secondary anilide and alkylating agent as starting materials and appropriate amounts thereof, the corresponding N- / alkoxymethyl is prepared. or alkenyloxymethyl / -2-haloacetanilides listed together with some physical properties in Table I.

Д4 гЧ d χ>

СО

Η

226 730

Г - гг

Ч..1 ф

Р

Рч ф Р о

1 — I CL. ф н

Q а. χ

οχ ο со <ο СА н 00 СП LfX сП 4 · о см Η сП СП см ОХ со сп со 00 п о см 00 сП CJO о см Г- о о кО гЧ (М 00 о <ο гЧ ко н ко гЧ ко гЧ

ко X со ох гЧ о х гЧ СО σχ с ** гЧ см (М X см ох со Л X ох см Ολ см 00 • ч * ч • ч Л • ч • ч ГЧ • ч • ч • ч • ч ГП Ό о см г- о о кЭ ι — 1 см с- о кО Г-Ч ко 1—1 ко н ко н

гЧ о гЧ Ο

3 X I ко X X Р 1 Л кО о О о ФО 1 гЧ ** см * ч гЧ ~ Í РЮ | гЧ (М гЧ ’4- Н X 1 X X X

ι I I

I!

^ч >> 1 ίΠ сП сП Л? 1 о о о о о 1 Н73 · Л - ^ - 4 • н о 1 гЧ ι — i гЧ гЧ н Ф 1 о о о о • р р 1 00 ко о кО а, о AND (М см см СМ а N 1 НН XI М > м '3 Р » 1 “Оо х LÍX X 1 гЧ гЧ гЧ гЧ t F о о О О Г 1 1 1 ч 1 1 см Р 1 1 1 О 1 ч X гЧ AND 1 1 1 см AND гЧ .й 1 Ч хм 1 см X о см 1 см 1 X 1 XI AND 1 см 1 1 гЧ гЧ гЧ -Р см X 1 ф 1 гЧ X X X ф 1 гЧ 1—1 d 1 X .й XI х: Й гЧ X д> • н г х: -Р Р Р X X XI XI й 1 Р> ф пЭ ф ф ^Г О X XI Р Р тэ ф 1 ф Й • Ч а а • н о Р ф ф • <ч > о 1 а 1 гЧ X 1 гЧ ! ф а а гЧ d 1 řx ч ч X ’ к лН 1—1 а X 1 • <ч о 1 X ко й о ко й 1 1 ч гЧ • о 1 3 си 1 ф й ’ ч со о кО ф со 1 -р X Р о X • Р ф кО • гЧ • Р 1 -Р 1 d X ф Р X ф • Р 1 гЧ d X ф 1 ю о о о < о о d X • н X) К о 1 о -Р со о -Р ф X) X Й 0 о ф 1 Ф d Р ф d ρ t о ф ф й Р • Н о о • н х> о см XI -Р • гЧ а о 1 X о гЧ X о гЧ X • Р ф X о гЧ 1 1 ф XI AND ф ч '• ‘-н 1 ф о 1 ф XI 1 • гЧ о • н о а ф • н о

N- (isobiixymethyl) -2'- ΟΟΟΗΗ 120 120 С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С С 9.96 10.03

ПЭ 0 н о

Л4 гЧ М со> Р н РцЮ

I I I I I I сп

<Α <ο

Table 1 / continued /

AND

AND

1 1 1 Ο β φ Ν 1 1 1 ο CM Λ ΤΟ Ο · * 00 00 IN* Η m · * cCM IN" 04 / • b Ο το • к -4 * «Η 04 Μ- · * οCM ν * CM ο • к CM 00 Λ rd ΤΟ ·. rd Ο- ν * what 1 Φ t CM 00 ο Η 00 Ο ηΧ Ο Ο CM 00 ο ΠΊ Ο Ν 1 Η 1 ΤΟ Η το rd ΤΟ r4 το Η το řb 1 C0 AND Η 1 and 1 WHAT 1 1 β 1 1 1 ο 1 1 β 1 00 στ Η Η- το Ο * Η rd Ώ 00 ΟΤ r — 1 rd rd 1 φ 1 CM οτ 00 CM CM m ΤΟ Ο- • = 4 · CM στ οο ΤΟ Ο- 1 -Ρ 1 1 χο 1 CM ο- ο m what О m Ο Ο 04 / C- ο γί ο- 1 ο 1 ΤΟ Η ΤΟ Η το rd ΤΟ Η ΤΟ F and 1 1 Ρ> » 1 1 > 1

Ad φ>

Ρ »ι — I Ο

226 730 co-Ρ rd - a зсо coo; \

C0 Ρη

4- ΤΟ X it X X (Ί X το Γ— • к Γ— IT СП m OJ Μ it CM O r — 1 in* cu in* in* 04 / • к Η rd rd CM rd 1T \ rd σ> rd CM X X X X X

O

Φ

AND?

Q d з

• rd

P O

N M F>

1 m ol 0Π m rn r O Q O O O 1 WITH ^Q with and 1 rd d d d d 1 O O WHAT O WHAT 1 IT 00 it IT it 1 CM CM CM CM CM 1 w 3Р and S4 S4 1 γ- WHAT 00 O- what 1 η d d Η d O O O WHAT WHAT

AND

I I

AND

1 1 1 f 1 1 β 1 CM ø-1 o H з O 1 3 1  TO CM 1 3 • o rH £ ^rd 1 x 1 3 O • H 1 o 0J • H 1 3 o rH Yeah OJ • rP l 3 O H CU 1 1 1 1 r4 CM x: 1  3 X rj 3 1 X CM X O 1 O X . at CM O • rd 1 d 1 d 1 X 1 CM 1 • 1 β 1 Р * э H OJ H rj 1 CM X CM Φ 1 X4 Г5 ..3 1 Px 1 X 1 d 1 XO 1 -p Xí 4P rd .3 d <—1 H rj d 3 and Φ -P Φ P > 1 > 5 x: O 1 and Φ and rd Φ .3 .3 з • p -β d 1 Pk and r> -p and • p -P P φ d-> WHAT 1 H 1 * X Φ Pk Φ Φ Φ and φ 1 O to / 3 O h Ό X 1 T3 and and • 3 Px 1 1 +> IT • rd and '-d O % • rd >> X • · d X X 1 3 1 d O TO d H it d X IT rH O it 1 .0 p >> • rd 3 2 d rx 1 • rd O 1 • d H 1 1 O X β and Pk β H rx β -3 Řk β Pb >> 1 what O WHAT 1 x ^a d X au p X WHAT d X 1 • rd and + » 3 O +> © O • P φ O P i — 1 O 1 X. O Φ X P Φ X -P Φ X -P Φ au P 1 1 Р O J 3 ϋ 1 3 O 1 d O | d 1 а and o> а X> CO & XJ WHAT а XJ WHAT а XJ

acetanilide Cl 10.43 10.45 d

co rd Ο Ad Η Ή 0J> 3 Ή РчЮ

AND

AND

AND

I I I

AND

I οο στ <χί

Η

- 13 226 730

The starting secondary anilides used in the above examples are prepared by methods known per se, for example by the haloacetylation of the corresponding primary amine with a haloacetylating agent such as haloacetyl chloride or haloacetyl anhydride. Typically, a suitable amount of a suitable primary amine is dissolved in a solvent, such as a methylene chloride containing a base, such as 10% sodium hydroxide, and strongly precipitated. with stirring with a solution of a haloacetyl halide, e.g. chloroacetyl chloride, while cooling, for example, to a temperature of 15 to 25 ° C. The layers were separated and the organic layer was separated; washed with water, dried and evaporated in vacuo.

The primary amines used for the preparation of secondary anilides can also be prepared by methods known per se, for example by catalytic reduction of the corresponding, suitably substituted nitrobenzene, for example 2-alkoxy-6-alkylnitrobenzene, in a solvent such as an alcohol such as ethanol using platinum oxide catalyst.

As mentioned above, the compounds of formula (I) are herbicidally active and are particularly useful as herbicides prior to application. however, post-emergence efficacy has also been found. Said pre-emergence tests were carried out both in the greenhouse and in the field. In the greenhouse tests, the herbicides are applied either to seed after sowing or vegetative sowing; by planting or by introducing it into the soil, which is applied as a coating to the test seeds in the test vessels previously sown. When field

- 14 226 730 tests with herbivxd. It can be introduced into the soil before roots ("VP» P · "), that is, the herbicide is applied to the soil surface, then worked into the soil by mixing, whereupon the crop plants are introduced or the herbicide can be applied to the surface . /P.N. - surface application / after the introduction of the seeds of the crop plant »» The test method of steam surface application in the glazing is carried out as follows: Containers, for example. aluminum bowls, · generally 24.13 cm x 13.34 cm x · 6.99 cm, or 9.53 cm x 9.53 cm x plastic mugs. 7.62 cm, having irrigation holes in the bottom, are filled to the brim with dusty soil, from Rae, then the soil is suffocated to reach 1.27 cm from the top of the cup. The mugs are then sewn with the species of test plants, covered with a layer of test soil. The herbicide is then applied to the soil surface, for example with a belt sprayer at a rate of 187 l / ha, at a pressure of 207 kPa. In each cup, it is poured in the form of a beaker / 0.64 cm of water. greenhouse for possible irrigation from below. In a variation of the method, irrigation in the form of watering may be omitted. Three weeks after treatment, a herbicidal effect was observed.

Heebic.the soil treatment · / ^и 3.1. ^м / when tested in a greenhouse, it is carried out as follows:

Potted soil good. The quaaites are introduced into the silly. bowl and pressed to a height of 9.525 mm to 12.7 mm · from the top of the bowl · to the soil surface / applied in advance · set number of seeds or planted vegeeative offshoots of different plant species, after the bowl ae = weigh the soil needed for alignment mls after sowing seeds

- 15 226 730 or after ... the deployment of vegetative offshoots. The known amount of active ingredient used in / in the form of a wettable powder and the soil is intimately mixed and ingested. After treatment, the plates are coated; the bowls are poured with water corresponding to rain 0 * 64 en and then humidified by bottom irrigation to provide the necessary moisture for germination and growth; With a replacement. procedure is omitted. The radiation is carried out. two to three weeks / after.

sown and ground.

