NL8101325A - HERBICIDE 2-HALOGENENE ACETANILIDS. - Google Patents

Description

* Fish. v

M

Herbicide 2-haloacetanilides.

The invention relates to 2-haloacetanilides and to their use in the agronomic technique, for example as herbicides.

The literature relevant to this invention includes numerous statements of 2-haloacetanilides, which may be unsubstituted or substituted with a wide variety of substituents on the anilide nitrogen atom and on the anilide ring, including alkyl- , alkoxy, alkoxy-alkyl, halogen, etc., residues.

As relevant to the compounds of the invention which are characterized by the presence of an alkoxymethyl or alkenyloxymethyl residue on the anilide nitrogen atom, an alkoxy or alkenyloxy residue on the one ortho position and hydrogen or a specific alkyl residue in the other orthos, the closest references may be cited in U.S. Pat. Nos. 3,442,945 and 3,547,620. The most relevant disclosures in the above two patents are the compounds 2, tert-butyl-2-chloro-N-methoxy-methyl-6'-methoxyacetanilide and its bromine analog (Examples 18 and 34 of U.S. Patent 3,547,620 to Examples 18 and 36 of U.S. Patent 3,442,945, respectively).

United States Patents 4,070,389 and 4,152,137 disclose a general formula comprising compounds of the type disclosed in United States Patents 3,442,945 and 3,547,620. However, the only specifically mentioned compound having an alkyl radical in one ortho position and an alkoxy residue in the other ortho position contains an alkoxyethyl radical on the anilide nitrogen atom; compounds of this type are described in more detail below.

Other less relevant literature references are Belgian Patent 810,763 and West German Patent 8101325 V% -2 Application 2,402,983; the compounds of these references include compounds of the type disclosed in U.S. Pat. Nos. 4,070,389 and 4,152,137 mentioned above, and are characterized by an alkoxyalkyl radical having 2 or more carbon atoms between the anilide nitrogen atom and the oxygen atom of the alkoxy portion. The most relevant specific disclosures in the said Belgian patent 810,763 and the German patent application 2,402,983 appear to be the compounds with an ethoxyethyl radical on the anilide nitrogen atom, a methoxy or ethoxy radical on the one ortho-position and a methyl or isopropyl - rest in the other ortho place. In this connection, reference is made to Belgian patent 810,763, compounds 7, 16 and 18; other less relevant homologues of these compounds have also been reported, for example compounds 6, 9 and 17, which have 15 methoxyethyl or methoxypropyl radicals substituted on the nitrogen atom, and a methoxy or ethoxy radical in one ortho position and a methyl radical in the other ortho place.

The above-mentioned US Pat. No. 3,442,945, which discloses the above-mentioned compounds with a chemical configuration most closely related to the compounds of the invention, provides some herbicidal data therefor and provides some data for other homologs and analogous compounds, which are less closely related in chemical structure. Analogously, some data are provided for compounds 6 and 9, in said Belgian Patent Specification 810,763. More specifically, these most relevant references, while reporting a herbicidal activity on a variety of weeds, do not provide data at all for compounds which have been found to additionally and / or simultaneously control the difficult to control narrow-leaf weeds , Johnsongras seedlings and / or brittle reed (shattercane), both of which belong to the same plant genus as sorghum, and other hard-to-kill weeds, such as redroot ("redroot"), pork grass and wild pseudo-millet ("wild proso 35 millet") , in addition to the less resistant weeds, such as yellow fox tail, coot and millet, while maintaining their safety against sorghum. Said Belgian patent 810,763 provides data showing that compound 6 destroys sorghum, while no data is provided for the effect of compound 9 on sorghum. As will be shown below, the novel compounds of the invention surprisingly have superior properties as selective herbicides in sorghum as compared to the homologous compounds of the prior art.

The object of the invention is to provide herbicides which selectively control difficult weeds, such as Johnson grass seedlings and / or brittle reed, and for certain compounds according to the invention, other difficult to kill weeds, such as red carrot, pork grass and wild pseudo-millet, control, in addition to less resistant weeds, such as yellow foxtail, coot, and blood millet, especially in sorghum, in a superior manner compared to the compounds known in the art.

The above and other objects of the invention will become apparent from the detailed description below.

The invention relates to herbicidically active compounds, herbicidal preparations containing these compounds as active ingredients, and to a method for the use of these herbicidal preparations in special crops, in particular sorghum.

It has now been found that a selective group of 2-haloacetanilides, characterized by specific alkoxymethyl or alkenyloxymethyl radicals on the anilide nitrogen atom, specific alkoxy radicals in one ortho position and hydrogen or the methyl residue in the other ortho position, surprisingly superior and exhibit excellent selective herbicidal properties as sorghum herbicides compared to those already known in the art, including homologous compounds of the most relevant known literature. A primary feature of the herbicidal compositions of the invention is their ability to selectively control narrow-leaved weeds, Johnseongrass seedlings and / or brittle reed, which are species of the same plant genus as sorghum; in fact, sorghum and brittle reed are both two-tone sorghum species. Thus, it is extremely difficult to selectively control brittle reed and Johnston grass seedlings in sorghum without simultaneously damaging the sorghum. In addition, some members of the compounds of the invention also control other hard-to-kill species, such as red carrot, hog grass, yellow nut sedge and / or white pseudo-millet, and all of the compounds of the invention control other species, such as yellow foxtail, coot, blood millet and other noxious weeds.

The compounds of the invention are characterized by the general formula 1, wherein R represents isopropyl, n-butyl, isobutyl, sec.-butyl, allyl or 2-methylbutyl, represents methyl, isopropyl, n-butyl or allyl and R2 and R ^ represent hydrogen or methyl, wherein R ^, R2 and R ^ are each methyl when R is n-butyl, isobutyl or sec-butyl, R2 and R ^ are each hydrogen when R is isopropyl, isobutyl or sec-butyl and R 1 is isopropyl or n-butyl, and R 2 is hydrogen and R 1 is methyl when R 1 is 2-methylbutyl or allyl and R 1 is allyl.

Preferred compounds of the invention are N- (isobutoxymethyl) -2'-methoxy-3'.6, -dimethyl-2-chloroacetanilide, N- (n-butoxymethyl) -2'-methoxy-3'.6'-dimethyl-2 -chloroacetanilide, N- (sec-butoxymethyl) -2'-methoxy-3',6'-dimethyl-2-chloroacetan-25 anilide, N- (allyloxymethyl) -2'-allyloxy-6'-methyl-2-chloroacetanilide , N- (2-methylbutoxymethyl) -2'-allyloxy-6'-methyl-2-chloroacetanilide, N- (isopropoxymethyl) -2'-isopropoxy-2-chloroacetanilide, 30 N- (isobutoxymethyl) -2'- isopropoxy-2-chloroacetanilide and N- (sec.-butoxymethyl) -2'-n-butoxy-2-chloroacetanilide.

The utility of the compounds of the invention as an active ingredient in herbicidal preparations formulated therewith and the method for their use will be described below.

The compounds of the invention can be prepared in a wide variety of ways in 8101325 * 5. For example, the compounds may be prepared by the azomethine route described in U.S. Patents 3,442,945 and 3,547,620 mentioned above. According to the azomethine process, the appropriate primary aniline is reacted with formaldehyde to form the corresponding methylene anilene (substituted phenylazomethine) which is then reacted with a haloacetylating agent such as chloroacetyl chloride or chloroacetyl anhydride, after which the product obtained is in turn is reacted with the appropriate alcohol to yield the corresponding N-alkoxymethyl or N-alkenyl-oxymethyl-2-chloroacetanilide as the final product.

