CS210642B2 - Herbicide and manufacturing method of its active substance - Google Patents

Description

The invention relates to a herbicidal composition and to a process for the manufacture of an active ingredient thereof. The herbicidal composition of the invention is suitable for controlling unwanted weeds that grow with monocotyledonous crops such as wheat, sorghum and rice, and with dicotyledonous crops such as diabetes and soybean.

Herbicidal compositions based on 2-haloacetanilides as well as processes for the preparation of 2-haloacetanilides having different substituents on the fepyl ring and the anilide nitrogen atom are known in the art. Various 2-haloacetanilides are described which may be substituted on the phenyl ring or on the nitrogen atom by alkyl, alkoxy and / or alkoxyalkyl groups or other substituents. See, for example, U.S. Patents Nos. 2,402,983 and 2,405,183 and U.S. Patents Nos. 3,966,811 and 3,976,471.

Said NSR Patent No. 2,402,983 describes herbicidal compounds which are substituted with alkyl and / or alkoxy groups at the 2 'and 6' positions and an alkoxyalkyl group on the nitrogen atom. However, in the above-mentioned Patent No. 2,402,983 with an alkoxyalkyl group on a nitrogen atom, the nitrogen and oxygen atoms must not have less than two carbon atoms between them, which distinguishes them from the 2-haloacetanilides which are substituted by an alkoxymethyl group. In addition, the above-mentioned NSR Patent No. 2,402,983 does not disclose any example of any 2-haloacetanilide having alkoxyalkyl groups on the anilide ring or any method for producing such compounds.

U.S. Patent No. 2,405,183 and U.S. Pat. Nos. 3,966,811 and 3,976,471 disclose 2-haloacetanilide compounds which are substituted with alkoxyalkyl groups on the phenyl ring, but not in ortho (2'- and 6'-) positions, as in the present invention. In addition, the substituents on the nitrogen atom in U.S. Patent Nos. 3,966,811 and 3,976,471 differ from the substituents of the present invention. U.S. Pat. No. 3,966,811 is a substituent

A 2,2-dialkoxyethyl group and in U.S. Patent No. 3,976,471 an alkylideneaminooxymethyl group.

Other less important compounds mentioned in the literature are 2-haloacetanilides which are substituted by an alkoxy or dialkoxyalkyl group on a nitrogen atom, but not on the phenyl ring, which may be substituted by other substituents. Such typical compounds are described in U.S. Patent Nos. 3,442,945, 3,547,620, 3,983,174, 3,952,056,

937,730, 4,019,894, 4,021,224, 4,025,554 a

086 080.

In the literature, the most important methods for making compounds analogous to the compounds of the present invention and disclosed in the present invention are those described in the aforementioned patents. Illustrations of methods disclosed in the literature are the haloacetylation of appropriately substituted aniline, e.g., secondary aromatic amines, which have substituents on the phenyl ring and nitrogen atom prior to haloacetylation. Another way is to treat the appropriately substituted aniline with haloalkanols, for example 2-halopropanol introduces a hydroxyalkyl chain to the nitrogen atom. This is followed by chloroacetylation and finally etherification of the hydroxyalkyl group with an alcohol. This produces the corresponding N-alkoxyalkyl compound.

Methods previously described include the haloacetylation of an appropriately substituted phenylazomethine. This produces an N-halomethyl adduct which, by further treatment with an alcohol, yields the corresponding N-alkoxyalkyl compound. Alternatively, the N-halomethyl adduct is treated with an appropriately substituted oxime salt to give the corresponding product; the aforementioned U.S. Patent No. 3,976,471.

One of the embodiments of the present invention described below, wherein silver or other heavy metal tetrafluoroborine is used as a catalyst, has a certain relationship in the work of J. C. Sheehan et al., J. Amer. Chem. Soc. 89, 362, and in particular 364 and 368 (1967), which discloses a neopentyl rearrangement of 2-bromo-3,3-dimethyl-N-tert-butylbutyramide using silver tetrafluoroborate. This process, however, is described as dehydrobromation resulting in the removal of the halogen atom at the 2-position. The procedure described by Sheehan et al. Thus shows the lability of the halogen atom at the 2-position in the presence of silver tetrafluoroborate.

The prior art describes a process for preparing 2-haloacetanilides by treating the alcohol with an ortho-benzyl halide intermediate to produce the corresponding ether derivative.

The present invention relates to a herbicidal composition and a process for the preparation of an active ingredient thereof.

The substance of the herbicidal composition according to the invention is characterized in that it contains 2-halogenoacetanild of the formula I as active ingredient,

O

in which they mean

X is chlorine or bromine,

R and R 1 independently of one another are hydrogen, alkyl of 1 to 4 carbon atoms or alkoxymethyl of 1 to 4 carbon atoms in the alkoxy group,

R2 is hydrogen or methoxy; and

R 1 is C 1 -C 4 alkyl, allyl, phenyl, p-nitrophenyl or p-methylphenyl.

The principle of the preparation of the active ingredient for this herbicidal composition by the process according to the invention is that the derivative of the general formula II,

O

N 'jJ-CW-X * (II) wherein

R, R 1, R 2 and X are as defined above and

X ¹ represents a chlorine, bromine or iodine atom, reacted with an alcohol of formula III,

R 1 OH (III) wherein R 1 is as defined above, wherein the reaction is carried out at -80 to 180 ° C and in the presence of heavy metal cations, Lewis acid, or, when X is chlorine and X ¹ is bromine or iodine, in the presence of an alkali metal or alkaline earth metal C 1 -C 10 alkoxy. It is advantageous to use an excess of the alcohol and silver tetrafluoroborate relative to the derivative of the general formula II. The reaction is carried out as previously. indicated in the presence of heavy metal cations such as silver, lead, mercury, etc., or in the presence of other Lewis acids such as aluminum chloride, tin chloride, zinc chloride, etc. The cations are derived from such compounds as acetates, oxides, nitrates, tetrafluoroborates and the like In the case where X ¹ is bromine or iodine, C 1 -C 10 alkoxides of alkali or caustic earth metals, for example methoxides, ethoxides, propoxides, butoxides, etc., of sodium, may be used instead of the compound of formula III potassium, rubidium, magnesium, zinc, cadmium and mercury.

The discovery of the above process is unexpected because the 2-halogen atom of the N-acetyl group is known to be labile. In the case of compounds (I) having halogen atoms substantially equally reactive or whose reactivity is relatively similar, there is a problem of replacing a halogen atom on an aryl radical substituted with a haloalkyl group, for example a benzyl halogen atom or a xylyl halogen atom, 2 of acetyl to produce the desired derivatives. For example, previous attempts by the inventor to react either an iodide or a methoxide anion with one or both haloalkylbenzyl residues to give 2 ', 6'-bis (chloromethyl) -N- (methoxymethyl) -2-chloroacetanilide resulted in partial replacement of the chlorine atom in all three A simple replacement of the chlorine atom by nucleophiles appears to be inadequate in such systems.

The inventor has discovered that a halogen atom of an aryl molecule substituted with a halomethyl group, such as benzyl halogen atoms, xylyl halogen atoms, etc., can be selectively activated with silver tetrafluoroborate (AgBFα) without activating the otherwise equally labile 2-acetyl halogen atom.

In addition, as noted above, in an alternative arrangement in some cases, for example, if the o-positions contain iodoalkyl or bromoalkyl groups, these groups can be etherified with an excess of alcohol by an equivalent of an alkali metal or caustic earth metal alkoxide, for example sodium alkoxide.