In Tables II and III. the results of the tests carried out to determine the herbicidal activity are summarized before the active compounds according to the invention; in these tests · the herbicides are used by the method of introduction into the soil · and only under the lower irrigation; the bracket / - / indicates that the plant has not been tested. The action is assessed by a fixed scale based on the percentage damage of each species of plant. This scale is as follows:

% damage to 24 to 49 to 74 to 100

Evaluation

The salivary species used in a number of tests, the results of which are given in Table II *, are indicated in the table®. II · by these letters

- 16 A thistle (Cirsium vulgare),

В řepeň,

C parasite, abutilone,

D povijnice _T

E merlíк white,

E rdfesno pepper *

G šáchon / yellow nutsedge /,

В creeping "

I Halep sorghum, <J sveřep / downy brome /,

К hedgehog corns leg

- '17 -

Table II · Compound according to example no Before emerging _{kg / ha} Species grew ^ · ^{730 J} ABCD. Έ. F ': G Η I 3 K

1 11.2 3 1 2 2 3 3 3 3 3 3 3 5.6 3 0 2 2 3 2 3 3 3 3 3 2 . 11.2 1 1 2 2 3 7 3 3 • 2 3 3 3 5.6 0 - 9 1 3 2 3 3 3 3 3 1.12 0 - 1 0 1 1 2 1 0 3 3 3 . 11.2 0 0 0 3 2 3 3 3 1 3 3 5.6 0 Q 0 0 2 1 1 3 3 3 3 4 11.2 3 0 2 2 3 3 3 3 2 3 3 5.6 2 1 2 2 2 2 3 3 1 3 •of 5 11.2 2 1 0 1 3 2 3 3 1 3 3 5.6 1 0 0 3 1 1 3 3 0 3 3 6 11.2 2 1 1 1 3 3 3 3 3 3 3 5.6 2 1 1 2 3 3 3 3 0 3 3 7 11.2 3 0 1 1 3 2 3 3 0 3 3 5.6 2 0. 2 1 3 2 3 3 1 3 3 8 11.2 3 1 0 2 3 3 3 3 3 3 3 5.6 3 2 0 2 3 3 3 ' ъ tv 3 3 3 9 11.2 3 0 0 0 2 1 3 2 1 3 3 5.6 3 1 0 0 2 1 3 2 0 3 3 10 11.2 - 0 1 1 2 2 3 3 3 3 3 5.6 - 0 0 0 3 2 2 3 3 3 3 11 11.2 3 1 2 2 3 2 3 3 3 3 3 5.6 2 1 2 2 3 2 3 3 ₁ 3 3 12 11.2 3 - 0 1 3 3 3 3 3 3 3 5.6 2 0 1 1 1 1 3 2 1 3 3

-18226 730

The active substances are: further tested as described above using the following plant species:

L soya,

M sugar beet,

N wheat, rice ;,

P sorghum,

В řepeň,

Q buckwheat,

D will say,

In hemp / hemp sesbania /,

E white goosefoot,

E rdesno pepper,

C colon, abutilone ^

J sveřep / downy brome /,

S millet

К hedgehog corns leg,

Ί1 bloody dew ·

The test results are shown in Table III

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WHAT what what what WHAT what WHAT what rH 0 WHAT what what CM WHAT WHAT what what CM rH what what what what CM what what what WHAT rH what what WHAT- rH what WHAT what what rH rH what what what CM 0 what what ΓΜ rH O what what rH rH what what what rH O O what what what what 0 what what what rH O what what rH O what what CM rH rH O · —1 0 0 0 0 rH 0 0 O O 0 0 O O rH 0 0 O O O ro CM rH 0 rH what CM rH 0 0 0 0 0 0 rd 0 0 0 0 0 WHAT what 0 O CM CM CM rH O O 0 O O O CM rH 0 O O 0 WHAT rH 0 rH 1 CM CM 0 1 O CM O O O WHAT WHAT 0 O 1 0 O 0 0 O O WHAT rH 0 0 O WHAT O O rH rH H 0 O 0 0 WHAT rH CM O O CM O 0 0 O O O O O rH O 0 O 0 0 O O O O O WHAT O 0 0 1 O O O O O O 0 O 0 0 WHAT WHAT WHAT CM O WHAT WHAT CM 0 0 what WHAT O O WHAT WHAT what rH 0 0 WHAT WHAT CM CM rH WHAT WHAT CM rH 0 CM WHAT O O WHAT what CM rH 0 0 WHAT 0 O O O WHAT CM CM O 0 CM rH O O WHAT what rH O 0 0 what rH O O O CM rH O O 0 rH O O O CM rH rH O 0 0 rH 0 O O O rH 0 O O 0 O O O O rH 0 O O 0 0

226 730 what what what what what what what what what what what rH 0 <0 what what cm 0 0 0 0 O 0 CM NO o O CM CM rH 0 O CO CM r — I CM CO CO CM O CO O CM CO CO OO CM CO CO rH O CO CO rH OO CO CO co OO co CM rO o CM CM rH rH rH CM OOOO

LO • 4 CM CO LO rH CM CO LO rH CM CO LO CM CO LO rH O kOrd CM O'O LO rH CM O O LO rH CM - O LO-rH CM O O O three · IK. TO.. · -. · - «... ·» · -. · - X. · - · - · - к : 1 in rH 0 0 0 IA HOOO IP rH O O ID rH 0 0 0 0

CM CO LO rH LO rH CM O O - **. - - V »

U0 rH 0 0 0

Φ rH to O O rH U OQ X co> 0 c • H 5

C to φ Φ XJ rH л O Ή

CM

CO XT in rH> o ω o.

к а III / continued Before emergence

го со со сч го со го сч η со СО со со 1 1 1 1 1 1 1 1 1 1 го го го ГЧ го ГО ГО гЧ го со СО со гч со со СО го о со со го со о ГО ГО ГЧ о го гч н гч со со со о о го го со о о со со со о о го ГО »4 о го го »-ч гЧ го го гЧ о о со Ή го гЧ гЧ со ГО со о о о ООО о о о о о о о о о о о о о о гч о о о о го со о о го гч о о го гч ГЧ гЧ о го гЧ о о о со гЧ он о го го о о со го о гЧ .'Ί гч со о о го о о о о со сч гЧ о о СЧ ООО <4 о о о со со гЧ * ч о сч гч о о о гЧ о о о о о ООО ГЧ о о о гч гЧ оо о • ч о о о о о »-Ч о о о ГЧ го о о ГЧ гч о 1 сч гч О <4 о со гч о о о ГО гЧ о о о гЧ ООО сч о о о сч <ч О! гЧ о о о о о о о о о о го ГО ГЧ о го гч о о со СО гЧ гЧ о го сч гЧ о о СО г-ч гЧ о о го гЧ гЧ о го ГЧ ГН о го гЧ ОО о со со гЧ о о со сч сч о о го гЧ гЧ О го гЧ О о го гЧ оо о го сч о о о со сч гЧ О о ГЧ нно гч гЧ гЧ гЧ сч гЧ ΟιΗ о гч о о о о СЧ гЧ гЧ о е гЧ ООО ООО о гч о оо гЧ сЧ о о о о о 1 о о о

• С СЧ СО 40 СЧ СО 40 СЧ СО 40 гЧ СЧ СО 40 гЧ СЧ СО 40 гЧ х> 40 Н сч о 40 Η сч о 40 гЧ СЧ О О 40 гЧ сч О О 40 ι-Ч СЧ О О • ч. · -. · * · - · - · - **. · -> · - *. * 4 ·· * - · *. · -. · - Сб Щ гЧ о о шноо 1Л гЧ о о о Ш ГЧ о о о шноо о еч •

ф. <ч

П5 о О гЧ а и м со> о а • н з С Ό

СО σι

* 4 Л

- 21 .с • н гЧ -к>

СО о £ <ω

Г)

Рч н tlili сосо со со о

О С «« «« «« «« О О О О О О О о

226 730 к а _____ III / continued /

Before emerging

CU о

S со со со со о сч см о о о СО СЧ О 1Л |

О О Ч М О М М М М М О О О О О О О О О О О О О О О О О О О О О О О О О О М О М М М С

О С <Ч 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 <40000 О С 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 гЧ о со »ч гЧ о о о о о о о н

СЧ 00 <0 гЧ VD гЧ СМ О О

Г'ч »-4. · «. «.

1Л гЧ о о о

СМ СО кО гЧ VO гЧ СЧ о о ^ «Ч. · - · · -

Ш гЧ о о о

2K 730

The herbicidal compositions according to the invention have an unexpectedly better property than. selective herbicides used for emergence; in 'sugar beet', especially for the selective destruction of difficult-to-control narrow-leaved weed plants, including paws. pea, oats of the deaf and 'downy brome', and other weeds, such as J. fox, annual rye /, hedgehog of corn. foot, and bloody dew. The selective destruction and control of the abovementioned weed plants and other weed rossiins by the henbicidal compositions of the present invention is possible in a variety of different crop plants including soybean, cotton, oily, oilseeds, rapeseed, rapeseed, tomato and tomato. The remarkably excellent herbicidal properties of the active compounds according to the invention are the most expensive in the selective control of annual weed plants in sugar beet.