Another method of preparing the compounds of the invention involves an N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent under basic conditions.

A modification of this N-alkylation process is described in Example I for the preparation of the compounds of the invention. The N-alkylation ring process described in Example 1 comprises the in situ preparation of halomethylalkyl ethers, which are used as starting materials in the N-alkylation process.

The invention is further illustrated but not limited by the following examples.

Example I

This example describes the use of an N-alkylation process to prepare the compounds of the invention. In the process embodiment of this example, the alkylating agent is formed in situ, providing an efficient, economical and simple implementation.

To a cooled mixture of 9.25 g (0.125 mol) isobutanol, 1.86 g (0.062 mol) anhydrous paraformaldehyde and 100 ml of methylene chloride were added 7.56 g (0.062 mol) acetyl bromide; the mixture was stirred until all the paraformaldehyde 35 had dissolved, i.e. about 45 minutes. 4.55 g (0.02 mol) of 2'-methoxy-3'.6'-8101325 V - - 6 - dimethyl-2-chloroacetanilide and 2.0g of benzyltriethylammonium chloride in 100 ml of methylene chloride were then added to the mixture. The mixture was cooled to 15 ° C and 50 ml of 50% NaOH were added in one go and then stirred for 5 minutes. 150 ml of cold water were added to the mixture. The layers were separated, washed with water, dried over MgSO 4 and evaporated on a Kugelrohr to give 5.0 g (yield 79%) of yellow liquid, boiling at 107 ° C at 0.02 mm Hg.

Anal. Calculated for C 11 H 14 ClNO C 61.24, H 7.71, C 11.30%. Found: C 61.24, H 7.72, C 11.28%.

The product was identified as N- (isobu-toxymethyl) -2'-methoxy-3'6'-dimethyl-2-chloroacetanilide.

Examples II-VIII

The procedure of Example I was repeated under the same conditions with the exception that the suitable secondary anilide and alkylating agent were used as starting materials and the appropriate amounts thereof to prepare the corresponding N- (alkoxymethyl) - and N- (alkenyloxymethyl) - Ι-ΙΟ haloacetanilides; these compounds, along with certain physical properties thereof, are listed in Table A.

25 8101325> * -Ι α οο ο <r on Ν ο oocn-vf co η ο mo \ o m co <! - τ 2 "ί I" «» 3 .- "a« "." I · ». -. a -aa ”v-5 1 8«: 3- = 3 »= 3" Ξ 3- = 3- = 3-Ξ> 0} <υ ο <η

g g 2SS SnS 8S3 8SS

oV: -V- «Vo ~ W -V- 2-2 μ a> - vO - · vo ^ -vo— Ό” Ό - \ θ - 0)

M

P

g

fj OKU U so O S U O K Ö oso CJWO UUJO

I-1

W.

Oz-N ^ - '^' - 'O O S' ° S no no ΌΟ mo g ~ 2 ° S °, ii = s = 5 = s = s -s = s ~ s

Jsd ^ <_, cn co and on m m

QJQJO ο Ο ο Ο Ο O

ai aS £ 1 ZZ! z 3 5 3 £ S o, £ Ö o Ö Ö Ö o • a 3 s «ssssn. 3 p axis axis axis axis axis wo, (4 ΚΙ cO fO ~ ~ O 2 2 | (2 u "cT o” d ™ cT uo

J, I

N - 1 It; ,,, A Vi mn (n ^ iu ^ -nI + j i Jj

»- ^ f, II I I y Tj Η · Η Q) * O

<U r-H Ο λΗ dl rH <D, -v <Ujj £> 0> I 2 M

as to t *. o i— * ^ .ts t * S 1-1 2 1 y &> · y P .Ü a H>, ai · ιΗ Ρ · Ι-Ι> ι · Η · ΗΡ · -ί0 X ^ Jl

OU r4 Pas .CPrH S-j £ ^ Ö P n R Yh O

to p, ρ ω ü ρω · Η as * HP | cöS * o P ^ jo

ö £ t β SI <UEfS | | β (U - P.> »O 33 R

• S «oirt Ρ, ινο) SiS>» Stö 6 m <u 5? Ö c ο, >> ui o> ^ ·> -ι}> 4 o <uo - <u R- yp >> y £? " y

X o X <U PXrH O I <U P <N <U O (O jl 3 «I

r \ «. o (j ^ O «H f — I> s O d I O 4J I ^ yQ O CN YY | C ^ I

μ dipped, JD ft ö ^ cd d O I ^ J, _2J ö you »2 3 o o £ 00« keep. ρ ai κ o yy32 £ τΐ ^ 13

^ m Sj Q οομΡι — It-HO O O | O * P CU ft) γΊ I ^ P

^ .Ηβ.ο · ι-ια.ω nj >> o <u as o örCas “Pfillfi’S'S'j imas 1 co o jr-ta! i <ua3 t y i X-.SS iacS

ÏZ-rHC) Z-iHCfl Zdü IS i O S g N ISlNgS SSgflS

I T3 M

^ -H _ w M

0 ω η ü M

οωΜ w>. ti ΰ S

J> .QM Μ M>>> ** 8101 325

i C

- 8 -

The secondary anilide starting materials used in the preparation of the compounds of the above examples are prepared by known methods, for example, by haloacetylation of the corresponding primary amine with haloacetylating agents such as a haloacetyl halide or anhydride. Typically, the appropriate amount of the appropriate primary amine is dissolved in a solvent, such as methylene chloride containing a base, e.g., 10% NaOH, and stirred vigorously with a solution of the haloacetyl halide, e.g., chloroacetyl chloride, under external cooling. , for example at 15-25 ° C. The layers are separated and the organic solvent layer washed with water, dried and evaporated in vacuo.

The primary amines used for the preparation of the secondary anilides can also be prepared by known methods, for example, by catalytic reduction of the corresponding suitably substituted nitrobenzene, eg 2-alkoxy-6-alkyl nitrobenzene, in a solvent, such as an alcohol, for example ethanol, using a platinum oxide catalyst; for 2-alkenyloxy (e.g. allyloxy) -6'-alkyl compounds, a chemical reduction using iron and acetic acid can be used.

As mentioned above, the compounds of the invention have been shown to be effective as herbicides, especially as herbicides to be applied prior to plant emergence, although their activity has also been demonstrated upon application after plant emergence. Tables B and C give the results of tests conducted to determine the herbicidal activity of the compounds of the invention when applied to the plants for emergence.

The plant application test was performed in the following manner:

A good top soil quality is placed in 35 aluminum pans and compressed to a depth of 0.95 cm to 3.27 cm from the top of the pan. On top of the soil, a predetermined number of seeds or vegetative propagules of varying plant species is placed 8101 325 J-9. The soil, which is necessary for filling the pans evenly after sowing or adding the vegetative propagules, is weighed in a pan. The soil and a known amount of the active ingredient, applied in a solvent or as a wettable powder suspension, are thoroughly mixed and used to cover the prepared pans. After the treatment, the pans are placed in a greenhouse bank, in which they receive an initial irrigation with water over the top, equivalent to 0.64 cm of rainfall, and then they are watered by sub-irrigation in an amount needed is to obtain a suitable moisture for germination and growth.

About 2 weeks after sowing and treatment, the plants are examined and the results recorded.

