NL8001735A - Novel ORTHO-ALKOXY SUBSTITUTED 2-HALOGENENE ACETANILIDES, METHOD FOR THE PREPARATION THEREOF, AND USE THEREOF AS HERBICIDES - Google Patents

Description

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Novel ortho-alkoxy-substituted 2-haloacetanilides, process for their preparation and use as herbicides.

The invention relates to 2-haloacetanilides, their preparation, herbicidal compositions containing these compounds as active ingredient, and methods of their use. More particularly, the herbicidal compositions of the invention are particularly suitable for controlling unwanted plants that occur in combination with monocotyledons, such as wheat, sorghum and rice, and dicotyledons, such as sugar beets and soybeans.

The preparation of 2-haloacetanilides with a wide variety of substituents on the phenyl ring and on the anilide nitrogen atom is known.

As more or less relevant to the compounds of the invention, the prior art discloses various 2-haloacetanilides, which may be substituted by alkyl, alkoxy and / or alkoxyalkyl radicals or other substituents on the phenyl ring and on the nitrogen atom, in connection with which reference is made to German patent applications 2,402,983 and 2,405,183 and U.S. patents 3,966,811 and 3,976,471.

German patent application 2,402,983 discloses herbicidal compounds which may be substituted by alkyl and / or alkoxyalkyl radicals in the 2 'and 6' positions and by an alkoxyalkyl radical on the nitrogen atom. However, the alkoxyalkyl radical on the nitrogen atom in the aforementioned German patent application must contain not less than 2 carbon atoms separating the nitrogen and oxygen atoms from each other to distinguish 2-haloacetanilides substituted by alkoxymethyl. In addition, the said German patent application does not give at all 800 1 735 t 2 examples of 2-haloacetanilides with alkoxyalkyl residues on the anilide ring or of a process for the preparation of such compounds.

German Patent Application Nos. 2,405,183 and 5 U.S. Pat. Nos. 3,966,811 and 3,976,471 disclose 2-haloacetanilide compounds, which may be substituted by alkoxyalkyl radicals on the phenyl ring, but not at one of the ortho positions (2 'and 6 sites) as required by the present invention. In addition, the nitrogen substituents 10 of said U.S. patents are different from those of the invention, that of U.S. patent 3,966,811 being a 2,2-dialkoxyethyl radical and that of U.S. patent 3,976,471 being an alkylideneaminooxymethyl radical.

Other less relevant known compounds are the 2-haloacetanilides, which may be substituted by alkoxyalkyl or dialkoxyalkyl radicals on the nitrogen atom, but not on the phenyl ring, which may contain other substituents thereon, and typical such compounds are described in U.S. Patents 3,442,945, 3,547,620, 3,983,174, 3,952,056, 3,937,730, 4,019,894, 4,021,224, 4,025,554, and 4,086,080.

As relevant to the processes for preparing the compounds of the invention may be mentioned the processes described in the above-referenced patents. Illustrative known processes include the haloacetylation of the suitably substituted aniline, for example secondary aromatic amines, in which the substituents on the phenyl ring and the nitrogen atom are present before the haloacetylation is performed. Another process involves the reaction of the suitably substituted aniline with haloalcohols, for example 2-halopropanol, to introduce the hydroxyalkyl chain at the nitrogen atom, followed by chloroacetylation and finally etherification of the hydroxyalkyl group with an alcohol to give the corresponding N-al-koxyalkyl compound.

An older process involves the haloacetylation of the suitably substituted phenylazomethine to form its N-halomethyl adduct thereof, which is then reacted with an alcohol to obtain the corresponding N- alkoxyalkyl compound. On the other hand, the N-halomethyl adduct is reacted with an appropriately substituted salt of an oxime to obtain the corresponding product (see U.S. Patent 3,976,571 mentioned above).