In order to demonstrate the unexpectedly superior properties of the active compounds according to the invention, both absolute and relative, greenhouse tests were carried out using: 1) homologous compounds known from the prior art. technique and closest to the fracture compound of the invention. of the invention and 2) other compounds which are not to be considered as humorous compounds. within the scope of the prior art, one of which has better ilattlooti as a beet herbicidal composition and two of which are; commercially available herbicide sprayers; All compounds in the comparative tests; are generally defined as the phenyl-N-hydroxycarbonyl, alkyl-2-hydroxy-substituted phenyl. The compounds known in the art are referred to in the following tables with the following letters:

- 23 226 730

A. N- (Methoxymethyl) -2'-methoxy-6'-tert. butyl-2-chloroacetanilide / Example 18 of U.S. Pat

442 945 and 3 547 620 /,

B. N- (methoxymethyl) -2'-methoxy-6'-tert. butyl-2-bromoacetanilides / Example: 34 in U.S. Pat

No. 547,620 and Example 36 of U.S. Pat

442 945 /

C. N- (isobutoxymethyl) -2 ', 6'-dimethyl-2-chloroacetanilide, commonly referred to as "dielachlor" (Example 31 in U.S. Patent 3,442,945) and Example 24 in U.S. Patent 3,547 620 /,

D. N- (allyloxymethyl) -2 *, 6'-dimethyl-2-chloroacetanilide (Example 47 in U.S. Patent 3,547,620),

E. N- (methoxymethyl) -2 ', 6'-diethyl-2-chloroacetanilide (U.S. Pat. No. 4,547,620 and U.S. Pat. No. 3,442,945), commonly referred to as ®; 'Alachlor ⁴ ', the active ingredient of LASSO, a commercial herbicidal product, a trademark of Monsanto Company,

For N- (methoxy-4-ethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide (compound number &lt; RTI ID = 0.0 &gt; 810763) &lt; / RTI &gt; 2 402 983 /,

G. N- (ethoxyethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide (Compound No. 7 in Belgian Patent®: No. 810 763), ^Г

- 24 226 730

N- (1-Methoxy-prop-2-yl) -2 * -methoxy-6'-methyl-methyl-tert-butyl} -Rait _; tidi / compound number · 9 in the Belgian patent no. '810 7 63 /

I. N- (Methylphenyl) -2'-ethoxy-6'-methyl-2-chloroethanilide. (Compound No. 16 in Belgian Patent No. 810,763),

J. N- (et al.) _; Ethyl-2'-ethoxy-6'-methyl-2-pyrimidine-aniline. (Compound No. 18 in Belgian Patent No. 810 7.63),

K. N- (Methoxy) Ethyl-2-Methoxy-6-cypropropyl-2-chloroacetamide / Sulfurent and No. 2 of the Belgian Patent No.

810 763, L. N - (isopropoxy-2-ethyl) -2'-methyl-6'-methyl-6'-methyl-2'-methyl-2'-methyl-N- (1-methoxyl) -2-methyl-2-yl] -2 * -ethll-6 * -methll-2-chlorothanililide / compound of U.S. Pat.

No. 937,730 and German Application No. 2 · 402,983, commonly referred to as meeolachorrh, the active ingredient of a commercial herbicidal herbicide. Ciba Geigy Colpolraion.

However, the compound designated as C. is less similar in structure than the hemi-herbicidal compositions of U.S. Patent Nos. 3,442,945 and 3,547,620. since it does not have an ortho position of alcohols, it is included in the tests to be carried out since it has better properties as a herbicide for the cultivation of diabetes than the other compounds mentioned in both the above mentioned patent claims. relationship of the prior art and have achieved commercial

- -. 25 '226 730 extension. Compounds - F. to L are included in the tests and have a similar structure to some of the active compounds of the invention.

In the pre-emergence herbicidal activity tests, the active compounds of the invention are compared with the prior art compounds -A to M / with respect to the destructive action on various weed plants, in particular the annual narrow-leaved species, which are predominantly in diabetes. occur. Test results - are listed below.

In the discussion below mentioned. results, useful references to the doses of herbicidal composition used are referred to as those in kioogaams per hectare (kg / ha) that are convertible into pounds per acre (lbs / А) by dividing the dose in kg / ha by number. . GR znamená represents the maximum dose of herbicidal composition required to cause 15% or less damage to the crop plant x GR ^ represents the minimum dose required to achieve 85% inhibition of weed plants. Dose x "GRg ae is used as a measure of the possible performance characteristics, i.e., suitable commercial herbicidal compositions may have. more or less destructive efficiency: on plants within reasonable limits ..

Another guide for assessing the efficacy of a chemical as well as a selective herbicidal composition is the selective fakrot (SE) / pro-herbicidal composition in a given crop plant and for a given weed plant. The seeective factor is a measure

- 26 226 730 relative degree of crop safety and weed deleteriousness, and is expressed as GR ^ / GRg_, that is, by dividing the GR ^ value for the crop plant by ΟΒθ ^ for the weed, with values in kg / ha / optionally 1hs (A).

In the following tables; optionally, the selectivity factor is given in parentheses after the weed level; the symbol KS means bearing ¹¹ ; the dash / - / for weed means a slight or undetermined selectivity, for example because the CR and / or GRq ^ doses are higher than the maximum sky or the minimum dose used in said acoustic treatment.

Since the tolerance for crop plants and the destructive effect on weeds are correlated, the brief discussion of this relationship is of importance with respect to the selectivity factor. In general, the safety factor for crop plants, i.e. the herbicidal tolerance value for crop plants, is desirable. high, since for one or the other reason it is often desirable to use lower concentrations of the herbicidal composition. On the contrary, it is desirable that the weed control dose be small, i.e., that the herbicidal composition has a high unit efficacy, for economic reasons and possibly for ecological reasons. However, small doses of the herbicide used may not be sufficient to control certain weed plants and ₄ may be carried desired higher doses the herbicidal compositions. Therefore, the best. herbicidal compositions are herbicidal compositions which destroy

226,730 a large number of weed plants using a small amount of herbicidal composition * while at the same time having the highest degree of tolerance for crop plants. Therefore, the selectivity factor, as defined above, is used to quantitatively assess the relationship between inertia to crop plants and the weed control. In view of the selectivity factor given in the following tables, the higher its numerical value, the greater the selectivity of the herbicidal weed control agent in a given crop plant.

In the following tables, unless otherwise indicated, values for compounds that have been tested in numerous trials are given, and mean values for conventional doses of herbicidal composition use are within 0.14 to 2.24 kg / ha / 0.125 to 2. 0 lb / А /. Otherwise, the various tables include data from a single downstream application rate test of herbicidal compositions to 0.07 kg / ha / 0.0625. lb / A / or up to 4.48 kg / ha / 4θ lb / A /.

In the first series of tests, the herbicidal activity before emergence in Table IV is reported in comparison with the relative potency of representative compounds of the invention with close compounds of the prior art as selective herbicidal agents against weed plants common in sugar beet cultivation. Weed plants used in the tests are indicated in the table with the following abbreviations: deaf oats (WO), hedgehog corn (BYG), bloody dew (LCG), field fox (BG), fox (YET) о

226 730

Ен Ьч X

О CQ

Х “Ч хч χ-χ О хч ^ Ч χ-χ —ч см о * ч о • ч * х • х 1 1 1 г ^ Л, КО Ч-Х ч> ~ ~ д

00 хг г * г * ^ 3 * Чф о о гЧ о о о гЧ гЧ • ч <ч ч. • ч. • ч • -Ч <ч • Х е · '• ч · * о о о о о о о о о о IN IN IN IN IN IN IN х-ч х — ч ко о х — ч ХЧ х-ч Х ~ Ч • • 04 / о о о хч хч X-ч ХЧ ко • • ч • ч • х ω ω ω ω гЧ гЧ гЧ 00 Γ * Ί 2 of of л А л * - * * л * г чх XX * - * ч-х Чх * - * г- г * 00 X г * г * м » <ч о о см гЧ о о со гЧ • Ч 00 • -Ч * 4 * 4 • ч • ч «Ч * ч »4 <ч ч о о о о о о гЧ о о о IN IN

β α

Λ4 гЧ

Д я

Еч

ХЧ ХЧ х-ч. ко о о о о о * ч хч х-ч хч • х X • ч • ч к СМ * <3 * ко гЧ 00 ко AND 1 1 • f4 гЧ гЧ / \ А А г * А А л * - * * —X * -— * * - * * - * ’Чх’ * —X ч-х Чх * г- г * г * г- г * М ¹ М ¹ * з * XÍ · о о гЧ о о о гЧ • ч гЧ гЧ * ч 1 «. • х • Ч • ч • х ♦ ч * ч • ч • х о о о о о о о о о о IN IN IN IN IN IN IN IN IN IN

о X

СО

ко о о х-ч о о ХЧ х-ч хч см * х • х * х о * ч * х * х М ⁴ ко гЧ • х ко 1 1 1 г * гЧ гЧ гЧ м · д А л. л. А л хх '* -х * чХ * - * * - * · xť -м * Г г * м * хг гЧ о * ч о о о гЧ гЧ • Ч • Ч * ч * ч • ч • ч • ч. • Ч • Ч • х • х  * ч о о о о о о о о о о IN IN IN IN IN IN IN IN IN

х-ч ХЧ хч г * хч хч о о гЧ х-ч х-ч х-ч Х-ч * ч г * <ч * 4. • ч • х ω СП ω со • X • Ч гЧ см гЧ 2 52 д см см х-х ЧХ Х- * ЧХ чх ч- * ЧчХ ЧХ XX о ’З’ о со со 00 со * <3 · о ш гЧ 00 см см го ко со г · ХЧ · »- · - • ч * ч • Ч * х • х о о о о о о гЧ л о о о

л> О mtn Д4 гЧК 3 о «о О

ко со * з * г- г * гЧ ш хг ш см со о о о о о см ш <* Ч « · —- • ч • -Ч ГЧ * -Ч * 4. • -Ч • о о о о о о гЧ см см • ч IN ν ' IN А л А

• · е д

d д

С Ά О Сч О> q p

д m <ϋ <4 со м * * о со гЧ гН д Л4 м «Č Ή X X * ч > ч > Я а а. Й-

226 730

Hoádioty in Table IV ucaazuí, - that with regard to harmlessness, for the cultural plant. / as it says. doses of GR for the lactose are effective. The compounds according to the invention excel at the compounds known from the prior art. OSpecially. In view of the prior art, the closest structure is, for example, compounds A and B. having the N-alkoxymethyl-2 * -alkoxy-6 * -alkyl-2H-logactactanide configuration, wherein the active compounds of the invention in Test 5 , 8. times more potent and 8.0 times safer in sugar beet than Compound B and approximately 2.8 times more potent and 4.0 times safer than Compound A. Even more worthy of attention. that. The active compounds according to the invention are 22 to 32 times more safely. with respect to cultivated diabetes than the prior art compounds referred to herein by the letters F, G and L, each having a greater than 15% adverse effect on diabetes at a very low dose of less than 0; 07 kg / ha.