Such results are shown in Tables B and C below. The herbicidal activity rating was obtained using a fixed scale based on the percentage damage of each plant species. The valuations are defined in the following way:% control Valuation 0-24 0 25-49 1 50-74 2 25 75-100 3

The plant species used in a set of experiments, for which the data are set out in Table B, have been identified by a letter as indicated in the list below: 30 A Canadian Thistle E Loosestrife I Johnsongras Seedlings B Burdock F Water Pepper J Gentle Swab C Mallow G Yellow nut sedge K Hanepoot D Dayflower H Cultivated grass 35 8101325

* V

- 40 -

Table B Before emergence

Connection 5 from front

image no. kg / ha ABCDEFGHIJK

I 11.2 3 3033333033 5.6 1 1 0 3 2 3 3 3 0 3 3 II 11.2 01131103033 10 5.6 0 0 1 2 0 1 0 0 0 3 3 III 11.2 3 0 1 1 0 2 3 2 0 3 3 5.6 00110130033 IV 11.2 31222230033 5.6 31113233333 15 V 11, 2 ---- 2 2 32133 5.6 0 0 0 0 0 1 3 1 0 3 3 VI 11.2 321233333 3 3 5.6 3 2 1 2 3 3 3 2 0 3 3 VII 11.2 32123333333 20 5.6 3 1 1 2 2 3 3 3 1 3 3 VIII 11.2 30002312133 5.6 0 0 0 0 0 0 1 2 2 3 3

The compounds were further tested for the following plant species using the procedure described above: L Soybean R Hemp Sesbania M Sugar Beet E Loosestrife N Wheat F Water Pepper 0 Rice C Mallow 30 P Sorghum J Gentle Swab B Burdock S Panicum Spp.

Q Wild buckwheat K Cinnabar D Dayflower T Blood millet

The results obtained are shown in Table C. 35 8101325-J1-S's

Table C Before emergence

Connection of

5 Ex. no._kg / ha LMNOPBQDREFCJSKT

I 5.6 3223222333203333 1.12 1203010022303333 0.28 0102000000001233 0.06 010101 1000000133 10 0.01 01000000-0000013 II 5.6 1223102223303333 1.12 0101002201003333 0.28 00000001 02002333 0.06 0000101 1 12002333 15 III 5.6 0 2 3 1 0 0 2 1 3 3 0 3 3 3 3 1.12 00231001 1 1002333 0.28 0022000000001 333 0.06 0001001000001 133 IV 5.6 2233302132313333 20 1.12 1223101011003333 0.28 120310001 1 103333 0.06 0101000011101233 0.01 0000000001000013 V 5.6 0222101 13220333- 25 1.12 010200001010333- 0.28 010100001 1 10313- 0.06 00000000 1000002- VI 5.6 222332223221333- 1.12 1223223220333- 30 0.28 01 1 1001 1 1 1 10233- 0.06 01 1 1001 12000123- 0.01 1 1000001 1000023- VII 5.6 223321323331333- 1.12 1213101 12220333- 35 0.28 0213001021 10233- VIII 5.6 0122101 1 1010333- 1.12 01 1 100000030333- 0.28 000000001030103- 0.06 000000000030000- 40 0.01 ooooooooooooooo-

The herbicides of the invention have surprisingly been found to possess superior properties as selective herbicides when applied to the emergence of the plants 45 for use in sorghum, particularly in the selective control of weeds which are difficult to kill, including one or more 8101325-12. of the weeds, Johnseong grass seedlings, brittle reed, red carrot, pork grass, yellow nut sedges and white pseudo millet, among other problem weeds such as yellow foxtail, coot and large millet. The selective control and suppression of some of the above and other weeds with the herbicides of the invention has been found in a variety of other crops, including soybeans, wheat, rice and sugar beet, as indicated in Table C above. however, remarkably good herbicidal properties of the compounds of the invention are most apparent when used for the selective control of weeds in sorghum.

In order to illustrate the surprisingly superior properties of the compounds of the invention both on an absolute basis and on a relative basis, comparative tests were carried out in a greenhouse with (1) homologous compounds of the prior art, which have a chemical structure are most related to the compounds of the invention, and (2) two other compounds, which, although not homologs, are within the scope of the prior art and one of which has superior properties as a sorghum herbicide and wherein both of these are technical herbicides. All compounds in the comparative tests described below can generally be defined as substituted phenyl-N-hydrocarbyloxyalkyl-2-haloacetanilides. The prior art compounds used for comparison have been identified in the data tables below in the following manner: A. N- (methoxymethyl) -2 '-methoxy-6' tert-butyl-2-chloroacetate anilide (Example 18, Am. os 3,442,945 and 3,547,620).

B. N- (methoxymethyl) -2, -methoxy-6'-tert-butyl-2-bromoacetanilide (Example 34, from Am. Os. 3,547,620 and Example 36 from Am. Os. 3,442,945).

C. N- (methoxyethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide (compound 6 of Belgian o.s., 810,763; also disclosed in West German Patent Application 2,402,983).

D. N- (ethoxyethyl) -2'-methoxy-6'-methyl-2-chloroacetanilide 8101325 -13- (compound 7 of Belgian patent 810,763) E. N- (1-methoxyprop-2-yl) -2'- methoxy-6'-methylchloroetanilide (compound 9 of Belgian patent 810,763).

F. N- (methoxyethyl) -2, -ethoxy-6, -methyl-2-chloroacetanilide 5 (compound 16 of Belgian patent 810,763).

G. N- (ethoxyethyl) -2'-ethoxy-6'-methyl-2-chloroacetanilide (compound 18 of Belgian patent 810,763).

H. N-isopropyl-2-chloroacetanilide (common name propachlor).

I. N-Onethoxymethyl) -6-diethyl-chloroacetanilide (Example 5 of Am. 3,547,620 and 3,442,945); common name "al- (R) achlor", active ingredient in the technical herbicide LASSO, registered trademark of Monsanto Company.

J. N- (isopropoxyethyl) -2T-methoxy-6, -methyl-2-chloroacetanilide.

Although the above compound H in structure 15 is less analogous than the said homologous herbicides in the

U.S. Pat. Nos. 3,547,620 and 3,442,945 in that it lacks an alkoxyalkyl or alkenyloxyalkyl substituent on the nitrogen atom and an alkoxy substituent on an ortho position, this compound has been included in the tests because of its disclosure in U.S. patents. 4,070,389 and 4,152,137 and exhibits superior properties as a technical sorghum herbide compared to other compounds in these patents. Analogously, compound I has been included in the tests because it falls within the scope of US patents 3,547,620 and 3,442,945 and has been accepted as a technical herbicide.

In herbicidal plant application tests, the compounds of the invention were compared with the prior art compounds AI in controlling various weeds, focusing on the hard-to-kill narrow-leaved species, which predominant infestations are in sorghum. The test results are shown below.

In the discussion of the data below, reference is made to the herbicidal application amounts, symbolized as "GR ^" and "GRg ^"; these amounts are indicated in kg per hectare (kg / ha), which can be converted to pounds per acre (lbs / A) by dividing the amount in kg / ha by 1.12.

GRi ^ defines the maximum amount of herbicide required to produce 15% or less of crop plant damage, and GRi ^ defines the minimum amount required to obtain 85% inhibition of the weeds. The GRi and GRg levels are used as a measure of potential engineering behavior, it being understood, of course, that suitable engineering herbicides may exhibit larger or smaller plant damage within reasonable limits.