As relevant to an embodiment of this invention described below, i.e., using silver or other heavy metal tetrafluoroborate as a catalyst, J.C. Sheehan et al., Journal

American Chem. Soc. 89: 2, p. 362 et seq., In particular 364 and 368, January 18, 1967, a neopentyl rearrangement of 2-bromo-3,3-dimethyl-N-t-butylbutyramide using silver tetrafluoroborate. However, this process has been described as a dehydrobromination which results in the removal of the 2-halogen atom. Thus, the method described by Sheehan et al. Shows the lability of the 2-halogen atom in the presence of silver tetrafluoroborate.

The prior art does not disclose a process for the preparation of 2-haloacetanilides by reacting an alcohol with ortho-benzyl halide intermediates to form the corresponding ether derivative.

The invention relates to new herbicidal 2-haloacetanilide compounds, a method for the preparation of these compounds, herbicidal preparations containing these compounds as active ingredient, and a method for their use, in particular for the control of harmful weeds in soybeans, sugar beet, wheat, rice and sorghum.

More particularly, the compounds of the invention have the general formula 1, wherein X represents halogen, R and independently represents hydrogen, C 1-6 alkyl, alkoxymethyl or alkoxymethyl, substituted by C 1-6 alkyl groups, R 2 and R independently represents hydrogen, C 1-6 alkyl or alkoxy groups, R 1 represents hydrogen, C 1-6 alkyl or alkenyl, phenyl or phenyl substituted by C 1-6 alkyl or alkoxy, halogen or nitro and n represents an integer from 0-4.

800 1 735. 1 4

The new process according to the invention comprises the preparation of compounds of the general formula 1 by reacting a compound of the formula 2 with a compound of the formula 3, wherein the groups R-R, mean the above. . 1 * 5 niches and X represents a chlorine, bromine or iodine atom, preferably in the presence of heavy metal cations, e.g. silver, lead, mercury, etc., or other Lewis acids, e.g. AlClg, SnCl 2, ZnC 3, etc. The cations are derived from compounds such as acetates, oxides, nitrates, tetrafluoroborates and the like. On the other hand, when X * represents a bromine or iodine atom, alkali metal and alkaline earth metal or alkoxides, for example the methoxides, ethoxides, propoxides, butoxides, etc., of sodium, potassium, rubidium, magnesium, zinc, cadmium and mercury can be used instead of the compound of formula 3.

The discovery of the above-described process is surprising because of the known lability of the 2-halogen atom to the N-acetyl moiety. For example, in compounds having halogen sites with substantially the same or relatively analogous reactivities, difficulties were encountered in differential replacement of the halogen atom to haloalkyl-substituted aryl moieties, for example, benzyl or xylyl halogen atoms, while maintaining the halogen at 2- acetyl site to provide the desired derivatives. For example, previous attempts to react either J or OCH2 anions with either or both of the benzyl haloalkyl moieties in the compound resulted in 2'6'-bis (chloromethyl) -N- (methoxymethyl) compound. -2-chloroacetanilide in the partial replacement of chlorine at all three halogen sites. Thus, the simple replacement of chlorine by nucleophilic groups in such systems was clearly not well possible.

It has now been found that the halogen in halo-methyl-substituted aryl molecules, for example benzyl halogens, xylyl halogens, etc., could be selectively activated without activation of the otherwise equally unstable 2-acetyl halogen using silver tetrafluoroborate (AgBF ^). . In addition, as noted above, in alternative embodiments, in some instances, for example when the o-positions are iodoalkyl or bromoalkyl radicals, these radicals may be etherified in an excess of alcohol with an equivalent alkali metal or alkaline earth metal alkoxide, for example sodium alkoxide.

The process conditions are not limited, although the process is best carried out at temperatures between about -80 and + 180 ° C, preferably at 0-125 ° C and especially at 25-100 ° C, but higher and lower temperatures may also be used over sufficiently long reaction times and at appropriate pressures (which may be sub-atmospheric or super-atmospheric) to ensure a complete reaction. Analogously, the concentrations of the reactants are not bound to any sharp limits, but it will be understood that the proportions of the reactants 15 will be suitably selected, referring to the detailed description and embodiments below.