Although not homolegem effective. The compounds of the invention are known to have unlabeled compounds. letter C _f has better properties as herb-CIDNA agent for diabetes with respect to other compounds protected in the aforesaid U.S. patents 3 442 945 and 3,547,620, which protects tqké compound A and B. Similarly tnlkoliv compound, which is designated 1111, it is not a homologue of the active compounds according to the invention, it falls within the scope of German patent application 2 402 983, which also protects the compound designated by the letter. F and G and oZice include the compound referred to as L1 compound,

226,730, referred to as the letter M, is an effective commercial vehicle as described above. G - in Table IV for the compounds ® designated as C and M, it is recalled that these compounds will find a greater degree of insecticide than other compounds known in the art. one half - an inactive substance of the invention - and compound M has only about one half to two thirds of countlessness than the active ingredient of the invention.

At the same time as the high safety level of the cultivated plants, the active compounds according to the invention have unit activities (i.e. phytoxicity per unit of plant weed). how to report the value of benefits - GR or -. less comparable to mamL.

The combination of high crop factor for crop plants and high unit activity against weed growth results in an excellent way of higher activity factors of the active compounds according to the invention with respect to the compounds known in the art. with the sole exception of the compounds of Example 4 in relation to the foxtail.

In particular, it is noted in Table IV, when comparing the efficacy factors of the compounds known from the tcc.Uiiiy state to that of the compound of Example 1, with respect to weeds in diabetes, that the compound of Example 1 is more selective than the known compounds. state of the art by a factor

226 730 approximately 2.4 to more than 4.7 times greater for deaf oats, approximately 2.1 to more than 14.6 times greater for hedgehog, corn and fox; and about 1.8 to more than

14.6 times larger with regard to the blood-grass and the fox.

Additional tests using the active compounds of the present invention are the restriction of the hedgehog's legs _in bloody crabs and field foxes and fox-tails at doses lower than or even less than 0.07 kg / ha (0.0625 lb). Thus, the compounds of Example 1 show a destructive effect on each of the above weed plants at a dose of 0.07 kg / ha or an even smaller compound of Example 4 have a destructive effect on a hedgehog, a bloody dew and a foxtail at a dose of less than 0. 07 kg / ha and the compound of Example 3 has a devastating effect on the hedgehog corns and on the dew at 0.07 kg / ha or less.

In other comparative tests it is determined; pre-emergence herbicidal action: and the selectivity factors of the compounds designated by the letters С, E, H and M of the prior art, and these compounds are compared to the compounds of Examples 1 to 8; the values obtained in these tests are given in the table; V. Individual weed plants are labeled in the same manner as in Table IV.

о x Η

X

Сб А

Η Um> <

Lf) tp;

о

> о Ci X о

со с • н а ф ю о гЧ СЛ

см ч кО Гч Р-Ч о «—Ч о ч # ~ ч о • ч о о • ч ^ Ч О * 4 ^ -Ч <-Ч * -ч * ^ ч <ч • Г • ч кО гЧ * ч кО ко о о г * гЧ со А гЧ со А А Гч ►х кО 1 1 л л А А л А А Л кО гЧ • ч— * • ч— * - * ч / Ч— ч ». ч- ^ 43 * 4Г 43 · 43 * 43 » 43 « 4У 43 · 43 · 43 * 43 * 43 * гЧ А гЧ А А А гЧ гЧ гЧ А А А · * • ч г * * ч ♦ ч »Ч • ч •> ч г » • ч Гч еч о О о О о О О о о О О О IN IN IN IN IN IN IN IN IN IN * —Ч ** 4 * -ч кО о σ \ ^ У * “Ч ♦ ч г-ч • -Ч * 4. о <-ч ^ -Ч о * —Ч * -ч * —Ч 43 · о кО гЧ * ч о о о со со со А * ч А д со * ч • -Ч • ч со £ 2 Л 00 А А ' со 43 * 43 · * - * ** - * ч ^ » * ч- * ч-и Ч- * ч ^ 00 гч Γ- 43 * 43 * 43 * гЧ см со кО кО СМ гч гЧ ΟΟ гЧ гЧ А со СП ш ю • * ч Г- ♦ v. Гч # 4 ГЧ »- • ч • ч * ч О гч А гЧ О о О о о о о о IN IN и-ч * - * # ^ ч кО ^ ч О * -ч * -ч ^ -Ч «Р-ч о гч • о • ' о о о о о · - ** - ч х-ч • -ч 43 * • кО кО г * А СО А А со ко кО ко Л 1 1 л Л А Л А А А гЧ • н Ч ^ Ч— Ч_ ^ Δ Ч - <* Л, А * - * 43 · * 3 « 43 · -43 · 43 * 43 * 43 * 43 * 43 * 43 * 43 * 43 · г — 1 А А гЧ гЧ н гЧ гЧ А гЧ гЧ • Н • ч ^ ♦ Чч «Ч Гч Г » • -ч * ч «Ч ГЧ г- о О О О о о о О о О о о IN IN IN IN IN IN IN IN IN IN IN IN X ф no хп Ф 2 хп х-ч о * —Ч ^ • Ч ко <ч о ^ -ч ^ • У г — ч г-ч х-ч X о о ГЧ О • ч о о о о о N X • -Ч ^ -ч ч ^ Ч 43 · * ч ко »Ч ГЧ г- ϋ кО гЧ со А н со ко ко ко X л 1 1 л л А А гЧ А л А А «Ч А А О 'Ь • С 1 О * ч - <* 4- ^ Ч— * of 4 ^> с ₄ ^ч >> 43 · 43 · 43 · 43 · 43 « 43 * 43 · 43 · 43 * 43 * 41 · 43 · ф а А А А гЧ гЧ гЧ А X А А гЧ А ► ф »4. · - • ч • ч. • ч · - Г * - · - »> 4 г *. о ► О о О о о о О О О О о О X о IN IN IN IN IN IN IN IN IN IN IN IN ф ГЧ X вч ► * О W Ом г · о О * - » ГЧ. ч > —Ч ^ -Ч • ч ^ -Ч х-ч гЧ Ч * —Ч Х-Ч 43 * о Г ^ · ГЧ 00 о о со о м со ω со А • -Ч Гч А Г " · —- ► > и < А 55 я Г \ ГЧ см ГЧ / л см н гЧ • о » Р ч> * - * 4- ^ ч— * »- » ч / ч * о кО кО со 43 · кО 43 * о ГЧ ГЧ • Μ * 00 and в со Ш со кО 43 * ю со 43 * А ГЧ кО ω ф • ч .. • ч г> · - г— г— г * • _ Ό Ό О о о А О о о о о А ГЧ гЧ Ф Ф л > β > й «Р Р No. ю

47 43 « 43 · гЧ ш ГЧ 43 * 43 · гч 43 « 43 * 43 * 00 «Н <Н о о гЧ гч кА гЧ гч гч гч  · «- * - * - • ч ь » · - г * г О о о гЧ ГЧ н гч гЧ н гч гч гч IN IN л А л

ÍÚ X о и и: p

д «3 н <м со 43 * кА кО Г * 00

I.E I.E Ό I.E Ό Ф I.E тз <0 ф > Ф Ф ф гЧ ф ω Ф гЧ VJ Н А гЧ X гЧ г-1 гЧ нч X X X X X X X | М> й Z4 м- X X > й X X X > й > й > й а > й > й Ь-Ц Ом. Рм Ом CU а Р <

226 730 о. ю • гэ о м • го

>> >> -Р о а Ό о эд

- 33 226 730

With respect to the values in Table V, it is recalled that? all active compounds of the invention have a significantly higher safety factor in diabetes than all other compounds known in the art. Particular attention is directed to the safety factor of the compounds of Examples 1, 3 and 6 to 8, which is 2.2 to; more than 16 times greater than the safety factor of the compounds of the invention. In addition to having a greater safety factor, the compounds of the invention have a uniform and superior selectivity factor than the prior art compounds except in individual cases, and the selectivity facts of the C-compound are slightly larger than the compounds according to Example 7 with respect to oat, deaf, somewhat greater selectivity factor than the compounds of Example 4 and the same as the compound of Example 6 with respect to foxtail. It is recalled that compounds known as E, H and M fail to selectively with respect to crop plants when used against deaf oat and foxtail, and that the selectivity of compounds referred to as E and H over the remaining plants is questionable. or at best slight; in any case, the low safety factors of these compounds show that these compounds are not suitable as herbicidal agents for the cultivation of diabetes.

Since the pre-emergence herbicidal activity values in Table IV and V are obtained using the same test procedure, it is possible to compare the herbicidal activity of the compounds of the invention listed in Table IV with those known from the prior art.

34 226 730 prior art. Again, it is clearly shown that each of the compounds of the present invention is superior to all compounds closest related and known in the art with respect to safety for crop plants without any exception and with respect to for the selective control of weed plants; is apparent from the factors of addition; again, with the exception of individual cases. Therefore, the additive factor of the special compounds known from the prior art / against certain weed plants. may be greater than certain compounds of the invention; but in each such. If the lower factor is poor for diabetes, these compounds known in the art are unsuitable as herbicidal agents for diabetes. seeeetivity (2.0). of the compound designated by the letter. B (Table IV) against Deaf oat in sugar beet is greater than for the compounds of Examples 7 and 8 / 1.0 µl, as shown in Table V. However, the factors. the safety of both of these compounds. they are 8 times greater than the compounds designated by B in the lactose and the selectivity factors of these compounds of the invention are at least 4 times greater than the additive factors of the compound referred to by letter B against the porcupine field foxes and the same as compounds designated by the letter B, field foxes ·

In yet another comparative test, the herbicidal activity of the compound of the invention. . of Example 1 and the compounds designated by the letters I. p J were tested. with regard to the effectiveness against deaf ears, the blood-throat of the leg, the blood-throat, the scribe

226 730 field and against scribe. The results of this test (representing the center of two repeated tests) are shown in Table VI; results read 48 days after treatment; the selectivity factors are in parentheses below the GRg hodnot values for each weed plant.