The conditions of this method are not critical. However, it is best to operate at temperatures in the range of about -80 ° C to 180 ° C, preferably 0 ° C to 125 ° C, even more preferably in the range of 25 to 100 ° C, although higher and lower temperatures may also be used temperatures after sufficiently long reaction times and at sufficient pressures (which may be below atmospheric pressure or not above atmospheric pressure) to ensure completeness of processing. Similarly, the concentrations of the reactants are not critical. However, one skilled in the art will appreciate that the ratios of the reactants are appropriately selected according to the following detailed descriptions and operating arrangements.

The term "alkyl" and compound forms of the term, such as "alkoxymethyl", mean primary, secondary and tertiary alkyl groups.

Preferred compounds are N, 2 ' -bis or N, 2 ', 6 ' -tris (alkoxymethyl) -2-haloacetanilides in which the alkoxymethyl groups have the same alkyl group in the alkoxy radical. These compounds are prepared using silver tetrafluoroborate as a catalyst dissolved in an alcohol solution of formula III wherein R 4 is the same alkyl group as in alkoxy R in formula II. In this case, selectively etherification occurs at the 2 'and / or 6' position (s) of the haloalkyl group, as exemplified in Example 18 below. If the alkyl group R 4 of the formula III is different from the alkoxy radical in the alkoxymethyl group R of the formula II, then transetherification may occur between the groups R 4 and R 4. The result is N, 12'-bis or N, 2 ', 6'-tris (alkoxymethyl) compounds having the same alkyl group R 4 in the alkoxymethyl group.

Another aspect of the invention relates to 2-haloacetanilide compounds with different alkoxymethyl groups on a nitrogen atom with different alkoxymethyl groups on a nitrogen atom and in the 2 'and / or 6' positions (i.e., ortho positions relative to the anilide nitrogen atom). Compounds of this type are prepared by treating N, 2'-bls or N, 2'-6'-tris (alkoxymethyl) -2-haloacetanides of the formula I with an alcohol of the formula III in which R4 is different and is usually longer than the alkyl moiety at the N- and 2'- and / or 6'-positions, in the presence of an organic sulfonic acid such as methylsulfonic acid, in which case the transetherification is selectively between the R 6 group and the alkoxymethyl group on the nitrogen atom. This type is discussed in Example 22. The transetherification process discussed in this paragraph is the subject of another invention.

The foregoing compounds having identical or different aicoxymethyl groups in the N-, 2'- and / or 6'-positions can be prepared by N-alkylating the anion of a secondary 2-haloacetamide having one or more o-alkoxymethyl substituents with an alkylating agent , such as haloalkyl ether, for example chloromethyl methyl ether.

The preparation of N, 2'-bis (alkoxymethyl) -2-haloacetanilides by this N-alkylation procedure is given in Example 23 below. Compounds of this type discussed in this and the preceding paragraph can also be prepared by treatment with salts of alcohols of formula III with metals, for example R4OM wherein M represents an alkali metal or alkaline earth metal with a compound of the formula · II, wherein R is an alkoxymethyl group, X is chloro and X ¹ represents bromine or iodine.

The herbicidal compositions of the invention are useful as selective herbicides in application instead of the undesired plants to be controlled and the desired plants to be protected.

The invention may be more clearly understood by reference to the following detailed description.

The compounds of this invention are derived from intermediates characterized in that they contain, as a substantial part, halomethyl substituents in one or both ortho positions of the anilide ring. These intermediates are novel in themselves and are the subject of another invention by the inventor who discovered a plurality of methods for making intermediates. Such methods include the radical halogenation of 2-haloacetanilides, preferably in the presence of ultraviolet light. The Chlo210642 race proceeds readily to form the monochlorinated derivative at the N-methyl and / or o-alkyl position. However, there is no reaction at the position or at the core. Bromination with elemental bromine, but especially with N-bromosuccinimide, is selective. Only o-alkyl monobromination occurs, even in the presence of the N-methyl residue. Examples of methods for making intermediates used in this invention are described in the following examples. The temperature is always given in degrees Celsius.

Example 1

This example describes alternative methods of preparing the starting compound N- (methoxymethyl) -2 ', 6'-bis (chloromethyl) -2-chloroacetanedde, which is used to produce the compounds of the invention.

1a) 2-Chloro-N, 2 ', 6 ' -trimethylacetanilide (21.1 grams, 0.1 mol) in 200 ml of carbon tetrachloride was placed in a 500 ml flask. The solution is irradiated with a UF source (0.2 amp) located inside the flask. Chlorine (0.1 mol, 7 g) was added under stirring to the surface of the reaction mixture. The reaction is slightly exothermic, the temperature is in the range of 20 to 40 ° C. Upon addition of the entire amount of chlorine, a substantially colorless solution is obtained. According to the NMR spectrum, a mixture was obtained in which the methyl groups of the nitrogen and the ring were substituted. Neither the group (CH 2 Cl 2) nor the hydrogen atoms on the ring were attacked. The mixture is cooled to about 57. An additional 0.1 mol of chlorine is added, while the NMR spectrum still shows that a mixture of monochlorinated methyl groups on the nitrogen atom and on the ring is present in the reaction mixture. Finally, after the third molar equivalent, the spectrum was simplified. The material was allowed to stand over Saturday and Sunday, then the solvent was removed to give a viscous oil. A portion of this oil was recrystallized from pentane-ether to give crystals of mp 70-75 °. Carbon disulfide is also a good solvent for recrystallization. The structure of this material, based on the NMR spectrum and its other reactions, was determined to be 2-chloro-N, 2 ', 6'-tris (chloromethyl Jacetanilide).

A portion of the viscous oil (7 g) was heated in a 250 ml methanol bath for 10 minutes, then cooled slowly and freed from methanol to 50 ml. White crystals are obtained, which are filtered off. Yield 5 g, mp 111-114 °. Recrystallization from carbon tetrachloride gave a material with a melting point of 117-118 °.

For C12H14Cl3NO2: calculated: 46.40% C, 4.54% H, 4.51% N,

Cl, 34.24. Found: C, 44.48; H, 4.33; N, 4.64.

34.96% Cl.

The product was identified as the above intermediate.

1b) The above intermediate can also be prepared from preformed N-chloromethyl-divertate (derived from chloroacetyl chloride and azomethine 2,6-xylidine). 2-Chloro-N- (chloromethyl) -2 ', 6'-acetoxylide (10 g' 0.04 mol) in 200 ml carbon tetrachloride is treated with 0.081 mol (5.8 g) chlorine at 40-45 °. An additional 1.4 g of chlorine is added to compensate for the losses due to the volatility of the chlorine. The solvent was removed and the residue was boiled for 1/2 hour with about 300 ml of methanol. Two thirds of the volume is then removed, the contents are scratched and the product is filtered off. 6.4 g are obtained.

Example 2 g of the compound of Example 1 (0.0065 mol), i.e. N- (methoxymethyl) -2 ', 6'-bis (chloromethyl) -2-chloroacetanilide, are added to 25 ml of methanol, dissolved hot and added. solution of 0.0135 mol (2.7 g) of silver tetrafluoroborate (AgBF4) in 10 ml of methanol. The material was stirred and heated to 35-40 °. Only 0.8 g of silver chloride is isolated by filtration. Small-scale research has shown that a slightly higher precipitate yield can be obtained if the filtrate is heated. More precipitate is obtained when more AgBFd is added and the mixture is heated. An additional 2.5 g of silver tetrafluoroborate is therefore added. The mixture was refluxed for three minutes and maintained above 55 ° for a further 10 minutes. The filtrate is boiled again in a filter flask on a stove, then filtered. An additional 0.1 g (total 1.6 g AgCl precipitated) was obtained. The filtered solution was left in the refrigerator overnight. An additional 2.0 g of AgBF was added and the mixture was boiled for about 5 minutes. An additional 0.1 g of AgCl (7.2 g total AgBF4) was obtained. The methanolic solution is evaporated to 1/5 of its original volume and added to a 5% sodium bicarbonate solution. Silver oxide (3.1 g) precipitated immediately. This was filtered off and the salt (NaCl) with dichloromethane was added. The aqueous brine solution was extracted several times with dichloromethane. After drying, the organic solution was distilled off in vacuo. 1.2 g of a pale yellow oil are obtained.