The term "alkyl" and combined forms thereof such as "alkoxymethyl" include primary, secondary and tertiary alkyl radicals.

The preferred compounds of the invention for use in herbicidal compositions are those in which (see Formula 1) X represents chlorine, bromine or iodine and in particular chlorine, R 1 and lower alkyl groups, especially methyl, R represents a C 3 alkyl or alkoxymethyl radical, especially a C 1-6 alkyl or alkoxymethyl radical, and R 1 and R 2 are hydrogen atoms.

Representative compounds of the invention are those in which the groups R @ 1 can represent methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl, secondary isobutyl and tertiary butyl, and the groups R, R 1 and R 1 can further represent n- amyl, branched amyl groups, the normal and branched hexyl, heptyl, octyl, nonyl and decyl groups, and correspondingly R 1, C 2-10 aikenyi groups, preferably 35 nyl groups, especially the allyl moiety.

In one aspect of the invention, 800 1 7 35 I 1 6 preferred compounds are N.2 "bis or N.2". Trisialkoxymethyl-haloacetanilides, wherein the alkoxymethyl radicals contain the same alkyl radical in the alkoxy portion. These compounds are prepared using silver tetrafluoroborate catalyst, dissolved in an alcohol solvent of the formula 3, wherein the alkyl is the same as that in the alkoxy portion of R in the formula 2.

In such a case, the etherification selectively occurs at the 2 'and / or 6' haloalkyl site or sites, as illustrated in Example XVIII below. On the other hand, when the R ^ alkyΙ-ΙΟ radical of the formula 3 differs from that in the alkoxy portion in the alkoxymethyl radical R of the formula 2, the trans-etherification may occur between the groups R ^ and R, resulting in N.2. bis or N.2'6'-tris (alkoxymethyl) compounds having the same R 1 alkyl residue at the alkoxymethyl sites.

Another aspect of the invention relates to 2-haloacetanilide compounds having various alkoxymethyl radicals at the N atom and at the 2 'and / or 6' sites (ie the ortho sites with respect to the anilide nitrogen atom). Compounds of this type are prepared by reacting N.2'-bis- or N.2'6'-tris (alkoxymethyl) -2-haloacetanilides of the formula 1 with an alcohol of the formula 3, in which R 1 differs of and usually is greater than the alkyl moiety at the N and 2 'and / or 6' positions, in the presence of an organic sulfonic acid, such as methyl sulfonic acid. In such a case, the trans-etherification selectively occurs between the R 1 and alkoxymethyl residue on the nitrogen atom; the preparation of compounds of this type is illustrated in Example XXII below. The transetheretheration process described herein is the subject of another invention.

On the other hand, the above compounds with the same or different dkoxymethyl residues at the N and 2 'and / or 6' sites can be prepared by N-alkylation of the anion of a secondary 2-haloacetamide with one or more o-al-koxymethyl substituents with an alkylating agent, such as a haloalkylalkyl ether, for example chloromethyl methyl ether.

Example XXIII describes this N-alkylation process to prepare N.2'-bis (alkoxymethyl) -2-halogen-80 0 1 7 35 1-7 acetanilides. The compounds of the type described herein can also be prepared by reacting metal salts of the alcohols of the formula 3, for example R 4 OM, wherein M is an alkali or alkaline earth metal, with compounds of the formula 2, wherein R 5 is alkoxymethyl, X chlorine and X * represent bromine or iodine.

The herbicidal compositions of the invention are useful as selective herbicides by applying them to the site of the unwanted plants to be controlled and the desired plants to be protected.

The invention will be described in more detail below.

The compounds of the invention are derived from intermediate compounds, which in the relevant part are characterized by the presence of halomethyl substituents on one or both ortho positions of the anilide ring. These intermediates are themselves new and are the subject of another invention which relates to various processes for the preparation of the intermediates. As such processes, mention can be made of the free radical halogenation, preferably in the presence of ultraviolet light, of 2-haloacetanilides. The chlorination proceeds quickly and results in mono-chlorination at the N-methyl and / or o-alkyl site, but no reaction occurs at the α or nuclear centers. Bromination with elemental bromine, but more particularly with N-bromosuccinimide, is selective, with only an o-alkyl monobromination occurring even in the presence of an N-methyl portion.