Table VI

Sou> Čenina by? example GEL _{For a} dose of 1 5 kg / ha of diabetes and wo X <1 * 12 0.35 * /> 3,2 / . AND <0.28 л> 0.99 • / NS / J <0.21 0.28 / NS /

Excellent priority

GI JBYG dose kg / ha LCG BG ΥΈΊ 4 0.14 <0.14 <0.14 <0.14 /? а, о / /> 8.0 / /> 8.0 / /> 8,0 / Z0, l < <0.14 0.21 <0,14? /^.,0/ 0 /// 0., 3 / /.^2,.0/ <0.14 <0.14 0.21 <0.14 Ad, 5 / Al, 5 / / NS / / 1,5 /

the compounds of Example 1 with respect to the compounds designated by I and J are illustrated with respect to the safety factor and selectivity with respect to all weeds tested; the compound designated by J is not selective with regard to deaf oats and field fox, and the compound designated with I is not selective with respect to deaf oats and is slightly selective with respect to foxtail in diabetes.

In one test, the compound of Example I was further tested

226,730 and the compounds labeled I and J with respect to downy brome (DB) with respect to Amaranth (R ‰) and annual rye (AR) in diabetes at the doses used in the art 0.07-1.12 kg / ha (0.0625-1.0 lb / A) was observed 18 days after treatment. The results of these tests are shown in Table VII; selectivity factors are shown in brackets below each weed plant.

Table VII

Fuse GR _4C . dose DB QRok dose kf? Ha RRP AR nina kg / ha of sugar beet according to at- • I put 1> 1.12 0,077 / 1,12 4’0.09 /> 16,0 / / - / / řl2,0 / AND 0.07 £ 0.14 0.07 0.28 / NS / / 1,0 / / NS / <0,07 / 40.09 40.07 ✓ Z 0.07 / NS / / - / / - / Values obtained even during the test, show that compounds

marked I and J adversely affect diabetes at doses lower than 0.07 kg / ha or less, and that the compound marked I is non-selective with respect to downy brome and annual rye, while the compound designated by the letter J is non-selective with respect to brome:

- 37 · 226 730 (downy brome) at low or unspecified doses below: 0.07 ke / ha · In contrast, the compound of Example 1 is safe for diabetes at a dose of 1.12 ke / ha / maximum test dose / at selective the destruction of bark beetle (downy brome) and annual rye (annuual rye) with a TEE of approximately 16 and 12, however, the destructive effect on bent-tailed pigworm is less than or not determined at a dose above 1.12 ke / ha.

Another test is carried out in a greenhouse to compare the compounds of Examples 2 and 5 with the compounds designated K and D, respectively. that is, to compare compounds most closely related. The compounds of the invention, Example 2 and the compound designated K, are characterized by an isopropyl group in one ortho position, an 11-alkoxy group in another ortho position, and a 11-alkoxyalkyl group on an α 1 H 2 and n 1 nitrogen atom. The compound denoted by D and the compound of Example 5 are characterized by 1, 2, 4, 6, 7, 7, 9, 9, 11, 11, 11, 11, 11, 11, 11, 11, 11, 12 at a nitrogen atom and a methyl group in ortho position. Hetbicidal compositions are applied to plants at a dose in the range of 0.07 to 1.12 ke / ha; Observations are made 19 days after treatment: The results are in Table VIII,

T a b at 1 k a VIII 226 730 Merge- · GR,> batch GR ₈₅ doses nina kg / ha WO BYG kg / ha LOG BG YFT according to the plan at- 2> 1.12 0,14- <0.07 0.07 0.24 Z 0.07 /> 8.0 / /> 16.0 / 160 160 > 4,7 / > 16,0 / TO 0.19 0.07 <0.07 <007 0.49 <0.07 / 2,7 / / 2,7 / / 2,7 / / NS / / 2,7 / according to the plan at- 5 1.12 0.14 <0.07 Z 0.07 0.78 0.09 / 8.0 / /> 16.0 / /> 16,0 / / 1,4 / / 11 * 1 / D 0.19 0.19 <0.07 <0.07 0.56 <0.07 / 1,0 / /> 3,7 / /> 2,7 / / NS / > 2,7 /

The values in Table VIII clearly show that the compounds of the invention have an excellent property with respect to the compounds designated by the letters D and K known in the art. Especially, the compounds of Examples 2 and 5 are safe when used in the cultivation of tincture at doses of 1.12 kg / ha and above, whereas the compounds referred to in letters D and K only exhibit doses of GR i. kg / ha. In addition, factors of seeedness. The compounds according to the invention exceed several times the known factors of the compounds of the prior art with respect to all the weeds tested in diabetes; · Compounds,

39 226 730 known from the prior art are non-selective with regard to foxtail in diabetes.

Other tests are performed to determine the superior herbicidal properties of other compounds of the invention. In a series of greenhouse tests, the compounds of Examples 9-12 were tested for deaf oats (WO), hedgehog (BYG). bloody dew (LCG), field fox (BG) and fox ´ YFT / in diabetes; the test results are given in Table IX.

T and Bulk IX

Combine GR.c dose θ ^Κ 85 dose

Sodium ^{kg / ha kg / ha}

P ^x 4 mm WOrYG T.CG

example diabetes WO BYG LCG BG YFT 9 ^a 1.0 0.55 / 1,8 / <0.14 / 7,1 / <0.14 / 7,1 / 0.19 / 5,2 / <0.14 / 7,1 / 10 ^ > 1.12 0.34 /> 3,3 / 40.14 / 78,0 / <0.14 / 78,0 / 4 0.14 / £> 8.0 / <0.14 /> 8,0 / II ^е / 1,12 0.19 /> 5,9 / <0.14 / 78,0 / <0.14 /> 8,0 / <0.14 /> 8,0 / <0.14 /> 8,0 / 12 > 1.12 0.84 // 1,3 / 40.14 <> 0,0 / 0.14 /> 8,0 / <0.14 /? 8.0 / 0.14 /> 8.0

values are the center of four repeated tests values are the center of two repeated tests values are the center of three repeated tests

- 40 226 730

Again, the compounds of the invention showed a higher herbicidal action before emergence, both in absolute and relative proportions with respect to the properties of the closest similar compounds known in the art /, as can be seen from Tables IV to VIII with regard to crop safety factors, unit efficiency, weed control, and crop / weed selectivity factors.

As noted above, the values for the test compounds in numerous assays were selected from herbicide application rates in the art of 0.14 to 1.12 kg / ha (0.125 to 1.0 Ib). However, additional tests on selected compounds of the present invention have shown safety for diabetes at doses of at least 4.48 kg / ha and selective control of various weed plants in juices. less than 0.07 kg / ha. For example, the compound of Example 1 exhibits selective control of more resistant weed and downy brome weeds and less resistant weed plants of the hedgehog cornices, bloody dew, foxtail and annual rye (annula rye) at doses less than 0.07 kg / ha. Similarly, other compounds of the invention also kill poison or several of the aforementioned less resistant weed plants at 0.07 kg / ha.

_K In the field test, the relative safety for bukrovkw and the weed control ability is assessed; the compound of Example 1 and compounds known in the art were tested,

226 730 marked with letters (Cj £ а M ее with regard to the hedgehog corns the foot) and the green foxtail (for application on the surface) and for the introduction in front of the plant ("VPP") in doses in the range 1.12 to 4 48 kg / ha. The treatment is carried out on Raye dust soil containing 1.8% of organic matter; The conditions correspond to a relative drought of only 0.03 cm of rain fell within the first 7 days after treatment · The results of the field test are given in Table X ·

E a b u 1 к a X P Г i ocel n t o v á i n h i b i c E Slou- Dose Sugar ovka Ježatka corns foot Psárka č enina kg / ha VPP PK VPP PN VPP PN according to 1.12 0 0 85 27 Mar: 85 57 example · du 1 ’2.24. 10 3 92 48 92 65 4.48 12 13 98 78 98 85 C 1.12 10 5 78 42 88 77 2.24 22nd 18 87 77 / 93 87 4.48 57 25 98 90 98 88 £ 1.12 30 30 87 68 88 85 2.24 80 63 100 ALIGN! 95 100 ALIGN! 95 4.48 100 ALIGN! 90 100 ALIGN! 98 100 ALIGN! 97 1.12 15 Dec 25 95 40 95 62 2.24 30 23 100 ALIGN! 78 100 ALIGN! 85 4.48 63 45 100 ALIGN! 93 100 ALIGN! 92

With respect to the values in Table X, it is recalled that all test compounds, except the compound according to

226 730 of Example 1 are harmful to diabetes, wherein = the compound of Example 1 is safe (i.e., damage up to 15%) for diabetes at doses up to at least 4.48 kg / ha (maximum test dose) with selective destruction as hedgehog chicken feet and foxtail (greten foxtail) at a dose of 1.12 kg / ha under the conditions of introduction of db of the soil in front of the plant ( ^И УРР ^И ); none of the prior art compounds selectively kills any weed plants at a dose of 2.24 kg / ha; the compounds do not selectively destroy both weeds under VPP conditions at a dose of 1.12 kg / ha but have poor tolerance to the crop plant.

The compound of Example 1 was also tested in field conditions to determine pre-emergence selectivity with respect to foxtail (spp), corn ear (BYG) and millet in a variety of crop plants; value / representative! three replicates (shown in Table XI) for both application on the soil (РЫ) and for introduction into the soil before the plant (VPP) of the herbicidal composition. Seeds are sewn into dusty soil under moderate humidity conditions. The seeds are sewn to a depth of 5.08 cm. The first 0.51 cm rainfall comes the day after treatment, the second 0.64 cm rainfall comes two days after treatment. Cumulative rainfall, 22 days after treatment corresponds to 4.57 cm. Observations are made 6 weeks after treatment *.