For C 14 H 20 ClNO 4: calculated: 55.72% C, 6.68% H, 4.64% N,

11.75% Cl;

Found: C 55.71, H 6.69, N 4.65,

11.78% Cl.

By repeating the procedure a second time using 3.1 g of the above intermediate, 2.1 g of the final product are produced.

The product was identified as N, 2 ', 6'-tris (methoxymethyl) -2-chloroacetanilide by NMR spectroscopy.

Example 1 and d 3

Κ N- (methoxymethyl) -2 ', 6'-bis (chloromethyl) -2-chloroacetanilide (2.5 g, 0.0081 mol) in 100' ml of isopropanol was added 8.6 g of AgBFα and the mixture was boiled for 1 hour 2.3 g of silver chloride are isolated, treated with 5% sodium bicarbonate solution, to ensure complete removal of silver ions and regeneration of the ether amide, the salt is added, and the mixture is extracted with dichloromethane. The solid material was filtered off, the organic solution was separated and the solvent was removed in vacuo to give 2.3 g of an oil.The NMR spectrum of this oil showed no CH3O group and three isopropoxy groups. 210 DEG (67 Pa) 1.3 g of amber distilled oil with unchanged NMR spectrum are obtained.

For C 20 H 32 ClNO 4 calculated: 62.24% C, 8.36 ° C, H, 9.19% Cl,

3.63% N;

found: 62.10% C, 7.84% H, 8.25% Cl,

4.16% N.

The product was identified as N, 2 ', 6'-tris (isopropoxymethyl) -2-chloroacetanilide.

Example 4

2 ‘, 6´-Bis (1-chloroethyl) -N-methyl-2-bromoacetanilide (0.01 mol) was added to a solution of 2.4 g (0.012 mol) of AgBFα in about 75 mL of methanol. The mixture was allowed to stand in the dark overnight. Filtration gave AgCl. The solvent was distilled off. The product was extracted with pure methylene chloride, the solution was washed with an aqueous solution of sodium chloride and sodium carbonate, dried over magnesium sulfate and filtered. The solvent was removed in vacuo. The residue is recrystallized and / or sublimed in vacuo.

Analysis calculated for: CisIHfeB BrNOs: C, 52.33; Br, 23.21; N, 4.07.

Found: C, 49.75; Br, 25.57; N, 3.98%.

The product, which was produced in 19% yield and had a m.p. of 86-95 °, was identified as 2 ', 6' - (bis-1-methoxyethyl) -N-methyl-2-bromoacetanilide.

Example 5

To 2 '- (bromomethyl) -6'-tert-butyl-N-methyl-2-bromoacetetamide (3.7 g, 0.01 mol) in 150 mL of methanol was added 2.4 g of AgBFα in 5050 mL of methanol. The material was allowed to stand for three hours. 1.6 g of silver bromide are filtered off. An additional overnight standing yielded an additional 0.1 g of AgBr (theory 1.9 g). The solvent was distilled off in vacuo. The residue was treated in the usual manner with dichloromethane-sodium chloride-10% sodium carbonate. After filtering off (cloth filter) the solvent is stripped off. An oil is obtained which crystallizes on standing. Recrystallization from hexane gave 2.1 g of product, mp 55-60 [ ^mu] , a second recrystallization from heptane gave a white solid, mp 72-74 [deg.].

For C15H22BrNO2: calculated: 54.88% C, 6.76% H, 24.34. % Br,

N, 4.27;

Found:% C, 54.87;% H, 6.77;% Br, 24.26.

4.29% N.

The product was identified as 2 '- (methoxymethyl) -6' -t-butyl-N-methyl-2-bromoacetanilide.

Example 6

2´-Bromomethyl-6‘-tert-butyl-N-methyl-2-chloroacetanilide (5 g, 0.015 mol) was dissolved in 250 ml of ethanol. To the solution was added a clear solution of 3.3 g AgBFα in 50 mL ethanol. Yellow silver bromide precipitated immediately. The material was allowed to stand overnight in the dark. The silver bromide is then filtered off and the ethanol is distilled off in vacuo. The residue was extracted with dichloromethane, washed with 150 ml of 10% sodium carbonate (to which something sodium chloride was added). After filtering the two liquid phases, the organic phase is separated, washed once more with water and the solvent is removed in vacuo. The residue was recrystallized from heptane. A second crystallization from ethanol gave 3.0 g of product, m.p. 77-78 °.

Analysis for C 16 H 24 ClNO 2: calculated: 64.52% C, 8.12% H, 4.70% N; Found:% C, 63.50;% H, 7.81;% N, 4.82.

The product was identified as 2 '- (ethoxymethyl) -6' -t-butyl-N-methyl-2-chloroacetanilide.

Example 7

2'- (Bromomethyl) -6'-tert-butyl-N-methyl-2-chloroacetanilide (1.7 g, 0.005 mol) in ethylene chloride was added to a solution of 0.7 p-cresol and 1.0 g AgBFi in ethylene dichloride. The theoretical amount of silver bromide precipitated immediately. After standing for not more than 1/2 hour, the solution is treated with sodium chloride solution. Filtration removes the last residual silver ions. The ethylene dichloride solution was then washed with 5% sodium hydroxide to remove phenol. After this wash, dichloromethane is added and the organic solution is washed with water for the last time.

210842 li

After drying over magnesium sulphate, filtering, removing the solvent in vacuo and recrystallizing the residue twice, 0.3 g of a white solid is obtained from isopropanol, m.p. 148-152 °.

H, 7.28; N, 3.89. Found: C, 69.93; H, 7.29; N, 3.84.

The product was identified as 2 '- (p-tolyloxymethyl-6'-tert-butyl-N-methyl-2-chloroacetanilide).

Example 8

2'- (Bromomethyl) -6'-tert-butyl-N-methyl-2-chloroacetanilide (1.6 g, 0.005 mol) in methanol was mixed with a solution of 0.95 grams of sodium nitrophenolate in methanol. It was cooled, scratched and filtered to give 0.8 grams of solid precipitate, mp 185-186 ° C. Recrystallization of portions from acetonitrile gave white crystals, mp 186-187 ° C. Analysis for C 20 H 23 ClN 2 O 4 calculated % C, 61.46;% H, 5.93;

7.17,% N;

Found: C 61.37, H 6.01, Cl 9.12,

7.09% N.

The product was identified as 2 '- (p-nitrophenoxymethyl) -6‘-tert-butyl-N-methyl-2-chloroacetanilide.

Example 9 '2'- (Chloromethyl) -6'-tert-butyl-N-methyl-2-chloroacetanilide (0.01 mol) was added to 75 ml of tert-butanol containing 2.4 grams (0.012 mol) of AgBFe The precipitated silver chloride is filtered off, the solvent is stripped off, the product is extracted with pure dichloromethane, washed with brine and sodium carbonate and dried over magnesium sulphate.After filtration and drying, the solvent is distilled off in vacuo. The residue was recrystallized and / or distilled in vacuo for C18 H28 ClNO2 Calc'd: C, 66.34; H, 8.66; N, 4.30 Found: C, 65.21; H, 8.49; , 41% N.