A further guidance as to the effectiveness of a chemical as a selective herbicide is the "Selectivity Factor" ("SF") for a herbicide in given crop crops and weeds. The selectivity factor is a measure of the relative degree of crop safety and weed damage and is expressed in terms of the GR ^ / GRg ^ ratio, i.e. the GR. ^ Amount for the harvested plant, divided by the GRg ,. quantity for the weeds, the two quantities being expressed in kg / ha (lb / A). In the tables below, the selectivity factors, if used, are shown in brackets after the weeds; the symbol "NS" means "non-selective". A marginal or unclear selectivity is indicated by a dash (-) after the harvest plant.

Since the harvest plant tolerance and the weed control are interrelated, a brief discussion of this relationship in terms of the selectivity factors is significant. In general, it is desirable that the harvest-plant safety factors, ie, the herbicide tolerance values, be high, because higher concentrations of herbicide are yeel-desirable for some reason. Conversely, it is desirable that the weed control amounts are small, i.e. the herbicide has a high unit activity, for economic and possibly ecological reasons. However, small application rates of a herbicide may not be suitable for controlling certain weeds and a larger amount may be necessary. Therefore, the best herbicides are the herbicides which control the greatest number of weeds with the smallest amount of herbicide and provide the greatest degree of crop plant safety, i.e. crop plant tolerance. Correspondingly, "selectivity factors" (as defined above) are used to quantify the relationship between crop plant safety and weed control. With reference to the selectivity factors indicated in the tables, it is noted that the higher the numerical value the greater the selectivity of the herbicide for weed control in a given harvest plant.

The plant emergence tests listed here include both greenhouse and field tests. In the greenhouse tests, the herbicide is applied as a surface application after planting the seeds or the vegetative propagation or by incorporation in an amount of soil to be applied as a coating on the test seeds in pre-sown trial holders. In the field trials, the herbicide is pre-planted ("PPI") into the soil, ie the herbicide is applied to the surface of the soil, then incorporated therein using agitators, followed by planting the harvest plant seeds.

The surface application test method, which is used in the greenhouse, is carried out as follows: containers, for example aluminum pans, typically with dimensions of 24.13 x 13.34 x 6.99 cm or plastic pots of 9.53 x 9.53 x 7.62 cm with drainage holes in the bottom, are evenly filled with Ray mud loam soil and the soil is then compressed to a height of 1.27 cm from the top of the pots. The pots are then sown with a plant species to be examined and then covered with a 0.127 cm thick layer of the test soil. The herbicide is then applied to the surface of the soil with a belt sprayer in the amount of 187 l / ha 35 or 2.11 kg / cm; other nebulizers, such as a DeVilbiss nebuliser, are also sometimes used.

8101325 - J6 -

Each pot receives 0.64 cm of water as overhead irrigation and the pots are then placed on greenhouse benches for subsequent sub-irrigation as necessary. As an alternative procedure, the irrigation from above can be omitted. The observations of the herbicidal effects are made approximately 3 weeks after the treatment.

The herbicide treatment by incorporation into the soil, used in greenhouse trials, is carried out in the following way: 10 A good quality topsoil is placed in aluminum pans and compressed to a depth of 0.95 cm to 1.27 cm from the top from the pan. A number of seeds or vegetative propagules of varying plant species are placed on top of the soil. The soil needed to evenly fill the pans after sowing or adding the vegetative propagulus is weighed in a pan. The soil and a known amount of the active ingredient, applied in a solvent or as a wettable powder suspension, are thoroughly mixed and this mixture is used to cover the prepared pans. After the treatment, the pans are exposed to an initial irrigation with water from above, equivalent to a 0.64 cm rainfall, and then they are watered by sub-irrigation using an amount necessary to obtain an appropriate moisture 25 for germination and growth. As an alternative procedure, the irrigation from above can be omitted. The observations are made approximately 3 weeks after sowing and treatment.

In the tables below, the data for the compounds tested by multiple tests are the average data from application rates within the range of 0.07-2.24 kg / ha.

In a first comparative test, the herbicidal activity values for application of which to emerge the plants are shown in Table D. The relative activity of the compounds of Examples I and V, representative compounds of the invention, were compared with relevant compounds 8101 325-17 gene of the prior art, namely compounds A, B, d, F and G, as selective herbicides against special weeds commonly found in sorghum. The weeds used in the experiments are indicated in the tables by the following abbreviations: red carrot pig's grass (RPW), John'song grass seedlings (SJG), brittle reed (SC), white pseudo millet (WPM), jack's paw (BYG), large blood millet (LCG) and yellow foxtail (YFT).

8101325 -18-- »»

^ / -S O

o O «

·> .— «'O

CM | / - \ 'CO - Λ I I I Λ Λ

Sw <* s »/ F» / Sw / w W

PQ ΛΛΛΛΛ ^ Λ

O O O O O O O

v v v v v v / ~ v o ^ Λ Λ ft CO CO CO CO CO CO - 13 0 S3 53 B S Λ

> w / w V-> V_ / V — X W

o CO VO CO -J CO <t Is <f

in N "N - O N

ft A Λ Λ Λ Λ Λ

CM Ο Ο Ο Ο CN CM

V * β • Η <ϋ 3 - Ο γΗ cö / ~ \ <> ° Ο Ο gjjjO Ο * Λ ΟΟ dj -V, ·> «νΟ Ο ** *> ω ν λ / -V λ« - Γ Ο Ο Ο Ο °? λ δ * i cs A I I I I Λ Λ CM I I Λ Λ _fi uj H 'w / ^ MM1 M * <ί · ί M pH'a-'sl-'a ·' ^ · ^ · ^ · ^

qq ^ ^ a A A Λ Λ Λ Λ Λ Λ A

3 ΟΟΟΟΟΟΟ ΟΟΟΟΟΟΟ Ο V V V V V V V νννννν y y • • Ο ο ο * ~ \ * ΓΗ * Ο νο

• 0) CM / ~ s r ~ \ / "Ν <-ν“ - Τ 'Ο Ο C1 C1 C

iQ Λ I I I I CO Λ COCOCOCOCO CO / -N

Ηΐ rh ν- ^ 3 S 13 S 3 3 I

ε2 μ g - »- 'WW ^ wn_ / w CQ'i-i'Ï'iMSf'Ct aiNcO-iOCOCOM ·

-3m-mmMDCM

n K A n ft n A ft A »1 Λ Λ« *>

O ~ O O O O - CM

V V V V V v Λ f “\ m Λ Λ Λ / · ν ^ ο ο 00“ Μ Μ Μ 05 Μ Μ Λ 2 53 £ 2 'S S3 7

ts 3 è 3 3 3 3 ι 3 3 3 I 3 3 A

Ε ί! · C ν s- '^ ν co ^ ^ ^ s— /' - '2 3 ί 0D 00 00 <f Μ Μ

CM CM CM CM CO CM CM i / -) - <* - «- CO O ~ CT

A A ft A A A A * \ A * * k Λ * * »

CMOOOOCMCM - - O O O CM

I Λ V V

t — I

a) a)> Ό.