Individual letters have the following meaning in Table XI: RČ - tomato, OK - cucumber, PO - peanuts, BV - barrel, soy - L, M - diabetes, Ř - rapeseed, YFT - psařka, BGř hedgehog corns, BP - millet / white millet Millet / ·

P <CQ

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СО СЧ co co

CO oo 04 04

226 730

СО 1Л co 40 00 04 05

CO Lf> О * r * r * 04 04 inhibition

- 44 228 730

The values in Table XI show that the compound of Example 1 generally has the same potency when applied to soil surface (PN) i. To soil (VPP) at a dose. 4.48 kg / ha / except in the case of killing for tomatoes, cucumber and millet at a dose of 4.48 kg / ha VPPj and against scribe and barley corn at a dose · P, 58 kg / ha / · Especially ua · of the PN-compound, the compound of Example 1 selectively kills foxtail and barley corn in all test chicken plants at doses slightly above; 1.12 kg / ha and millet at a rate of 4.48 kg / ha. Under VPP conditions, the barley leg is selectively destroyed at a rate of 1.12 kg / ha and a typist at a rate of 1.12 and 2.24 kg / ha, and for crop safety up to 4.48 kg / ha for all cultivated plants. With the exception of tomato, cucumber and shrub bean.

A significant predicament of the herbicidal composition is its merchantability in a wide variety of soil types. Therefore, the values in Table XII show a comparative herbicidal effect of the compound of Example 1 and the compounds labeled C and M on different annual grasses in diabetes. content of organic substances and clay. In these tests, the mugs are filled with Rayei working soil, stoked at · 0.95 cm from the rim of the mug, seared with diabetes, noisy oats, barley chicken legs,. bloody tree fescue, blackgrass and foxtail these seeds are covered with 0.127 cm of soil from Reaye, mud from Florida, sand from Florida, clay · Wabash, dusty Drummer soil or hard clay Sarpy. The herbicide was applied by spraying twice with a sprayer at a rate of 187 liters / ha under a pressure of 207 kPa by the method of surface application. 0.64 cm of irrigation was added to each cup before being placed on the greenhouse shelves for subsequent irrigation from below. Observations are made 15 days after painting. The results for the test soil are predicted to be the midpoints of the two replicate tests, as shown in Table XII; seeectivity factors are given in parentheses after the dose values GR for weeds. The types of soil tested are as follows:

P г ocentový obs and h Type of soil Organic Substance-Of CLAY Dust Sand PH value AND great soil from Ray. 1,2 6.4 74.8 18.8 6.5 (B) Mud from Florida 22.1 N® ^and Na? No ^and 5.2 C Sand from Florida 2.3 1,8 No? No ^and 6.1 D Drnmmer dusty soil 3.6 12.4 52.8 34.8 7.0 E Clay Wabash. 2,7 / 44.4 34.8 20.8 6.2

^ .. is not

In the following Table XII, the individual soils are designated by the abovementioned letters, which have the meaning given above.

226 736

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О χ-χχ-χ х-х х-ч —Ч —X —ч Х-Х Х -Ч —X г * г * г * · • _ч о о О О -х • ЧОО • х ·> Х кО • χ ч ♦ ч «х А о гч сч • Ч * 0 * СЧ 1 СЧ <4 сч <4 Δ ^ χχχ Δχ- чф ХГ чф чт чт «г Гч СЧ 40 • Ч чТ чф r-Ч гЧ гЧ гчсч сч О гЧ Ш гч »ч» ч • X «Ч • 'Х • х »4 А А А * χ ООО ГЧ сч сч • ч «ч о о о о v v V А IN х-х о о х-ч к ·> ч х · Ζ4 г * kD чт - —Ч хч Ч — ч х-ч т · ' ю ťgg Х- * ’х-’ Х- * чт чо чф ЧТ ЧТ чф чф чф СО 40 СО гЧ гЧ Ш СЧ СЧ СЧ сч сч сч СЧ Ш 40 · * · Χ К * х «ч * х * х * Х ' .г ·· ГЧ х ООО см см см сч ГЧ сч ООН АЛЛ Л А А ZX О Х-Х-Х —X —X о чО О -X О х-х о о * х х> 40 · χ * х А • \ ххч 40 —чЧф гЧ Т СЧ 1 гЧ 1 сч гч ω • ч ω * ч Л А А ^ А ^ Ч- * хх · Д, gH * · * ' XX-Х XX XX Чф Чф Чф ЧУ чф чф сч сч м чф 40 СО гЧ сч сч сч гЧ »Ч СЧ нш сч · - * 4. »*. • X. · *. »* Ч _ гч X Гх • х · χ. ООО сч сч сч • Ч гЧ СЧ ООО IN А А · IN х-ч х-ч х-х Х-Ч '' О О Х-Ч г * с < , хО х * х —ч —ч о 40 чф · χ О гч Г * _Ah гЧ СЧ 1 1 1 οΓω ω • Ч * - - λΔδ д ss д х ^ сч X— Х-Х хх чф -чф чф ТТ Чф Чф СЧ чф чт • ч ’чф «Ч ЧЧЧ сч сч сч • ч сч сч СЧ гЧ н · - X .. X • х * 4 Чч. · - X. * «X. * Х ООО сч сч сч • ч гч сч ООО V V V А А А А х-ч -> хх хч —X О О z-х — X XX. —X • х — ч XX » • ми 1 1 1 I ω ω сч ω ω C1SS ASS СЧ СЧ СЧ чф чт чф Чф Чф Чф см см см гЧ СЧ СЧ СЧ сч сч сч • Ч гЧ гЧ «Х. Xχ, «X • х · χ 4> ч ►χ · χ. · Χ · *. «X гЧ сч сч сч сч сч сч • 4 4 » А АЛ л л

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А

- 00 00 СЧ со со * х · 'гм о о л added 0.56 2.24 (NS) 0.52 (1.1) 0.56 (1.0) 2.24 (NS) 0.43 (1.3 )

С _х 1.12 1.12 (1.0) 0.28 (4.0) 0.56 (2.0) 1.12 (1.0) 0.28 (4.0)

М 1.68> 2.24 (NS) 0.28 (> 6.0) 0.96 (> 1.8)> 2.24 (NS) 0.56 (> 3.0)

- 47/226 730

The values in Table XII show that the compound of the example. 1 has significantly higher 'security. for '.cukrovku higher than facto selektivity- compounds, designated by the letters C and' M with respect 'to all the weed Roštín _/,: avšik with - the two. minor exceptions /, in three of the five soil types, that is, in the dusty soil of Rat, in the sand of Florida ,,, and, in, 'clay' Wabash. In particular, the compound of Example 1 is the only selective compound for controlling oat deaf, in Ray's dusty soil and in Wabasb clay, for controlling hedgehog corns in the sand of 'Florxdy' and groundbuckle in clay, Wabash. Rather, the results are; Indefinite in Florida mud (22.1% organic matter). however, at high test rates, soils with a high organic content should reduce the potency of each test compound. The compound of Example 1 does not have the same potency in dusty Drummer soil as the compounds known in the art, but generally have higher potency in different soil types. - · »

For laboratory tests, the determination is relative. And. .

odoojnost. of the herbicidal compositions according to the invention and the compounds known from the state of the art are incorporated into the soil leaching and have an herbicidal activity. In these tests, the compounds of Example 1 and the compounds designated C and M were injected in acetone and injected.

of various concentrations of the weighed soil contained in the pot. maícíc. The filter paper covered with the outlet opening at the bottom of the cup. Mugs containing edited

228 730 soil, are, leached, placed, on a rotating table · · that rotates underneath! two ·, types ·· tank nozzles? to water calibrated to discharge 2.5 cm of water per hour to mimic the past · Extraction rates are set by varying the time on the turntable · Water introduced into the soil · Allowed to flow · Filter paper, mug outlet · Mugs do not finish after · The treated soil in the pots is then removed, crumbled, and placed as a coating on top of »other mugs containing Ray dust, sown with diabetes, but oatmeal (WO). hedgehog (BYG), bloody dew · WG, greengrass (BG) and greengrass (YFT) · The mugs are then placed on shelves in the greenhouse, watered from the bottom and the seeds do not feel any growth. visual assessment of percent growth · Test compound values represent the center of two repeat tests · Test results · See Table XIII · The same abbreviations as above tables and as mentioned above ·

22В 730

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226 736

The values in Table XIII show that the compound of Example 1 is safe for lactose and up to at least a dose of 2.24 kg / ha and selectively kills all weed test plants under a 10.16 cm simulated rainfall except for deaf oats ® which is destroyed up to 7.62 cm. At a dose of 2.24 kg / ha, the compounds labeled С and M damage diabetes up to a dilution of 5.08 cm of rainfall, under which condition the compound labeled C does not selectively destroy the deaf compound or the compound labeled M , does not selectively destroy the common fox. Using the lowest dose / herbicidal composition, 0.14 kg / ha, the compound of Example 1 selectively kills all weeds under the tested rainfall conditions up to 1.27 cm and the hedgehog chicken leg, bloody dew and feathertail up to 5.08 cm rainfall. In contrast, at a dose of 0.14 kg / ha, neither the C compound nor the M compound selectively destroys field fox, nor the C compound selectively destroys deaf oats under all rainfall conditions, and both they lose selectivity with respect to all weeds in sugar beet at 5.08 cm rainfall. Thus, it is clearly shown that the compounds of the invention are much more resistant to leaching into the soil under varying rainfall conditions than the compounds of the prior art and thus provide a much more reliable and prolonged herbicidal action.