Product, it. 65-67 °, produced in a yield of 46 ° / o, was identified as 2 '- (tert-butoxymethyl) -6' -t-butyl-N-methyl-2-chloroacetanilide.

Example 10

The procedure was as in Example 9, except that propanol was used instead of tert-butanol. The product is obtained in the form of a white solid, m.p. 53-54 °, yield 64%.

H, 8.40; N, 4.49. Found: C, 64.42; H, 8.15; N, 4.63.

The product was identified as 2 '- (propoxymethyl) -6‘-tert-butyl-N-methyl-2-chloroacetanilide.

Example 11

Following the same procedure as in Example 6, but replacing ethanol with methanol, a white solid was produced which recrystallized from methanol gave m.p. 74-75 °. Yield 70%.

H, 7.81;% M, 4.94;% calculated for C15H22CINO2; Found:% C, 63.47;% H, 7.83;% N, 4.97.

The product was identified as 2 '- (methoxymethyl) -N-methyl-2-chloroacetanilide.

Example .12

To a solution of 2 '- (bromomethyl) -6'-tert-butyl-2-chloroacetanilide (1.6 g, 0.005 mol) in 25 ml of methanol was added 1 g (about 0.005 mol) of AgBFα in 20 ml of methanol. The theoretical amount of silver bromide precipitated immediately. Without further waiting, the filtered solution was distilled off in vacuo. A 10% sodium carbonate solution, methylene chloride and sodium chloride were added to the residue. The solution is filtered through a sintered glass funnel. The methylene chloride layer was separated and the solvent was distilled off in vacuo. The solid residue, m.p. 70-90 °, 0.8 g, is recrystallized from various solvents, preferably cooled aqueous methanol. For analytical purposes, a sample of the product is sublimed under vacuum from an oil bath at 100-110 ° (6.7 Pa), m.p. 101-102 °.

Analysis for C 14 H 20 ClNO 2 Calcd: 62.33% C, 7.47% H, 13.14% Cl,

5.19 ·% Ni found: C 61.45, H 7.40, Cl 12.82,

5.01% N.

The product was identified as 2 '- (methoxymethyl) -6‘-tert-butyl-2-chloroacetanilide.

The above product can also be prepared by treating 3.2 g of the above 2-bromomethyl starting material in methanol with 0.01 mol of sodium methoxide (7.0 mL, 1.48 M NaOCH 3 in methanol). The reaction mixture is heated to 50-60 °, cooled, allowed to stand, the solvent is stripped off and a mixture of dichloromethane and water is added. The Di210642 chloromethane solution was distilled off and the residue was recrystallized from methylcyclohexane. A product is produced which is identical to the product described above.

Example 13

Following the same procedure as described in Example 12, but replacing the above alcohol with ethanol, a white solid is obtained after recrystallization from heptane, m.p. 110-112 °. H, 8.16; N, 5.15. Calculated: C, 61.87; H, 8.16; Found:% C, 61.02;% H, 7.55;% N, 5.07;

The product has been identified as 2 '- (ethoxymethyl) -6`-tert-butyl-2-chloroacetanilide.

Example 14

If the procedure was as described in Example 13, but using isopropanol as the alcohol, a gray solid of m.p. 98-100 ° was obtained in 50% yield.

Analysis for C 16 H 24 ClNO 2: calculated: 64.53% C, 8.12% H, 4.70% N; Found:% C, 64.35;% H, 8.09;% N, 4.72.

The product was identified as 2 '- (isopropoxymethyl) -6`-tert-butyl-2-chloroacetanilide. Example 15

If the procedure is as described in Example 13, but using butanol as the alcohol, 2 '- (butoxymethyl) -6)-tert-butyl-2-chloroacetanilide is produced in 45% yield. 75-77 °.

H, 8.40; N, 4.49. Found: C, 65.47; Found: C 65.53, H 8.41, N 4.54. Example 16

In the same manner as described above in Example 4, but using propanol as the alcohol, 2 '- (propoxymethyl) -6'-tert-butyl-2-chloroacetanilide, m.p. 40 °, was produced in 40% yield.

Analysis for C 16 H 24 ClNO 2: calculated: 64.52% C, 8.12% H, 4.70% N; Found: C, 63.33; H, 7.89; N, 4.73. Example 17

To a solution of 2 '- (bromomethyl) -6'-tert-butyl-2-chloroacetanilide (3.2 g, 0.01 mol) in 75 ml of allyl alcohol is added 2.4 g (0.012 mol) of silver tetrafluoroborate in 75 ml of allyl alcohol . The mixture was allowed to stand overnight in the dark. The solution is filtered and the solvent is distilled off. The resulting oil was dissolved in dichloromethane, washed once with brine and then twice with water. The organic layer was dried over magnesium sulfate. The solvent was distilled off. An oil is obtained which is crystallized from pentane. Yield

1.7 g, mp 65-67 °.

H, 7.50; N, 4.74. Found:% C, 63.85;% H, 7.21;% N, 4.88.

The product was identified as 2‘- (allyloxymethyl) -6‘-tert-butyl-2-chloroacetanilide.

Example 18

To a solution of 2 '- (bromomethyl) -6'-tert-butyl-N- (methoxymethyl) -2-chloroacetanilide (4.2 g, 0.0113 mol) in 250 mL of methanol is added 50 mL of a solution of 3.3 g of tetrafluoroborate The mixture was left in the dark overnight, after which 89% of the theoretical amount of silver bromide was filtered off. The organic phase is separated off and the solvent is distilled off, leaving 3.0 g of an oil whose NMR spectrum is consistent with the structure. yield 59 percent.

Analysis calculated for: C 16 H 24 ClNO 3:% C, 61.24;% H, 7.71;% N, 4.46.

11.38% Cl;

Found: C 60.95, H 7.77, N 4.55,

11.44% Cl.

The product was identified as 2 '- (methoxy, methyl) -6'-tert-butyl-N- (methoxymethyl) -2-chloroacetanilide.

Example 19

By following the procedure of the preceding example, but replacing the starting materials therein with 2 '- (bromomethyl) -6'-tert-butyl-N- (ethoxymethyl) -2-chloroacetanilide and ethanol, a white solid was prepared with m.p. 114-116 °.

Analysis calculated for: C 16 H 28 ClNO 3:% C, 63.24;% H, 8.26;% N, 4.10;

Found:% C, 62.24;% H, 7.90;% N, 4.87.

The product was identified as 2 '- (ethoxymethyl) -6' -t-butyl-N- (ethoxymethyl) -2-chloroacetanilide.

Example 20 g of 2'-formyl-6'-tert-butyl-2-chloroacetanilide is dissolved in 10 ml of methanol. To the solution was added 10 g of (CH 3 O) 3 CH; a few drops of thionyl chloride, which is also added, form a catalytic amount of hydrochloric acid. The mixture was boiled in a water bath for 45 minutes, then allowed to stand overnight at room temperature (not required), a few drops of 50% sodium hydroxide was added to neutralize the acid, and the cooled solution was distilled off in vacuo. The pH of the solution was adjusted to about 12-14 by the addition of sodium hydroxide and water. The resulting solid was filtered off, the cake on the filter was washed with water, and dried in an oven at 60 ° for 2-3 hours. 2.1 g (87% yield) of a white solid The analytical sample was recrystallized from isopropanol, mp 127-132 °.