The preparation of the intermediates used is illustrated in the examples below.

Example I

This example describes alternative methods for the preparation of the intermediate starting material, N- (methoxymethyl) -2'6'-bis (chloromethyl) -2-chloroacetanilide, which is used for the preparation of a compound according to the invention .

1 (a), 2-chloro-N.2'6 * -trimethylacet- 800 1 7 35, 1 8 anilide (21.1 g, 0.1 mol) was placed in 200 ml CCl 4 and an internal 0, 2 amp UV source was activated within the 500 ml flask. Chlorine (0.1 mol, 7 g) was added below the surface with stirring. The reaction was mildly exothermic and the temperature rose from 20 ° C to 40 ° C. After all the chlorine had been added, an almost colorless solution was obtained, which according to nmr comprised a mixture in which the two -CH2 groups on both the ring and the N-atom had been substituted. Neither the ClCi (CiO) nor the ring H portions were affected. The mixture was cooled to about 5 ° C and an additional 0.1 mole of chlorine was added, after which a mixture of mono-chlorinated N-CH 3 and ring -CH 2 was present, according to nmr. Finally, a third molar equivalent of chlorine was added, with significant spectral simplification.

The material was allowed to stand during the weekend and then the solvent was removed to yield a viscous oil. Portions thereof were recrystallized from pentane ether to obtain crystals with a melting point of 70-75 ° C. Carbon sulfur was also a good solvent for the recrystallization. On the basis of the nmr 20 (and further reactions thereof) this material was assigned the structure 2-chloro-N.2'.6'-tris (chloromethyl) acetanilide.

Most of the viscous oil (7 g) was heated on a steam bath in 250 ml of methanol for 10 minutes, gradually cooled and then stripped to remove all of the methanol except about 50 ml thereof. White crystals were developed and 5 g of them were filtered off; melting point = 111-114 ° C. After recrystallization from carbon tetrachloride, the melting point was 117-118 ° C.

Analysis: Calculated for C. H, ClO NO: 30, C 46.40, H 4.54, N 4.51, Cl 34.24%

Found C 44.48, H 4.33, N 4.64, Cl 34.96%.

The product was identified as the above intermediate.

1 (b). It was also shown that this intermediate could be prepared from the pre-formed N-chloromethyl compound (obtained from chloroacetyl chloride and azomethine 8001735 t 9 of 2,6-xylidine). 2-chloro-N- (chloromethyl) -2 '. 6'-acetoxylidide (10 g, 0.04 mol) in 200 ml CCl 4 was reacted with 0.081 mol (5.8 g) chlorine at 40-45 ° C. An additional 1.4 g of CI 2 was added to supplement the losses due to the volatility of chlorine. The solvent was removed and the residue was boiled with about 300 ml of methanol for 30 minutes, then 2/3 of this volume was removed, the contents were scratched and finally filtered to yield 6.4 g.

Example II

2 g (0.0065 mol) of the compound of Example I, i.e. N- (methoxymethyl) -2'6'-bis (chloromethyl) -2-chloro-acetanilide, were placed in 25 ml of methanol, the mixture was warmed to give a solution and 0.0135 moles (2.7 g) of silver tetrafluoroborate (AgBF4), dissolved in 10 ml of methanol, were added. The material was stirred under heating at 35-40 ° C. Only 0.8 g of AgCl were collected on filtration. A small-scale study showed that little more precipitate could be collected from this filtrate after heating, but that more precipitate was obtained on heating if more AgBF4 was added. Therefore, 2.5 g of AgBF4 were added and the material was refluxed for 3 minutes and kept above 55 ° C for an additional 10 minutes. The filtrate was again boiled in the filtration flask on a hot plate, then filtered to yield 0.1 g (total AgCl precipitate 1.6 g). The filtered solution was placed in a refrigerator overnight. Then 2.0 g AgBF ^ were added and the material was boiled for about 5 minutes, yielding 0.1 g AgCl (total 7.2 g AgBF ^). The methanol solution was reduced to 1/5 of its volume and then added to a 5% NaHCOg solution. A precipitate of Ag20 (3.1 g) was immediately formed. This was filtered off and salt (NaCl) was added with C 2 Cl 2. The aqueous salt solution was extracted several times with C 2 Cl 2. After drying, the organic solution was treated in vacuo to give 1.2 g of a pale yellow oil.