Finally, to further substantiate the unusual nature of the

52BB 730 of the unexpectedly superior properties of the compounds of the present invention are given in Table XIV further values of the herbicidal action of the pre. vZejiíími. for other compounds of similar structure including homologues of the compounds of the invention. Letters N 'to T in the board? XIV has the following meaning:

N. N- (isopropoxymethyl) -2'-methoxy-6'-methyl-2-methyl-2-carboxylic acid,

O. N- (isobutoxymethyl) -2 * -ethoxy-2 ·· chloraceeanilide _r

P. N- (Isobutoxymethyl) -2-methyl-2-hydroxy-2-carboxamide:

Q. N / isobutoxymeelh ^R l / 2 ^_ * 6 * -ílethoxy -meehhl -chlorac etanílid-2,.

R. N / ethoxlmeei: hl / -2'-methoxy-6 &apos;_{-methyl-2-chloracetthailid>}

S. N- (1-Ethyropropolylthiyl) -2-methyl-6-methyl-2-chloro-5H-ethanediamine

T. N- (ethoxylmethyl) -2'-isopropoxy-6'-trans-2-chloroacetanilide.

о со

В и »м

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226 730

хч КО ХЧ хч ХЧ ХЧ о ч хч • ч хЧ 1 1 со 1 | см А 52 А / \ чх чх чх чх чх ЧХ чх КГ ”3 * г * м * гЧ Г-Ч г — 4 г-4 о о Г-Ч * ч * ч ♦ ч • ч Ч ч О о О о о о о

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- 54 226 730

It will be appreciated that the compounds designated by the letters N to T1. like the compounds of Examples 1 to 12, they are within the general scope of the aforementioned U.S. Patents Nos. 3,442,945 and 3,547,620, but are not specifically disclosed. Therefore, it would be expected that species of compounds of the kind of compounds protected by the aforementioned US patents would generally have comparable herbicidal properties. However, the perfectly unexpected and excellent type properties of the compounds of the present invention with respect to homologous and closely related compounds (The compound circles are further exemplified by the values for the compounds designated by the letters K to T in Table XIV). other compounds known in the art, as shown in particular in Tables IV to VIII, have a very low safety factor for diabetes, as is apparent from the doses of GR &lt; 4 &gt; used.

In addition, none of the compounds listed in Table XIV have a selective destructive effect on deaf ears in diabetes. It is also interesting that the compound designated P is non-selective against any of the weeds tested and that similarly the compound designated N, 0, Q and R is perfectly non-selective and / or slightly selective with respect to all weeds tested. Of the compounds in Table XIV, only the S and T compounds have a selective destructive effect on the hedgehog of corn, bloody dew and field fox and foxtail. However, it is again recalled that unacceptably:

55 226 730 low tolerability for diabetes of the S and T compounds is associated with non-selectivity with regard to deaf oats and with low selectivity with respect to other weed species tested, and therefore these compounds are completely unacceptable as herbicidal agents for diabetes. In addition, it is recalled (with respect to the values in Tables IV to VIII) that: the safety factors in diabetes and the selectivity factors for the compounds according to the invention with respect to the abovementioned weed plants are surprisingly better than those designated S and T _e

Thus, it is fully understood that the compounds of the present invention have unexpectedly and excelledly demonstrated superior herbicidal properties both absolutely and comparatively with respect to the most structurally related compounds, other related homologues and analogs including the prior art 2-haloacetanilide formulations. In particular, the compounds according to the invention have shown excellent harmlessness to diabetes and selectivity factors, particularly with regard to hard-to-control weed plants such as deaf oats, fox-tail, fox-tail and brome and other difficult weed plants such as hedgehog, annual rye and similar plants as exemplified in Tables II to X.

The herbicidal compositions of the invention include concentrates which must be diluted prior to use, comprising at least one active ingredient and excipients; in liquid or solid form. The herbicidal compositions of the present invention

56,226,730 prepared by mixing the active ingredient with excipients - including. . diluents, extenders, carriers and conditioning agents to form finely divided solid particles, granules, pellets, suspension or dispersion solutions. The active ingredients can now be used with an adjuvant such as a finely divided solid, liquid of organic origin, water, a darkening agent, a dispersing agent, an emulsifying agent or any suitable mixture of these.

Heebicidal compositions according to the invention,. in particular liquids and compatible powders, preferably contain a conditioning agent, one or more surface-active agents in sufficient quantity. so that the mixture is readily dispersed in water or oil. The surfactants of the herbicidal composition according to the invention greatly enhance its effectiveness. The term surfactant is. is understood to mean mixtures, dispersing agents, suspending agents and emulsifying agents. Anionic, cationic - or nonionic agents can be used equally easily.

Preferred wetting agents include the alkylsulphine sulphates and alkylphthalene salts, sulphated fatty alcohols, amines or midylacetate, long-chain sodium isothionate esters, sodium sulfosuccinate esters _of sulphated or sulphonated fatty acid sulphonates. , sulfonated vegetable oils, di-tertiary acetylenic glycols, polylxytthylene derivatives of alkylphenols (especially isooctylpheno- and nonylphenol) and polyo-yethylene derivatives

226,730 mono-higher fatty acid esters of hexitolanohydride / such as e.g. sorbitan /. Preferred dispersing agents are methyleeluloza, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonates and polymethylene bisnaphthalenesulfonates.

Wettable powders are water dispersible mixtures containing one or more active ingredients, an inert solid extender and one or more wetting agents and dispersing agents. Inert solid extenders are rules of a mineral origin such as clays, diatomaceous earth and synthetic minerals derived from silica and the like. examples of such extenders include kaolinity, attapulgite clay and synthetic magnesium silicate. The wettable powder compositions according to the invention generally contain 0.5 to 60 parts, preferably 5 to 20 parts active substance, about 0.25 to 25 parts, preferably 1 to 15 parts wetting agent, about 0.25 to 25 parts, preferably 1.0 to 15 parts of a dispersant and about 5 to 95 parts, preferably 5 to 50 parts of an inert solid extender, all parts being by weight and referring to the weight of the herbicidal composition as a whole, or about 0.1 to 2, Parts of the solid inert extender may be replaced by a corrosion inhibitor, or by an anti-foaming agent or by these agents.

^u akožto Other formulations include dust

58 226 730 concentrates containing 0.1 to 60% by weight of active ingredient on a suitable extender; these powders may be diluted for use in concentrations of about 0.1 to about 10 weight percent

Aqueous suspensions or emulsions can be prepared by mixing an aqueous mixture of a water-soluble active ingredient and an emulsifying agent until uniformly dispersed and then homogenizing to form an emulsion of finely divided particles. The resulting concentrated aqueous suspension is characterized by an extremely small particle size, so that after dilution and spraying it provides a very uniform coating. Suitable concentrations are about 0.1 to 6.0%, preferably 5 to 50%, by weight of the active ingredient, the upper limit being determined by the solubility limit of the active agent in the solvent.

In another form of the aqueous suspension, the water-immiscible herbicide is encapsulated to form a microcapsule phase dispersed in the aqueous phase. In one embodiment, tiny capsules are formed by contacting an aqueous phase comprising a lignin sulfonate emulsifier and a water-immiscible agent and a polymethylene polyphenylisocyanate, dispersing the water-immiscible phase in the aqueous phase and then adding the polyfunctional amine. The isocyanate and amine compounds interact to form a solid urea shell wall around particles of a water immiscible chemical to form microcapsules therefrom. Generally, the concentration of the microencapsulated material is about 480 to 700 g / liter of the composition as a whole, preferably

59 is 480-600 g / liter.

226 730

Concentrates are generally solutions of the active ingredient in a water-immiscible or partially water-miscible solvent containing a surfactant. Suitable solvents for the active ingredients of this invention include dimethylformamide _R dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters and ketones. However, other highly concentrated concentrates may be prepared by dissolving the active ingredient in a solvent and then diluting it, for example, with kerosene to a sprayable concentration,

The concentrate compositions generally contain 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 surfactant and optionally 4 to 94 parts of solvent, all parts being meant by weight and refer to the total weight of the emulsifiable oil.

Granules are physically stable particulate formulations containing the active ingredient adhered or dispersed in a matrix of an inert, finely divided, particulate carrier. As a rule, to assist in the leaching of the active ingredient from the particles, such compositions comprise a surfactant of the above type. Examples of suitable classes of particulate mineral extenders include natural clays, pyrophyllites, illite and vermiculite. Preferred extenders are porous, adsorptive, preformed particles.

- 60 22β 730 such as preformed and sieved attapulgite particles, or heat expanded vermiculite particles and finely scattered clays such as kaolinite clays, hydrated attapulgite or bentooitic clays. granulate.

The granulated herbicidal compositions of the invention may contain about 0.1 to 30 parts, preferably about 3 to 20 parts by weight of active ingredient per 100 parts by weight of clay and 0 to 5 parts by weight of surfactant per 100 parts by weight of clay particles.

The herbicidal compositions of the present invention may also contain other ingredients such as fertilizers, other herbicidal compositions, other pesticidal compositions, safety ingredients and the like as excipients or in admixture with the aforementioned excipients. Chemicals useful in the compositions of the present invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ether, and the like such as :

Nitrogen / sulfur-containing heterocyclic derivatives 2-chloro-4-ethylamino-6-isopropylamino-sym-triazine, 2-chloro-4,6-bis (isopropylamino) -sym-triazine,

2-chloro-4,6-bis (ethylamino) -symtriazine,

3-Isopropyl-1H-2,1,3-benzothiadiazin-4- (3H) -d 2,2-dioxazine.

3-amino "4.2 l _t-triazole, _"""

6,7-dihydrodipyrido / l, 2-a: 2 ', 14-c / pyrazidiinii ^ _r ^^ salt of a bromo -434í ^ ^ C ^ R ^ rc ^ ^ 4 propyl- meteij ^^ <^ uracil, 1,1 * idiniethdl-4,4 * -bi / dridinium salt.