For C15H22CINO3: calculated: 60.10% C, 7.40% H, 4.67% N;

Found:% C, 58.92;% H, 7.12;% N, 4.77%.

The product was identified as 2- (dimethoxymethyl) -6-tert-butyl-2-chloroacetanilide.

Example 21

A solution of 5 g (0.012 mol) of 2 ', 3'-bis- (bromomethyl) -6'-tert-butyl-2-chloroacetanilide in 175 m of methanol is mixed with 7.0 AgBFa, which is dissolved in the same solvent. The mixture was allowed to stand overnight in the dark. The silver bromide is filtered off. The methanol was distilled off, dichloromethane was added to the residue and the solution was treated with NaCl / Na 2 CO 3, filtered with clay and washed once more with water. After drying, the solvent was distilled off. The solid was recrystallized from ether. The analytical sample is sublimed in vacuo. 115 to 117 ^Ď .

For C16H24ClNO3: calculated: 61.24% C, 7.71% H, 11.30% Cl,

4.46% N;

Found: C 58.05, H 7.42, Cl 10.64,

4.24% N.

The product, a gray solid produced in 50% yield, was identified as 2 ', 3'-his- (methoxymethyl) -6'-tert-butyl-2-chloroacetanilide.

The acetetanilide starting material of this example is produced as follows:

Dissolve 15 g (0.059 mol) of 2'-3'-dimethyl-6'-tert-butyl-2'-chloroacetanilide in 600 ml of carbon tetrachloride in a one-liter flask. The reaction apparatus also contains two white reflectors. The reaction mixture was heated to reflux and then purged with nitrogen. A solution of bromine (9.44 g, 0.059 mol) in 50 mL of carbon tetrachloride was added dropwise. During bromine addition, the reaction was monitored by NMR spectroscopy. The treatment is not carried out gradually, but rather both arylmethyl groups are brominated at about the same rate. A total of two molar equivalents of bromine are added. The NMR spectrum at this stage showed that reaction ¹ was in good yield. The mixture is allowed to stand over Saturday and Sunday. The reaction mixture was then filtered. Mp 180-182 °, recrystallization 187-189 °. Vacuum sublimation gave a sample for elemental analysis, mp 195-197 °. Yield 50%.

For C 14 H 18 Br 2 ClNO: calculated: 40.85% C, 4.41% H, 3.40% N;

Found:% C, 40.60;% H, 4.37;% N, 3.40.

This product was identified as the product mentioned in the introductory sentence of this example.

Example 22

This example illustrates the preparation of compounds with different alkyl radicals and different alkoxymethyl radicals of the alkoxymethyl group at the N- and o-positions.

g of 6'-methyl-N, 2'-bis (methoxymethyl) -2-chloroacetanilide are mixed with 75 ml of butanol and 5 microdrops of methylsulfonic acid and boiled under a soxhlet filled with molecular sieve (0.3 nm). The reaction is distilled off, the residue containing some butanol is dissolved in benzene, washed once with sodium bicarbonate, and the solvent is distilled off. g oil (87% yield).

Analysis for C 16 H 24 ClNO 3 calculated: C 61.12, H 7.71, N 4.46.

Found: C, 62.12; H, 8.01; N, 4.29.

The product was identified as 2 '- (methoxymethyl-6-methyl-N- (butoxymethyl) -2-chloroacetanilide by NMR spectroscopy).

Example 23 g of 2'-methyl-6 '- (methoxymethyl) -2-chloroacetanilide was dissolved in a mixture of 200 ml of diethyl ether with tetrahydrofuran (80:20). The solution was treated with well washed potassium hydride to release the theoretical amount of hydrogen gas. After working up and washing with water, the distilled middle fraction, according to gas chromatography, corresponds to the crude product (yield 26 g, 84 g / o), which gives 19 g of oil at 180 DEG (6.7 Pa).

For C 13 H 18 ClNO 3 calculated: 57.46 ° / q C, 6.68% H, 5.15% N; found: 57.32 O / o C, 6.72% H, 5.13% N.

The product was identified as 2'-methyl-N, 6‘-bis (methoxymethyl) -2-chloroacetanilide.

The procedure used in this example can be modified with halomethyl alkyl ether using a starting acetanilide having different alkoxymethyl groups at the ortho positions and the nitrogen atom.

Example 2 4 to 28

In a similar manner as described in the above examples, other compounds of the above general formula (I) are produced. These compounds and some of their physical properties are listed in the table below.

AND.

210 6 4 2 Example Empirical Compound 1.1. ° C analysis

No formula t _v 'element off. nal.

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00 rd rd CM 00 r— < rd cn CD rd > N > N 5? > N > N CD CD P “f O CD «3 CO in cn O ζθ rd rd oo CD WHAT rd rd

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O f “—4

O p

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O-IH ffio

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M

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1 CM Φ IN 1 CM and q "honor cm honor 2 CM ⁵ 8 Tt * io WHAT c> 00 CM CM CM CM CM

As noted above, the compounds of this invention are effective as herbicides in partially or totally inhibiting undesirable vegetation. Tables IIIA and IVA summarize test results to determine pre-emergence herbicidal activity and Tables IIIB and IVB test results to determine postemergence herbicidal activity of representative compounds.

The pre-emergence test is performed as follows:

A good topsoil is put in aluminum bowls. The topsoil is compressed so that the surface is 0.95 to 1.27 cm from the top of the dish. A predetermined amount of seeds or vegetative cuttings of different plant species is placed on the soil surface. The soil, which is needed to level the trays after planting the seeds or adding vegetative cuttings, is weighed into the dish. A known amount of the active ingredient is applied in a solvent or in the form of a wettable powder. The soil is mixed and used as a coating for pre-prepared dishes. After processing, the dishes are transferred to a greenhouse. They are watered from below as needed to provide adequate moisture for germination and growth.

Unless otherwise noted, approximately 2 weeks after sowing and processing, the plants are observed and the results recorded. These results are summarized in Tables IIIA and IVA below. The herbicide rating is determined using a fixed scale based on percent damage to each plant species. The rating is defined as follows:

% regulation evaluation

Post-emergence tests were performed as follows:

The active ingredient is sprayed onto two or three week old samples of different plant species. A spray, wettable powder solution or suspension containing the appropriate dose of active ingredient to obtain the desired test dose, and a surfactant are applied to the plants. The treated plants are placed in a greenhouse. Unless otherwise indicated, after approximately two weeks, effects that vary between no response and total inhibition are observed and recorded. The results of the post-emergence herbicidal efficacy are as follows:% regulation evaluation

0 to 24 0 25 to 49 1 50 to 74 2 75 to 99 3 100 ALIGN! 4

The plant species used in these tests are identified by letters in accordance with the following legend:

A = Thistle Thistle

B = Beet

C = colon

D - broom

E = white goosefoot

F = pepper plant

G - bay

H - Creeping wheatgrass

I - Halle sorghum

J = Spruce Brome

K = corn foot

0 to 24 0 25 to 49 1 50 to 74 2 75 to 100 ALIGN! 3

Table IIIA - Preemergence treatment of the compound kg / ha of Example no.

kind of plants

ABCDEFGHIJK

5.6

5.6

11.2

5.6

5.6

5.6

11.2

11.2

5.6

5.6

0 1 0 O 1 2 1 0 3 3 00 0 01000313 00010010000 0001000 0 011 0 0 1 1 3 3 0 0 0 3 3 111132331 2 3 30103211033 1 0 010000033 1 0 0 1 0 0 1 0 0 1 1 000020 3 2023 from example no.