<u · η g 0 OJ ^ tp i3 3 dj £ co-j <iM- <rcM <f VCMCM - - · - - - CM I_! fc>> S ^ ΛΛΛΛΛΛΛ 00 Γ — iy * - ωοοοοοο - cm 0 _ 3 ^ <! WVVVVA * yy 3 3 rhw rO i — t I- *

w ö <dM03ü <uaJ

• h a) a)

n A

H J-1 M

s> h> «go • h 'd' ϋ!>!>

Art pH tH

d a> <i)

• H <3 W 0) CU

_Q * Q, Π tl £ £ a) 00> 00 ^>> 8101325 - 19 -

The values shown in Table D show that with respect to harvest plant safety (as indicated by the amount of sorghum), the compounds of the invention exhibited extraordinary superiority over the compounds of the prior art. More specifically, with respect to the known compounds of the prior art, which are most related in structure, it appears that compounds A and B with the N-alkoxymethyl-2 '-alkoxy-6' -alkyl -Z-haloacetanilide-JO configuration, that the compounds of the invention in the test were at least 8.0 to greater than 16.0 times safer on sorghum than Compound B and about 4.0 to greater than 8.0 times safer than compound A. In an analogous manner, the connections. gene of the invention 8.0 to more than 16 times safer on <1 / K 15 sorghum than the homologous already known compounds, F and G, each causing damage of more than 15% in sorghum at the very low amount of less than 0.14 kg / ha.

With regard to the weed control indicated by the GRg application rates under each weed, it can be noted that all known compounds in the test except compound A were either completely non-selective or unclear or marginally selective over all weeds. in the sorghum test. Compared to compound A, the compounds of the invention were about 4.0 to 8.0 times more effective against Johnston grass seedlings, large millet and coot, and 2.0 to 4.0 times more effective against yellow foxtail. The compound of Example V also showed a positive selective control of brittle reed and yellow nut sedge and a marginal selectivity with regard to red-carrot-pork grass and white pseudo-millet, while compound A did not show this control.

In another comparative test, the compound of Example I in terms of its herbicidal activity when applied to the emergence of the plants was compared to that of compounds C, D and; the results obtained in this test are given in Table E.

8101325 * * - 20 -

r — N

O

* k

/ —S / —s CO

I I I Λ v / V w Η> ί · ί · ί * i 1¾ - - «#» ft * Λ

O O O O

V V V V

a-v o

Tl / - \ / —s Λ h • rl | | | 00 (U O ^ ^ w λ Λ U w r-l x ~ \ J · ί> ΐ <ί <dj ca - - - - <U A3 * * * «

> O O O O.

CU 00 v V V V

O Ai A3 ^

ιΛ / - "N

00 O

p3 Λ

O CO

/ N I I A

0 I V ν 'W

IS sr sr sisi-

n A fi A

o o o o

V V V V

w

i-t C

-Q CO CO CO “ca ü a 8 b - H 1-5 w w w w

CO

«A · oo -a- si · - cm - oo

fk A A A

o o © © • ti o A! / -s i-j ca a) a3 0) ^!> oo δ rM.

o ^ S

A- 3 <t st -ί N

, β * - * A-M Ψ- * LT) & Q e »r \ #» c »- J-t o o o - pi Ο v v v v

Ü CO

00 H

¢ 3 • Η Ό r-t ö a)

• rl <U

rO -f & ë> (2 8101 * * - 21 -

The values indicated in Table E show that the compound of Example I according to the invention had a considerably higher safety factor in sorghum than the already known compounds, that is to say at least 8.0 times safer. In addition, the compound of the invention, in addition to a higher harvest plant safety factor, exhibited uniform and highly superior selectivity factors compared to the already known compounds against each of the weeds used in the test. It should be noted that the already known compounds C, D and no positive crop plant J showed selectivity against Johnseong grass seedlings and the selectivity of these compounds against the remaining weeds was unclear or marginal at most; in any case, the low safety factors of these compounds make them unsuitable as sorghum herbicides.

Further values of the herbicidal application on emergence of the plants from other tests for the compounds of Examples I-VIII are shown in Table F.

Table F shows the GR and GRg amounts for each compound of the invention in sorghum and the relevant weeds, respectively; the selectivity factor values are indicated in brackets. The values from the multiple runs are presented as the averages of the number of runs indicated. A blank space under a special weed indicates that this weed was not present in the given test for the relevant compound.

8101325 -11- <u <u <u Q) Ό Ό Ό Ό i—) i—) r “) f—)

<U eü <ü <U

Ό 'O Ό Ό ^ T3 TJ Ό Ό «oo o-« o-ooo SöSCöced ft A «t« κ ^ * Λ Λ Λ ΨΦΦΨΦΦΦΟ) ι- * ΐΠ <· νΟ · - »νΟΓ * ·% ί & Q> Ö0 > Ö0> Ö0>

'~' <? AAAAAA 0) <U <U <U

0 LT) w 'w' -MO -PO -MO -MO

> J WNOOWvO «OiCO CD M CD M OM CD M

P3 OC-JCMO - ^ OCN

«« IJtflAAft * II II

OOOOOOOO d -M fl-U d M d-M

P V V V * 1 “) te * 1-) cd * 1-] to -T—) te

• H Cd «M td · Η Cd» H Cd NdNÜNCJNÜ * r) · Η * rl * H

dr-1 SH dr-C d H

eDPCDPCDdiCDO.

, -s, -s y-v O ld® fl® ue

00 Q0 / - \ O "MM MM MM MM

-. ·. r «. λ o td cd td cd «oo»> uo -> cd i— cdLn cd <n cd co - Λ - 'A A is. £. £: S = ηρ) 0 v-c w A ^ 'd d (3 d • H co r> ιλ -d · f-> ocd eü cd cued cued ο cn, -. 00--0 p> p> p> p>

Γ} A A A A A

r-C. O O —t Ο O O ^ <D -td V V cd p o tj <D p ^ w v_ / v_ /> CD 00 Ο P / -> o—>

_0 '-' O, / -S \ f> · -— \ / -. 0 "N ✓" N / "S /" N / "N

·> Ο O -tf »> O <t O ^ O-O-z-sCM ^ COO

[ƒ-) CN - Λ Λ CO Λ - Λ 1 / "| ΛΛ - ^ - ΛΛΛΛ 00 —iCO ^ fvO— <lOvO <f«> r>. oj ·> for r * * «el · pel Λ Λ Λ Λ Λ Λ <? Λ ΡιΑΛνΟΛΑΛΛ 0 0 s »/ -w- s * / v 'w' EJ --—- v ^ - v—- --—- -— '- ÜOi-iOOmN <fW CMCNOvOCTiVO—' 000

PO— · <ΝΟ ~ —'— ’O ')> c -’ - -ei · O CO - O CM

AAAAAAAA AAAAAAAA

OOOOOOOO OOOOO OO O

P · V V V V Λ VV

iH

• <3)

CÖ O / ** N / * N

Η V — V COVOO -— vOOCO CM / -. CO

0-0 Λ Λ Λ 0 Λ - LO, VO CO Λ ·> ΛίΜΟΟΟΟ *> Γ''ιΛ * co Λ Λ- oo 0CMwAAAinAA S - <2ü -. CO Λ i “5 -_- -—sv '—y _- -—' -w-- -w- -w '- ^' w '' - COCOvOvOPCO'd'O'— §“ "> -4 · / - <j-cnm— <cm—> ocM r- ï ^ nn AAAAAMAA a OOOOOOOO oo - oo VV Λ

/ *> / —N

00 / -s / -s O

λ c0 O Λ

CNJ · »Λ CN

A <- | m Λ w s- / v * / w s- / [5 ^ and <f ^ m N - - * f0

| (¾ A A A A A

> -) O O <N O O

CD A A

<D \ / -> / - \

S.O CO VOCMVO ^ S

(D * r) Jg -I r. Λ - CO

O CD \ S>) <»-.- 1-.¾ xirdedd - w -«? w w d N N N 4 <N ^ in '-' CO'd · in sMn ^ -mNNN "O 00 O <1 · 00 π Λ ΛΛΛ ·>

pd —d O —f - - t 3 CM O O —1 - * O - O O

0 CO ΛΑ Λ ΛΑ Λ

00 ÖO

d. d ^

Ή / - \ / —i "d * H \ TJ

d 'd / -> ρ, -νΟ' - 'Η

pi Cd Hs - '^ ^ HH d t®HH' - 'Ü' - / HH

• W WHH> '-' HHH 'HHH

p -hHWW ·· >>>> PH HH >>>> 1 ëe-ieêêê'e leeëÈgéeë 8101325 - 23 -

The values shown in Table F first show that each compound of the invention, tested on both Johnston grass seedlings and brittle reed, selectively controlled these weeds in sorghum at application rates within the range of 0.57-2.24 kg / ha , a result which is as far as known not yet achieved with any already known compounds, including the technical herbicides compounds H and I, wherein compound H is a generally accepted technical sorghum herbicide. Moreover, with three exceptions, each compound of the invention showed positive selective control of each weed tested; the exceptions were the lack of a positive selectivity of the compound of example IV over white pseudo millet and of the compound of example VII against yellow nut sedge and the marginal selectivity of the compound of example V against red carrot sward grass.