Ureas

N ^from -C4-corudor-inoxh-ihyd-N, - ^τ 6dimehУ _< ydmččvv-nCo

N, N-dimethyde-N-β-quin-4-teethdiendl / drug

3 [beta] (3,4-dichlorophenyl) -1,6-dimethylamino-active

1,3-iieiehhy343- / b-iinzhtCiczolmlmichonCna,

Зо-су ^ ОСогТ ennl / -0,6-dieiehhyliiOchivinCo

1-Buyl-3- [3,4-dCchior-3-chloro-1-ethanediurea _t

KarbamltyhtУ-Articlekabbamáth

O-chlralldldeethyddithioCcbCamate,

S- (4-cydorobenzyl) -1-N-diethylthiolCabbamato

- soprop / d-N-C3-chlorophenylcOk-Arbc / lt,

S-2.03-d ichdorc ddy-10, N-di10 / thioocabbamate, ethyl-N, N-dihydro-4-oxoylthiol cabbamate, S-prop / d-di / dioylth10Coababamate.

Ac - {, с / 1.6уСсс etcnilidd / cmi-iocCamidd

O-chloro-N-N-diclldCaceCamido

N, N-dimethyl-2, O-6-phenyl-lactate / ii,

N- / C-04-6met yto5- / ~~ 'c / trifluirmeehyd / iuifindl _^ 7 ^{amino4^О,} -П1] _^) ^ с с ^ -' ^ ^ с 1-6о

- 62 N-isopropyl-2-chloroacetanilide

226 730 6 * ₁ * -diethyl-N-methoxymethyl-2-chloroacetanilide methyl _R! E ^/ -ethyl-N .- / 2-methoxyprop-2-yl / -2-chloroacetanilide ;, alpha, alpha, alpha trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine, N- (1,1-dimethylpropynyl) -3,5-dichlorobenzenamide.

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-2,5-dichlorobenzoic acid,

2.3.6- trichlorophenylacetic acid,

N-1-naphthylphthalamic acid,

Sodium 5- (2-chloro-4- (trifluoromethyl) phenoxy) -7-2-nitrobenzoate,

4,6-dinitro-o-sec-butylphenol,

N-phosphonomethyl / glycine and its monoalkylamine having 1 to 6 atoms / carbon and alkali metal salts and mixtures thereof.

Ethers

2,4-dichlorophenyl-4-nitrophenyl ether,

2-chloro-alpha, alpha, alpha-trifluoro-o-tolyl-3-ethoxy-4-nitrodiphenyl ether. _t

Different

2,6-dichlorobenzonitrile, monosodium hydrogen methanarsonate, disodium methanarsonate.

бз 226 730 ^d as fertilizers suitable for use in admixture with the active compounds according to the invention are, for example, ammonium nitrate, urea, potash and superphosphate. Other suitable additives include materials in which plant organisms are grown and in which they grow, such as compost, fertilizer, humus, sand and the like.

The herbicidal compositions described above are exemplified by:

are further

1. Emulsifiable concentrates% by weight

A. Example compound 150.0

A mixture of potassium dodecylbenzenesulfonate (polyethylene ethers) for example. Atlox ^R 3437F and Atlox 3438F / 5.0

Monochlorobenzene4 £> «0

100.0

B. Example 285.0

Kale iumdodecylbenzenesulfonate / plkylarylpolyetheralcohol

Aromatic hydrocarbon solvent of 9 carbon atoms 11.0

100.0

C. Compound of Example 11

A mixture of kaleium dodecylbenzenesulfonate / polyoxyethylene ethers (e.g., Atlox 3437F)

Xylene

5.0

1.0

94χ0

100.0

- 64,226,730

II. Liquid concentrates ·

AND. The compound ppHe of Example 1. % Шк ^ по ^ и! 10.0 Xylene 90.0 100.0 B. Compound according to example 2 85.0 Dime thyl sulfoxide  15 <.0 100.0 C. Example 11 compound 50.0 N-№eУppyиόlidln 100.0 D. Example 10 compound 5.0 Ethyl: ethyl castor oil 20.0 Rhodamin B · . 0.5 Diisopropylphenyl 1 (1 74.Л: 100.0

% hmoonootní

III. Emulsion

A. Compound of Example 340.0

The block copolymer of poly (ethylene) / poly (prlyl) with butanol / for example ' ^τ τ® ^ ϊο1 ^{Ρ χ} Η ^/ 4,

Water560

100.0

B. Snake Compound 45.0

Block copolymer. polyosoreethrrole / polyylpropylpropylene with iutanol 3, 5

Water91.5

100.0

IV. Wettable Powders /

A. Compound of Example 5

Sodium N-methyl-N-methyl-sodium sodium salt.

Amoofic silica (synthetic)

B. The compound of Example 6.

Sodium dioctylsulfosuccinam Calcium lionosiuonate Ammonium silicon dioxide (synthetic)

C. Compound of Example 7 Sodium Lionosulfonate, Sodium N-Methhl-N-ooeeytaurate Colinite Clay

V. Pills

A. Compound of Example 1

B. Compounds, according to Case 8

Monmmirilc ^ o ^ n · ^

C. Compound of Example 9

Beenoont

226 730% hmoonoot

25.0

3.0

1.0

71.0

100.0

80.0

1,25

2.75

16.00

100.0

10.0

3.0

1.0

86.0

100.0% by weight

2,0

...

100.0

60.0

40.0

100.0

30.0

77.0

100.0

D. Compound of Example 12

226 730% by weight

Kieselguhr

VI · Granules% by weight

A. Compound of Example 1 15.0 Granular attapulgite / 20/40 mesh / 85 <0 100, c B. The compound of Example 11 30.0 Kieselguhr / 20/40 / .70.0. 100.0 C. Compound of Example 10 0.5 Bentonite / 20/40 99.5 100.0 Compound of Example 3 5.0 Parof / 20/40 95.0 100.0 M ^x Crocodile % by weight A. Compound of Example 1 en- 49.2

encapsulated in polyurea shade

Sodium lignosulfonate (e.g. Reas 88 ^ B) 0.9

Water

ΪΟΟ, Ο

- 67 226 730% hmoonoot β · Compound according to example 12 encapsulated in polymorphic »envelope wall10,0

Potassium lignin sulphate / for example

Reax R 0-21 / 0.5

Water89.5

10 (0.0

C. Compound of Example 10 encapsulated in a pllymilic envelope wall 80.0

Magnesium lignlsulfate / for example.

Treas ^R LTM / 2.0

Water, 18.0

100.0

When the herbicidal compositions of the present invention are ingested, an effective amount of the acetoanide is introduced into the soil of the plant or into the aqueous medium by any conventional means. Treatment of the soil with liquid or particulate formulations is possible in any conventional manner, for example, with a powder sprayer, a boom and a hand sprayer and a sprayer. The herbicidal compositions may also be applied from the aircraft in the form of a powder or spray, as they are effective in small doses. Treatment of aquatic plants with the anti-bactericidal compositions of the present invention is generally accomplished by adding the compositions to the aquatic environment where it is desirable to destroy the aquatic plants.

- 68 226 730

The use of an effective amount of an active compound of the formula I according to the invention in a place where weed weeds is important and of decisive importance. The exact amount of active compound to be used depends on various factors, including the type of plant and its development, the type and conditions of the soil, the amount of rainfall, and the type of acetanilide used. For selective use before emergence of the plant or in the soil, doses of 0.02 to 10 are generally used

11.2 kg / ha, preferably 0.04 to 5.6 kg / ha or suitably 1.12 to 5.6 kg / ha. Lower or higher doses may be sufficient or may be desirable in certain cases. The skilled artisan can readily determine the optimum dose for each particular case based on the above.

The term soil is used herein in the broadest sense, and it includes all common soils' as defined in Webster New Internationa ^ Dietionary, II. published by Unabridgedi (1961). The term “soil” therefore refers to any substance or environment in which plants can be rooted and in which they can grow, and includes not only soil but »

also compost, mud, sludge, sand and similar substrates on which plants grow.

While the invention is described with reference to specific modifications, the details are not to be construed as limiting,

Claims (4)

A herbicidal composition comprising, in addition to adjuvants, a herbicidally effective amount of a compound of formula I II (I) where is R is an ethyl, n-propyl, isopropyl, isobutyl, allyl or butúenyl group, R 1 is methyl, n-propyl, isopropyl, n-butyl, isobutyl or isoamyl; and Rg is methyl, ethyl or isopropyl, provided that when Rg is isopropyl, it is R is ethyl ε R is n-butyl, when Rg is ethyl, R is ethyl, n-propyl or allyl and R ^ is n-butyl or isobutyl, when Rd is n-propyl isopropyl n-butyl or pyruvate, R 'is isobutyl, and when R is isopropyl, Rj is isobutyl, 226,730 when R is isobutyl, n-propyl, isopropyl, isobutyl or isoemyl; and when R is butanyl, R ^ is methyl; 2. A herbicidal composition as claimed in claim 1, characterized in that N- (n-propoxymethyl) -2'-isobutoxy-6-methyl-2-chlorination tannilide is the active substance. 3. A herbicidal composition according to claim 1, characterized in that: It contains N- (ethoxymethyl) -2'-isobutoxy as the active ingredient 6'-ethyl-2-chloroacetanilide · 4. A herbicidal composition as claimed in claim 1, wherein the active ingredient comprises a compound selected from the group consisting of a compound of formula I wherein R is alkyl and C2-4 or allyl and R3 is 3 or 4 alkyl. carbon atoms and Rg is as defined in point 1, a compound of formula I wherein R R is isobutyl, R 2 is C se-C alky alkyl or allyl and Rg is as defined in point 1, N- / 1 sabutoxymethyl (2'-Isobutoxy-6'-methyl-2-chloroacetanilide, H- (1-isopropoxymethyl) -2'-isobutoxy-6'-methyl 1-2-chloroacetanilide, N- (allyloxyHsethyl) -2 * N-ethoxymethyl-2'-n-butoxy-6'-isopropyl-2-chloroacetanilide, N- (laobutoxymethyl) -2'-isopropoxy-6'-methyl-2- chlorination of the folk, K- (isabutoxyiaethyl) -2'-n-proxy-6'-methyl-2-chloroacetanilide, N- (n-propoxymethyl) -2'-n-butoxy-6-methyl-2-chloroacetanilide, №- (allyloxymethyl) -2'-nb utoxy6 * -ethyl-2-chloroacetanilide.