kg / ha type of plant

ABCDEFGHIJK

10 5.6 0 0 0 0 3 1 2 1 0 3 3 11 5.6 0 0 0 1 3 1 2 0 0 1 3 12 5.6 0 0 1 2 3 1 2 1 0 2 3 13 5.6 0 0 1 0 2 1 2 1 0 2 3 14 5.6 0 0 1 1 3 0 3 1 1 3 3 15 Dec 5.6 1 0 1 0 2 2 3 3 0 3 3 16 11.2 0 0 1 0 3 1 3 3 1 2 3 16 5.6 0 ..0 1 0 1 0 2 2 1 2 3 17 11.2 0 1 1 1 2 1 1 2 0 2 3 17 5.6 0 0 1 0 3 0 1 1 0 0 3 18 5.6 0 0 1 1 3 1 1 2 1 3 3 19 Dec 11.2 0 0 1 1 2 0 1 2 1 1 2 19 Dec 5.6 0 0 1 0 2 0 1 2 1 1 2 20 May 11.2 1 0 1 1 3 1 1 1 0 1 3 20 May 5.6 0 0 0 0 2 0 1 0 0 0 2 22nd 11.2 1 1 1 1 1 1 2 3 1 3 3 22nd 5.6 1 1 1 1 1 0 1 3 1 2 3 23 5.6 0 0 0 0 2 0 0 0 0 0 1 24 5.6 1 1 2 2 3 3 2 0 0 3 3 25 5.6 3 0 0 0 1 2 0 1 0 1 3 26 11.2 3 2 2 2 3 3 3 2 0 3 3 26 5.6 3 1 1 2 3 3 2 1 0 3 3 27 Mar: 11.2 0 0 0 0 0 0 0 0 0 0 3 27 Mar: 5.6 0 0 0 0 0 0 0 0 0 0 3 28 11.2 3 2 1 3 3 3 3 2 0 3 3 28 5.6 2 2 1 2 3 1 3 2 0 3 3 Table IIIB - Post-emergence processing . _r ., ...... .... ,, -> compound kg / ha kind of plants from example no. AND (B) C D E F G H AND AND TO 2 5.6 0 1 0 1 0 0 0 0 - 0 1 4 11.2 0 1 0 1 4 1 0 1 0 0 0 5 11.2 0 1 1 2 1 0 0 0 0 0 0 6 11.2 1 1 1 1 2 1 0 1 0 0 2 7 11.2 0 1 0 0 1 1 0 0 0 0 1 8 11.2 1 1 0 0 0 0 0 0 0 0 0 9 11.2 1 1 0 1 4 4 0 0 0 1 2 10 11.2 1 1 1 1 1 1 1 1 1 0 2 11 11.2 0 1 0 1 1 0 0 0 0 1 1 12 11.2 0 1 0 1 0 0 0 0 0 0 0 13 11.2 1 1 0 1 1 1 0 0 0 0 1 14 11.2 0 0 0 1 1 0 0 0 0 0 1 15 Dec 11.2 1 1 0 1 . 1 1 0 0 0 0 1 16 11.2 1 1 1 1 2 1 1 1 0 0 2 17 11.2 0 1 0 1 1 0 1 0 0 0 2 18 11.2 1 1 0 1 1 1 0 0 - 0 2 20 May 11.2 0 0 1 1 0 0 1 1 0 0 0 23 11.2 0 0 1 0 0 0 0 0 0 0 ^! 0 24 11.2 0 1 0 1 0 2 0 0 0 0 2 25 11.2 0 1 0 1 0 0 0 0 0 0 2 26 11.2 0 1 0 1 - 1 1 0 0 0 2 28 11.2 0 1 1 1 0 0 1 1 0 1 1

The compounds were further tested as described above on the following plant species:

L = soybean

M = diabetes

N == wheat

O = rice

P = sorghum

B = beets

Q = buckwheat

D - broom

The results are summarized

R = Hemp Sesbania E == white goosefoot F - red pepper C = parsnip J - spiny brome S = millet K = corn leg T = dewcap Tables IVA and IVB.

Table IVA - Pre-emergence treatment compound kg / ha plant species of Example No. LMNOPBQDREFCJSKT

2 5.6 0 1 1 0 2 1.12 0 1 0 1 2 0.28 0 0 0 0 2 0.06 0 0 0 0 3 1.12 0 0 0 0 3 0.28 0 0 0 0 3 0.05 0 0 0 - 5 1.12 1 0 0 2 5 0.28 0 0 0 0 5 0.06 0 0 0 0 6 5.6 1 2 2 3 6 1.12 0 1 1 1 6, 0.28 0 0 0 0 6 0.06 0 0 0 0 7 5.6 0 1 0 1 7 1.12 0 0 0 1 7 0.28 0 0 0 0 8 5.6 1 2 0 0 8 1.12 0 1 0 0 9 1.12 3 1 1 1 9 0.28 3 1 0 1 9 0.06 3 0 0 0 10 5.6 1 3 2 3 10 1.12 Ί 2 2 2 ' 10 0.28 1 1 1 1 10 0.06 0 0 0 1 ' 11 5.6 2 3 1 2 11 1.12 1 2 0 0 11 0.28 1 1 0 0 11 0.06 1 0 0 0 12 1.12 • 2 1 3 3 12 0.28 1 0 0 1 12 0.06 0 0 0 0 13 5.6 3 3 3 3 13 1.12 2 1 2 2 13 0.28 1 1 0 1 13 0.06 0 0 0 1 13 0.011 0 0 0 0 14 5.6 2 2 3 3 14 1.12 2 1 2 3 14 0.28 1 0 0 0 14 0.06 0 0 0 0 14 0.011 0 0 0 0 15 Dec 5.6 2 3 3 3 15 Dec 1.12 1 2 2 3 15 Dec 0.28 0 1 0 1 16 5.6 1 2 1 3 16 1.12 0 1 0 1 16 0.28 0 0 0 1 16 0.06 0 0 0 0 17 5, β 2 2 3 2 ' 17 1.12 1 0 1 0

100112100333 20 0 01010 2,333 000000000233 000000 0 00 0 1 0 00 0 00000 0 023 000000000011 oooooooooooooo 301011100233 0 0 0 0 0 0 0 0 0 0 2 3

00000000 '0 011 · 30101110' 233 3

2000 0 1001233 200 0 010 0 1222 000000 0 00 0 10 000010100233 00 0 001001333 000 0 00000 0 22

000 01 0 0 00032

0 0 0 0 0 0 0 0 0 1 1,231 0 12111233

130011010122 0 3 0 000000000

300 12 3313333

0 0 0 0 1 1 0 2 3 3 3

000 0 01 0 2232

0000 0 0100112

0001 2 22 2 333

1000121 0133 3 '

0 0 0 0 0 0 0 0 0 0 0

0000000 0 0 11 i 30011 1 003333 1 00010002223 000 0 00000001 3 3 2 3 3 3 3 1 3 3 3 3