Since the herbicidal plant application activity data shown in Tables D-F were obtained according to identical routine procedures, a comparison of the herbicidal activity of the compounds can be

according to the invention in Table F are also made with respect to the herbicidal action for the already known compounds in Tables D and E. Here again it is clear that each of the compounds according to the invention is highly superior to all most relevant already known compounds with regard to harvest plant safety, without exception, and total selective weed control, as evidenced by selectivity factors, again with exceptions in isolated cases. More specifically, of all 30 compounds already known, only Compound A showed

(Table D) a positive selective control of Johnsong grass seedlings, blood millet, coot and yellow foxtail in sorghum; compound A was nonselective of the remaining weeds in the experiment. Against the weeds, which were not selectively controlled by compound 35 A, the compounds according to the invention showed an extremely higher selectivity, from 8101325 d 6.

Healthier the compounds of Examples II and III, which behaved similarly to compound A against Johnston grass seedlings. In any case, again the low sorghum safety factors and / or the non-selectivity or unclear selectivity of the relevant already known compounds against all weeds in the above tests render these compounds completely unsuitable as sorghum herbicides.

As mentioned above, compounds H and I are mentioned in the above patents and these compounds are the active ingredients in technical herbicides; compound H is widely used as a sorghum herbicide. Although none of these compounds are homologs, isomers or analogues of the compounds of the invention, these compounds were tested in an identical manner and against the same weeds as used in the tests for the compounds of the invention, as indicated in Tables DF, in order to determine the herbicidal activity in their application before the emergence of the plants in comparison with that of the compounds of the invention. It was determined (based on averages from 5 replicate tests of compound I and 9 replicate tests with compound H) that no compound selectively fought brittle cane in sorghum and that compound H did not show positive control of seedling Johnston grass while compound I showed only marginal selectivity with a selectivity factor of the order of about 3.2 against seedling Johnston grass. Incidentally, compounds H and I did show selective control of the remaining weeds listed in Tables D-F. Accordingly, it will be appreciated that the compounds of the invention provide significant advantages, even over technical herbicides, in the selective control of weeds in sorghum.

The compounds of the invention exhibit selective herbicidal activity in a wide variety of crop plants other than sorghum, as indicated in Table C above. In still other experiments, the compound of Example V was shown to be useful in amounts of 81013 as well. 2 - 25 - Example V was also useful in amounts of more than 1.12 kg / ha in soybeans, field corn, cotton, cucumber, snap beans, garden peas, tomatoes and peanuts.

Therefore, it will be apparent from the above detailed description that the compounds of the invention have surprising and highly superior herbicidal properties, in both absolute and relative sense as compared to the most structurally related compounds, other related homologs and analogues, including the prior art technical 2-haloacetanilides. More particularly, the compounds of the invention have extremely high harvest-plant safety in sorghum and good selectivity factors, particularly with respect to hard-to-kill weeds such as seedling Johnston grass and brittle reed, and other problematic weeds such as red carrot pig grass, yellow nut sedge, white pseudo millet, yellow foxtail, coot, blood millet, etc., as shown in the results of tables BF.

The herbicidal compositions of the invention, including concentrates to be diluted before application, contain at least one active ingredient and an additive in liquid or solid form. The compositions are prepared by mixing the active ingredient with an additive, including diluents, cutters, carriers and conditioners, to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions . For example, the active ingredient can be used with an additive, such as a particulate solid, an organic liquid, water, a wetting agent, a dispersant, an emulsifying agent, or any suitable combination thereof.

The compositions according to the invention, in particular liquids and wettable powders, preferably contain as conditioner one or more surfactants in sufficient amounts to make a given composition easily dispersible in water or in oil. The inclusion of a surfactant in the compositions greatly enhances its effectiveness. The term "surfactant" includes wetting agents, dispersants, suspending agents, and emulsifying agents. Anionic, cationic and non-ionic agents can all be easily used.

Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfoated fatty acid esters, sulfonated sulfonated ethylsulfonated sulfonated ethylsulfonated sulfonated glycols polyoxyethylene derivatives of alkylphenols (in particular isoctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitolarihydrides (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymers alkyl naphthalene sulfonates, sodium naphthalene sulfonate and polymethylene bisnaphthalene sulfonate.

Moisturable powders are water-dispersible preparations containing one or more active ingredients, an inert solid cutting agent and one or more wetting and dispersing agents. The inert solid cutting agents are usually of mineral origin, such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such cutters are kaolinites, ataapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the invention usually contain about 0.5-60 parts (preferably 5-20 parts) of active ingredient, about 0.25-25 parts (preferably 1-15 parts) of wetting agent, about 0 25-25 parts (preferably 1.0-15 parts) of dispersant and 5 to about 95 parts (preferably 5-50 parts) inert solid cutting agent, all parts being parts by weight based on the total composition. If necessary, about 0.1-2.0 parts of the solid inert cutting agent can be replaced by an corrosion inhibitor or anti-foaming agent or both.

Other formulations include substance concentrates containing 0.1-60% by weight of the active ingredient on a suitable cutting agent; these fabric preparations may be diluted prior to application 8101325-27 to concentrations within the range of about 0.1-10 wt%.

Aqueous suspensions or emulsions can be prepared by stirring an aqueous mixture of a water-insoluble active ingredient and an emulsifying agent until a uniform mixture is obtained and then homogenized to obtain a stable emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed a very uniform coating is obtained. Suitable concentrations of these preparations are about 0.1-60% by weight and preferably 5-50% by weight of the active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent.

i

In another form of aqueous suspensions, a water immiscible herbicide is encapsulated to form a microencapsulated phase dispersed in an aqueous phase. In one embodiment, very small capsules are formed by combining an aqueous phase containing a lignin sulfonate emulsifying agent and a water-immiscible chemical, and polymethylene polyphenyl isocyanate, dispersing the water-immiscible phase into the aqueous phase, and then adding polyfunctional amine. The isocyanate and amine compounds react to form a solid urea shell wall around particles of the water-immiscible chemical to form microcapsules thereof. Generally, the concentration of the micro-apsed material will range from about 480 to 700 g / l total preparation, preferably 480-600 g / l.

Concentrates are usually solutions of active ingredients in water-immiscible or partially water-immiscible solvents together with a surfactant. Suitable solvents for the active ingredient of the invention include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones. Other liquid concentrates with high 8101 325

* 'V

However, strength can be formulated by dissolving the active ingredient in a solvent and then diluting it, for example with kerosene, to obtain a spray concentration.

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

Granules are physically stable particulate preparations containing active ingredient, adhered or distributed by a basic matrix of an inert, finely divided particulate cutting agent. In order to promote leaching of the active ingredient from the particulate material, a surfactant such as any of the surfactants mentioned above may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of useful groups of particulate mineral cutting agents. The preferred cutters are the porous, absorbent, preformed particles, such as preformed and sieved particulate attapulgite or heat-expanded, particulate vermiculite, and the finely divided clays, such as kaolin clays, hydrated attapulgite or bentonite clays. These cutting agents are sprayed on or mixed with the active ingredient to form the herbicidal granules.

The granular compositions of the invention can contain from about 0.3 to about 30 parts, and preferably from about 3 to 20 parts, by weight, of active ingredient per 100 parts of clay, and from about 30 to about 5 parts, of surfactant, per 100 parts, of particulate contain clay.

The compositions of the invention may also contain other additives, for example, fertilizers, other herbicides, other pesticides, safeners and the like, used as additives or in combination with one or more of the additives described above. Chemicals that can be used in combination with the active ingredients of the invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic or phenol derivatives, thiol carbamates, triazoles, benzoic acids, nitriles, biphenyl ethers 5 and the like such as:

Heterocyclic nitrogen / sulfur derivatives 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 10 3-isopropyl-1H-2.1.3-benzothiadiazin-4- (3H) -one-2,2-dioxide 3-amino-1,2,4-triazole 6,7-dihydrodipyrido (1,2-a: 2f.1f-c) -pyrazidinium -salt 5-bromo-3-isopropyl-6-methyluracil 1.1 * -dimethyl-4,4'-bipyridinium 15 Urea N * - (4-chlorophenoxy) -phenyl-NN-dimethyl urea NN-dimethyl-Nf- (3-chloro-4 -methylphenyl) -urea 3- (3,4-dichlorophenyl) -1,1-dimethylurea 1,3-dimethyl 1-3- (2-b and so thiazo ly 1) -urea 20 3- (p-chlorophenyl) -1.1- dimethyl urea 1-butyl-3- (3,4-dichlorophenyl) -1-methyl urea Carbamates / Thiol carbamates 2-chloroalldiethyl dithiocarbamate S- (4-chlorobenzyl) -NN-diethylthiol carbamate 25 Isopropyl-N- (3-chloro-phenyl-carbamate) S-carbamate NN-diisopropylthiol carbamate Ethyl NN-dipropylthiol carbamate S-propyl dipropylthiol carbamate. Acetamides / Acetanilides / Anilides / Amides 30 2-chloro-NN-diallylacetamide N. N-dimethy1-2.2-diphenylacetamide N- (2,4-dimethyl-5- / 7 (trifluoromethyl) sulfonyl / amino / phenyl) acetamide N-isopropyl -2-chloroacetanilide 35 2 *. 6 ^ diethyl-N-methoxymethyl ^ -chloroacetanilide 2 * -methyl-6 * -ethyl-N- (2-methoxyprop-2-yl) -2-chloroacetanilide 8101325-30-

V

- Ή a, a, a-trifluoro-2,6-dinitro-NN-dipropyl-p-toluidine Ν- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide Acids / Esters / Alcohols 2,2-dichloropropionic acid 5 2-methyl-4- chlorophenoxyacetic acid 2.4-dichlorophenoxyacetic acid

Methyl 2- / 4- (2,4-dichlorophenoxy) phenoxy / prop ionate 3-amino-2,5-dichlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid 10 2,3,6-trichlorophenylacetic acid-N-1-ethylphthalamic acid

Sodium 5- / 2-chloro-3- (trifluoromethyl) phenoxy / -2-nitrobenzoate 4,6-dinitro-o-sec-butylphenol N- (phosphonomethyl) glycine and its C 9 monoalkylamine and alkali metal salts and combinations thereof.

Ethers 2,4-dichlorophenyl-4-nitrophenyl ether 2-chloro-a.a-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether Miscellaneous 2.6-dichlorobenzonitrile 20 Monosodium acid methanesaronate Disodium methanesarsonate.

Fertilizers that can be used in combination with the active ingredients are, for example, ammonium nitrate, urea, potash and superphosphate. Other useful additives are materials in which plant organisms root and grow, such as compost, manure, humus, sand and the like.

Below are exemplary some illustrative embodiments of herbicidal compositions of the types described above.

30 I. Emulsifiable Concentrates ______ uÊW · 7o (A) Compound of Example I 50.0

Calcium dodecylbenzene sulfonate / polyoxyethylene ethers mixture (e.g.

Atlox (R) 3437F and Atlox 3438F) 5.0 35 Monochlorobenzene 45.0 100.00 8101325

Wt% - 31 - (B) Compound of Example II 85.0

Galcium dodecyl sulfonate / alkyl aryl polyether alcohol mixture 4.05 CQ aromatic hydrocarbon solvent 11.0 100.00 (G) Compound of Example III 5.0 10 Calcium dodecyl benzene sulfonate / polyoxyethylene ethers mixture (e.g.

Atlox 3437F) 1.0

Xylene 94.0 100.00 15 II. Liquid concentrates

Wt% (A) Compound of Example IV 10.0

Xylene 90.0 100.00 (B) Compound of Example V 85.0

Dimethyl sulfoxide 15.0 100.00 25 (C) Compound of Example VI 50.0 N-methylpyrrolidone 50.0 100.00 (D) Compound of Example VII 5.0 30 Ethoxylated castor oil 20.0

Rhodamine B 0.5

Dimethylformamide 74.5 100.00 35 8101325

Wt% - 32 - III. Emulsions (A) Compound of Example VIII 40.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol (eg.

Tergitol (XH) 4.0

Water 56.0 100.00 (B) Compound of Example I 5.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol 3.5

Water 91.5 100.00 15 IV. Moisturable powders

Wt% (Δ) Compound of Example III 25.0

Sodium lignosulfonate 3.0

Sodium N-methyl-N-oleyl taurate 1.0 20 Amorphous silica (synthetic) 71.0 100.00 (B) Compound of Example V 80.0

Sodium dioctylsulfosuecinate 1.25 Calcium lignosulfonate 2.75

Amorphous Silica (Synthetic) 16.00 100.00 (C) Compound of Example VI 10.0 30 Sodium Lignosulfonate 3.0

Sodium N-methyl-N-oleyl taurate 1.0

Kaolinite clay 86.0 100.00 35 8101325 * - 33 - V. Dust preparations

Wt% (A) Compound of Example III 2.0

Attapulgite 98.0 100.00 (B) Compound of Example IV 60.0

Montmorillonite 40.0 100.00 10 (C) Compound of Example V 30.0

Bentonite 70.0 100.00 15 (D) Compound of Example VI 1.0

Diatomaceous earth 99.0 100.00 VI. Granules

Wt% 20 (A) Compound of Example VII 15.0

Granular attapulgite (20/40 mesh) 85.0 100.00 (B) Compound of Example VIII 30.0 25 Diatomaceous earth (20/40) 70.0 100.00 (C) Compound of Example I 0.5

Bentonite (20/40) 99.5 30 100.00 (D) Compound of Example II 5.0

Pyrophyllite (20/40) 95.0 100.00 35 8101325 r *

Wt% - 34 - VII. Microcapsules (A) Compound of Example IV encapsulated in a polyurea shell wall 49.2 Sodium lignosulfonate (e.g. Reax 88 ^ B) 0.9

Water 49.9 100.00 10 (B) Compound of Example V encapsulated in a polyurea shell wall 10.0

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

Water 89.5 15 100.00 (C) Compound of Example VI encapsulated in a polyurea shell wall 80.0

Magnesium salt of lignosulfate 20 (Treax (R) LTM) 2.0

Water 18.0 100.00

In the practical application of the present invention, effective amounts of the acetanilides of the invention are applied to the soil containing the plants, or are incorporated into aqueous media in any convenient manner. The application of liquid and particulate solid preparations to the soil can be carried out using conventional methods, for example, using energetic dusting devices, tree and hand sprayers and spray dusting devices. The formulations can also be applied from airplanes in the form of a pollen or a spray because of their effective action at low doses. The application of herbicidal preparations to aquatic plants is usually carried out by adding the preparations to the aqueous media in the area in which it is desired to control the aquatic plants.