0 2 220123 33

0 0 2 1 0 0 0 1 3 3 3

1000 1 0 0 0 Ό 009 0 3 0 0 0 0 0 0 0 0 0 0

3102232 3, 333.3

0 01221 13333

10000000 0 14 3

00000000 0 0 9

0300.0 000 0 000

310 133213333

0 00210 0 2233

00000001122 310 T 232 13333

100011102333 0 00011001 2 23 0,000 0,000 0,012

0 2 ί 1 1 1 0 3 3 3 3

100 0 0 000112 3

Example compound no. kg / ha L M N O P (B) plant type Q D R E F 1 n AND :WITH TO T 17 0.28 O 0 0 0 0 0 0 0 0 0 0 0 0 1 2 '2 18 5.6 2 2 2 2 3 0 2 2 2 3 2 1 3 3 3 3 18 1.12 1 1 1 1 2 0 1 2 2 2 1 0 2 3 3 3 18 0.28 0 0 0 0 0 ' Ol 0 0 0 0 0 0 ΰ 1 2 2 18 0.06 0 0 0 1 0 0 ' 0 1 0 0 0 0 0 0 1 2 19 Dec 5.6 1 2 3 3 3 0 0 2 1 i2 2 0 3 3 3 3 19 Dec 1.12 1 1 0 1 3 0 O 1 1 1 1 0 3 3 3 3 19 Dec 0.28 0 1 0 1 1 0 0 0 1 1 0 0 2 2 2 2 20 May 5.6 2 1 2 2 3 0i 1 1 1 1 1 r 3 3 3 3 20 May 1.12 O 0 0 0 0 0 0 0 1 0 0 ' 0 1 1 2 2 22nd 5.6 0 0 1 1 2 0 0 1 1 1 0 1 ' »3 3 3 3 22nd 1.12 0 0 0 1 1 0 0 O 0 1 0 0 2 2 3 3 22nd 0.28 '0 1 0 0 0 0 0 0 0 1 0 0 0 0 1 2 22nd 0.06 and 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 24 5.6 0 2 0 1 3 2 3 2 2 3 3 2 1 3 3 3 24 1.12 0 1 0 0 2 0 0 1 1 1 1 0 0 3 3 3 24 0.28 0 0 0 0 0 0 0 0 0 0 1 0 0 3 3 3 24 0.06 0 10 0 0 0 0 0 0 0 0 0 0 ’’ 0 0 0 2 25 5.6 0 1, 1 0 3 1 1 2 3 0 1 3 ' 1 3 3 3 25 1.12 0 - 0 0 1 0 2 0 0 3 2 0 2 3 3 3 25 0.28 0 1 2 0 0 0 0 0 0 0 2 0 1 3 3 3 25 0.06 0 0 0 1 0 ‘ O 0 0 0 0 0 0 0 0 3 2 25 0.011 O 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 26 5.6 '1 2 2 3 3 3 2 3 3 - 3 1 3 3 3 3 26 1.12 0 3 1 3 3 1 3 1 3 - 3 0 ’ 3 3 3 3 26 0.28 0 2 1 2 3 0 0 0 2 - 2 0 1 3 3 3 26 0.06 0 0 0 0 0 fl ¹ 0 0 0 -. 1 0 0 1 3 3 26 0.011 O 0 0 0 0 · 1 0 0 0 - 2 0 0 0 3 2 27 Mar: 5.6 0 0 0 0 0 0 1 0 1 3 3 0 0 0 3 3 27 Mar: 1.12 0. 0 0 0 0 0 0 0 - 3 1 0 ' 0 0 2 3 27 Mar: 0.28 0 0 0 0 0 0 0 0 0 0 0 0 ' 0 0 0 1 28 5.6 0 3 2 3 3 2 3 3 3 3 3 0 ' 3 3 3 3 28 1.12 0 2 0 2 3 1 3 2 2 3 3 0 3 3 3 3 28 0.28 0 1 O 0 1 0 0 0 0 3 3 0 0 3 3 3 28 0.06 0 0 O, 0 0i 0 1 0 0 3 2 0 0 0 2 2

Table IVB

Post-emergence treatment of compound kg / ha plant species of Example No. LMNOPBQDREFCJSKT

5,6 2 1 0

1,12 10 0

0.28 1 0 0

The effect of a herbicidal composition according to the invention comprising a compound prepared according to the procedure of Example 16, i. 2 '- (n-propoxymethyl) -6‘-t-butyl-2-chloroacetanilide, was compared to a similar 2'-ethyl-N-t-butyl-2-bromoacetanilide based formulation (US Patent No. 2,863,752). By comparison, the compounds according to the invention, at a dose of 0.28 kg / ha, are effective in controlling undesirable and widespread weeds. The grade is 3 (75 to 100

1111212110133

0 01111010022

O 0 1 1 1 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 percent). On the other hand, the aforementioned ¹ composition has little effect on this weed even at a rate of 5.6 kg / ha (grade 1, i.e. 25-49%).

This comparison was made by the preeroergence test as described in the description just before the ΑΠΑ table, with a predetermined amount of the weed seeds being sown in the trays. The results can be expressed as follows:

ί

Degree of assessment

Compound of the Invention:

Rate, kg / ha

2‘- (n-propoxymethyl) -6‘- 5.6 3 t-butyl-2-chloroacetanilide 1.12 3 0.28 3 Known compound: 2'-ethyl-N-t-butyl-2-bromoacet- 5.6 1 anilide

This comparison results in higher efficacy of the herbicidal compounds of the invention.

The herbicidal compositions of the present invention, including concentrates requiring dilution, prior to use, comprise at least one active ingredient and an adjuvant in liquid or solid form. The formulations are prepared by mixing the active ingredient with an adjuvant. Adjuvants include diluents, fillers, carriers and adjuvants. Such compositions are in the form of ground solids, granules, tablets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with such excipients as finely divided solids, liquids of organic origin, water, wetting dispersing and emulsifying agents or any suitable combination thereof.

The compositions of the present invention, in particular liquids and wettable powders, preferably contain one or more surfactants in an amount sufficient to allow the composition to disperse readily in water or oil. The inclusion of a surfactant in the compositions greatly increases their efficacy. The term "surfactant" refers to wetting and dispersing agents, suspending and emulsifying agents. Anionic, cationic and nonionic agents can also be suitably used.

Preferred wetting agents are alkylbenzene and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long-chain sodium isothionate esters, sodium sulfosuccinate esters, sulfated or sulfonated petroleum sulfonate fatty acid esters, sulfonated vegetable oils, sulfonated vegetable oils, diterated vegetable oils polyoxyethylene derivatives of alkylphenols, especially isooctylphenol and nonylphenol; and polyoxyethylene derivatives of higher fatty acid esters of hexitol anhydrides, for example sorbitan. Preferred dispersing agents are methylcellulose, polyvinyl alcohol, sodium lighinsulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonate and polymethylene bisnaphthalenesulfonate.

Wettable powders and water dispersible compositions contain one or more active ingredients, an inert solid filler and one or more wetting and dispersing agents. Inert solid fillers are usually of mineral origin, such as natural clays, diatomaceous earth, and synthetic minerals derived from silica and the like. Examples of such fillers include kaolinity, attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the present invention typically comprise from about 0.5 to 95 parts, preferably from 5 to 20 parts of the active ingredient, from about 0.25 to 25 parts, preferably from 1 to 15 parts of the wetting agent, from about 0 to 20 parts. 25 to 25 parts, preferably 1.0 to 15 parts of dispersant and from 5 to about 95 parts, preferably 5 to 50 parts of inert solid filler. All parts are parts by weight of the total composition, if desired. replace from about 0.1 to 2.6 parts of a solid inert filler with a corrosion inhibitor or antifoam agent, or both.

The aqueous suspension may be prepared by mixing and grinding a slurry of the water-insoluble active ingredient in the presence of dispersants. A concentrated slurry of very finely divided solid particles is obtained. The resulting concentrated emulsion is then characterized by an extremely small particle size so that uniform dilution occurs upon dilution and spraying.

Emulsifiable oils are usually solutions of the active ingredient in a water-immiscible solvent or a water-miscible solvent together with a surfactant. Suitable solvents for the active ingredient of the present invention include hydrocarbons and water-immiscible ethers, esters or ketones.