8101325 - 35 -

The application of an effective amount of the compounds of the invention to the site of the unwanted weeds is essential and critical to the practice of the present invention. The exact amount of active ingredient to be used depends on varying factors, including the plant species and their development phase, the type and condition of the soil, the amount of rainfall and the specific acetal anilide used. In the selective application for the emergence of the plants on the plants or on the ground, usually an amount of 0.02 to about 1.2 kg / ha, preferably about 0.04 to about 5.60 kg / ha or suitably 1.12-5.6 kg / ha acetal anilide used. Lower or higher amounts may be required in some cases. One skilled in the art can easily determine the optimum amount to be applied in each special case from the above description, including the examples.

The term "ground" is used in its broadest sense and includes all the usual "grounds" as defined in Webster's New International Dictionary, Second Edition, Unabridged (1961). Thus, the term refers to any substances or media in which a vegetation may take root and grow, and includes not only soil, but also compost, manure, waste ("muck"), humus, sand, and the like. to support plant growth.

8101325

Claims (28)

1. Compounds of general formula 1, wherein R represents isopropyl, n-butyl, isobutyl, sec-butyl, allyl or 2-methylbutyl, R 1 represents methyl, isopropyl, n-butyl, or 5 allyl and R 1 and R 1 represent hydrogen or methyl, wherein R 1, R 2 and R 1 are each methyl when R is n-butyl, isobutyl or sec-butyl, R 1 and R 1 are each hydrogen when R is isopropyl, isobutyl or sec-butyl and R 1 is isopropyl or n -butyl and R2 is hydrogen and R2 is methyl when R2 is 2-methylbutyl or allyl and R1 is allyl. 2. N- (isobutoxymethyl) -2'-methoxy-3 *, 6'-dimethyl-2-chloroacetanilide. 3. N- (n-butoxymethyl) -2'-methoxy-3 '. 6'-dimethy1-2-chloroacetanilide. 15 4. N- (sec-butoxymethyl) -2'-methoxy-3'-6'-dimethyl-2-chloroacetanilide. 5. N- (allylo 2 methyl) -2, -allyloxy-6'-methyl-2-chloroacetanilide. 6. N- (2-methylbutoxymethyl) -2'-allyloxy-6'-methyl-21-chloroacetanilide. N- (isopropoxymethyl) -2, -isopropoxy-2-chloroacetanilide. 8. N- (isobutoxymethyl) -2'-isopropoxy-2-chloroacetanilide. 25 9. N- (sec-butoxymethyl) -2, -n-butoxy-2-chloroacetanilide. 10. Herbicidal compositions, characterized in that they contain an additive and a herbicidically effective amount of a compound of the formula 1, wherein R represents isopropyl, n-butyl, isobutyl, sec-butyl, allyl or 2-methylbutyl, Rj represents methyl, isopropyl, n-butyl or allyl and R2 and R ^ represent hydrogen or methyl, wherein Rj, R2 and R ^ are each hydrogen when R is n-butyl, isobutyl or sec-butyl, R2 and R ^ are each hydrogen when R is isopropyl, isobutyl or 35 sec-butyl and R 1 is isopropyl or n-butyl and R 2 is hydrogen and R 1 is methyl when R is 2-methylbutyl or allyl and R 1 is allyl. 8101325 - 37 - Preparation according to claim 10, characterized in that the compound is N- (isobutoxymethyl) -2'-methoxy-3,6 '-dimethyl-2-chloroacetanilide. 12. A composition according to claim 10, characterized in that the compound is N- (n-butoxymethyl) -2'-methoxy-3 '. 6'-dimethyl-2-chloroacetanilide. Preparation according to claim 10, characterized in that the compound is N- (sec-butoxymethyl) -2'-methoxy-3'6'-dimethyl-2-chloroacetanilide. Preparation according to claim 10, characterized in that the compound is N- (allyloxymethyl) -2'-allyloxy-6'-methyl-2-chloroacetanilide. 15. Preparation according to claim 10, characterized in that the compound is N- (2-methylbutoxymetbyl) -2, -allyloxy-6,6-methyl-2-chloroacetanilide. Preparation according to claim 10, characterized in that the compound is N-8isopropoxymethyl) -2'-isopropoxy-2-chloroacetanilide. 17. A composition according to claim 10, characterized in that the compound is N- (isobutoxymethyl) -2'-isopropoxy-2-chloroacetanilide. Preparation according to claim 10, characterized in that the compound is N- (sec-butoxymethyl) -2 * -n-butoxy-2-chloroacetanilide. 19. A method of controlling undesired plants which occur in combination with sorghum, characterized in that a herbicidically effective amount of a compound of the general formula 1, wherein R represents isopropyl, n- is applied to the place of these plants. butyl, isobutyl, sec-butyl, allyl or 2-methylbutyl, R 1 represents methyl, isopropyl, n-butyl or allyl and R 2 and R 1 represent hydrogen or methyl, wherein R 1, R 1 and R 1 are each methyl when R 1 n-butyl, isobutyl or sec.-butyl, R2 and R1 are each hydrogen when R1 is isopropyl, isobutyl or sec-butyl and R1 is isopropyl or n-butyl and R2 is hydrogen and R1 is methyl when R 2-methylbutyl or allyl and R 1 is allyl. 8101325 - ^ - 38 - r « A method according to claim 19, characterized in that the compound is N- (isobutoxymethyl) -2'-methoxy-3T.6T-dimethyl-2-chloroacetanilide. 21. A method according to claim 19, characterized in that the compound is N- (n-butoxymethyl) -2'-methoxy-3'.6'-dimethyl-2-chloroacetanilide. 22. A method according to claim 19, characterized in that the compound is N- (sec.-butoxymethyl) -2'-methoxy-3'6'-dimethyl-2-chloroacetanilide. 23. Process according to claim 19, characterized in that the compound is N-Callyloxymethyl-D-allyloxy-methyl-2-chloroacetanilide. 24. Process according to claim 19, characterized in that the compound is N- (2-methyl-butoxymethyl) -2'-allyloxy-6'-methyl-2-chloroacetanilide. Process according to claim 19, characterized in that the compound is N- (isopropoxymethyl) -2'-isopropoxy-2-chloroacetanilide. 26. Process according to claim 19, characterized in that the compound is N- (isobutoxymethyl) -2'-isopropoxy-2-chloroacetanilide. A method according to claim 19, characterized in that the compound is N- (sec.-butoxymethyl) -2'-n-butoxy-2-chloroacetanilide. 28. Compounds, preparations and methods as described in the description and / or examples. 8101325 -JonCCH.C CHOR λ \ * N RivA- ori from Monsanto Company, St. Louis, Missouri, United States of America 8101325