Formulations in the form of aqueous suspensions and emulsifiable oils usually contain about 5 to 95 parts, preferably 5 to 50 parts of active ingredient, about 0.25 to 50 parts, preferably 1 to 25 parts of surfactant, and preferably about 5 to 95 parts. about 4 to 94 parts of solvent. All parts are parts by weight based on the total weight of the emulsifiable oil.

Granules are physically stable particulate formulations characterized in that the active ingredient adheres or is dispersed in a basic system of inert finely divided filler particles; to facilitate leaching of the active ingredient from the solid particles, surfactants such as those indicated herein may be present in the composition. Examples of useful solid particulate mineral fillers are natural clays, pyrophyllites, illite and vermiculite. Preferred fillers are porous, absorbent, preformed particles such as preformed and screened attapulgite particles or heat expanded vermiculite particles and finely ground clays such as kaolin clays, hydrated attapulgite or bentonite clays, these fillers being sprayed or mixed with the active ingredient. . Herbicidal granules are prepared.

The granular compositions of the present invention typically comprise from about 5 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surfactant per 100 parts by weight of clay in the form of solid particles. Preferred granular compositions comprise from about 10 parts to about 25 parts by weight of active ingredient per 100 parts by weight of aluminum.

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

3-amino-2,5-dichlorobenzoic acid, 3-amino-1,2,4-triazole,

5-amino-4-chloro-2-phenyl-3 (2H-pyridazinone),

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine,

2-chloro-N, N-diallylacetamide,

2-chlorallyl diethyldithiocarbamate,

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

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

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

2,2-dichloropropionic acid,

S-2,3-dichlorallyl-N, N-diisopropylthiolcarbarate,

2-methoxy-3,6-dichlorobenzoic acid,

2,6-dichlorobenzonitrile,

N, N-dimethyl-2,2-diphenylacetamide,

6,7-dihydropyridol (1,2-a: 2 ‘, l´-c) -prazrazinium salt,

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

4,6-dinitro-o-sec-butylphenyl,

1,3-Dimethyl-3- (2-benzothiazolyl) urea, ethyl N, N-dipropyl-thiolcarbamate,

2.3.6- trichlorophenylacetic acid,

5-Bromo-3-isopropyl-6-methyluracil

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

2-Methyl-4-chlorophenoxyacetic acid

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

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

N-1-naphthylphthalamic acid, 1,1'-dimethyl-4,4´-bipyridium salt,

2-chloro-4,6-bis (isopropylamino) -1,3,5-triazine, 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine,

2,4-dichlorophenyl-4-nitrophenyl ether, α, α 1, α-trifluoro-2,6-dinitro-N 1, N-dipropyl-o-toluidine,

S-propyl dipropylthiolcarbamate,

2,4-dichlorophenoxy acetic acid,

N-isopropyl-2-chloroacetanilide,

2 ', 6'-diethyl-N-methoxymethyl-2-chloroacetanilide,

2'-Methyl-6'-ethyl-N- (2-methoxyprop-2-yl) -2-chloroacetanilide, sodium hydrogen methanesansonate, sodium methanarsonate,

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

2-chloro-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether, 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobemzoic acid, sodium salt, 2- [4- (2,4-Dichlorophenoxy) phenoxy] propionic acid methyl ester,

4-Aixiino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one, N- (2,4-Dimethyl-5 - {[(trifluoromethyl) sulfonyl] aminophenyl) acetamide ,

3-isopropyl-1H-2,1,3-benzothiadiazin-4- (3H) -one,

2,2-dioxide,

3-methyl-4-amino-6-phenyl-1,2,4-triazin-5-one,

N-phosphonomethylglycine and its monoalkyl (1 to 6 carbon atoms), amine and alkali metal salts and combinations thereof at doses of 1,12 to 4,48 kg / ha to 1,12 to 11,2 kg / ha of the compounds according to this Regulation invention.

Fertilizers that are useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate. Other useful ingredients include materials in which the plants have roots and in which they grow, such as compost, manure, humus, sand and the like.

When working in accordance with the present invention, effective amounts of the acetanilides of the present invention are either applied to the soil with the plants or incorporated into the aqueous medium by any suitable means. Application of the compositions (both liquid and particulate) to the soil can be accomplished by conventional methods such as mechanical sprayers, frame sprayers, hand sprayers and sprayers, and can also be applied from airplanes in the form of dusts or sprays due to their low dosing efficiency. The application of herbicidal compositions to aquatic plants is usually accomplished by adding the compositions to an aqueous environment in an area in which control of aquatic plants is desired.

Applying an effective amount of the compounds of this invention to the site of undesired weeds is essential and critical in the practice of the invention. The exact amount of active ingredient used depends on various factors, such as the type of plant, the degree of its development, the type of soil and soil conditions, the amount of precipitation and the specific acetanilide used. For selective pre-emergence application to plants or to the soil, acetanilide is generally used at doses of from 0.02 to 11.2 kg / ha, preferably from about 0.04 to 5.60 kg / ha, more preferably from 1.12 to 5 kg. 6 kg / ha. In some cases, lower or higher dosages may be desirable. Based on this specification, including examples, those skilled in the art can readily determine the optimum application rate in any particular case.

The term “soil” is used in its broadest sense. It includes all types of conventional “soil” as described in Webster's new International Dictionary, 2nd edition, Unabbridged (1961). Thus, the term refers to any substance or environment in which vegetation can have roots and in which it can grow. This includes not only land, but also compost, manure, manure, humus, sand, and the like, which promotes plant growth.

Claims (6)

Herbicidal composition, characterized in that it contains, as active ingredient, a 2-haloacetanilide of the formula I, O (I) wherein ¹ X represents a chlorine or bromine atom, R and R 1 independently of one another are hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxymethyl in alkoxy, R @ 2 is hydrogen or methoxy; R 6 is C 1 -C 4 alkyl, allyl, phenyl, p-nitrophenyl or p-methylphenyl. OF THE INVENTION 2. The herbicidal composition of claim 1, wherein the active ingredient is 2'- (methoxymethyl) -6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2'- (methoxymethyl) -6'-methyl. -N- (methoxymethyl) -2-chloroacetanilide, 2'- (methoxymethyl) -6'-methyl-N- (butoxymethyl) -2-chloroacetanilide, 2'- (propoxymethyl) -6'-tert-butyl-2-chloroacetanilide or 2 '- (methoxymethyl) -6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide. 3. A process for the preparation of 2-haloacetanilide of the formula I as defined above, wherein X, R, R1, Ra and Ra are as defined above, as active ingredients for the herbicidal composition of claim 1, O \} CH- _CHX in which R, R 1, R 3a, X are as defined above and X ¹ represents a chlorine, bromine or iodine atom, reacted with an alcohol of formula III, R 1 OH (III) wherein ----- TT> Pi R 4 is as defined above, wherein the reaction is carried out at a temperature of -80 to 180 ° C and in the presence of heavy metal cations, Lewis acid, or, if X is chlorine and X ¹ is bromine iodine, and in the presence of an alkali or alkaline earth metal alkoxide having from 1 to 10 carbon atoms. 4. The process of claim 3, wherein the reaction is carried out in the presence of silver tetrafluoroborate. 5. Method according to claim 3, characterized in that the reaction is carried out in the presence of sodium methoxide. Where X ¹ represents bromine or iodine, and X is chlorine. 6. A process according to claim 4, wherein the reaction uses an alcohol of the above formula (III) and silver tetrafluoroborate in excess of the above derivative of the formula (II).