800 1 735 i '10

Analysis: Calculated for C 11 H 20 CINO: 14 20 4 C 55.72, H 6.68, N 4.64, Cl 11.75%

Found: C 55.71, H 6.69, N 4.65, Cl 11.78%.

By repeating the described procedure using 3.1 g of the intermediate, a final product yield of 2.1 g was obtained.

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

Example III

10 N- (methoxymethyl) -2'6,6-bis (chloromethyl) -2-chloroacetanilide (2.5 g, 0.0081 mol) was charged in 100 ml isopropanol with 8.6 g AgBF4, then 1 heated to reflux for one hour and then cooled. AgCl (2.3 g) was collected. The material was treated with 5% NaHCO 2 solution, then extracted with C 2 C 2 with addition of salt to ensure complete Ag + removal and ether amide recovery. The mixture was filtered off, the organic solution separated and the material treated in vacuo to remove the solvent to give 2.3 g of oil, which oil, according to nmr, contained no CH 2 O and three isopropoxy groups. The crude material (1.7 g) was distilled in a "Kugelrohr" at 200-210 ° C (0.05 mm) to yield 1.3 g of an amber oil; the nmr remained unchanged.

Analysis: Calculated for ^ 20 ^ 32 ^ N ^ 4: 25 C 62.24, H 8.36, Cl 9.19, N 3.63%

Found: C 62.10, H 7.84, Cl 8.25, N 4.16%.

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

Example IV

2'6'-Bis (1-chloroethyl) -N-methyl-2-bromoacetanilide (0.01 mol) was placed in about 75 ml of methanol containing 2.4 g (0.012 mol) of AgBF4. After standing overnight in the dark, the mixture was filtered to remove AgCl, stripped of solvent, taken up in pure methylene chloride, washed with an aqueous solution of NaCl and ^ 2 ^ ^ and dried over MgSO2. After filtration and drying 800 1 735 11, the material was treated in vacuo to remove solvent and the residue recrystallized and / or sublimed in vacuo. Analysis: Calculated for C 15 H 22 BrN ° 3: C 52.33, Br 23.21, N 4.07%. Found: C 49.75, Br 25.57, N 3.98%.

The product, obtained in a yield of 19% and with a melting point of 86-95 ° C, was identified as 2,6'- (bis-1-methoxyethyl) -N-methyl-2-bromoacetanilide.

Example V

2, - (bromomethyl) -6, -t-butyl-N-methyl-2-bromoacetanilide (3.7 g, 0.01 mol) was added in 150 ml of methanol and 2.4 g of AgBF2 in 50 ml of methanol were added. The material was allowed to stand for 3 hours, after which 1.6 g of AgBr were filtered off; after further standing overnight, 0.1 g 15 AgBr (theory 1.9 g) was obtained. The material was treated in vacuo to remove the solvent and the residue was treated with conventional mixture of C 1 / C 2 / NaCl / 10% 2 200. After the filtration (canvas filter), the filtrate was stripped to give an oil which crystallized on standing. Recrystallization from hexane gave a product with a melting point of 55-60 ° C; 2.1 g.

A second recrystallization from heptane gave a white solid; melting point = 72-74 ° C.

Analysis: Calculated for: C 54.88, H 6.76, Br 24.34, N 4.27%. Found: C 54.87, H 6.77, Br 24.26, N 4.29%.

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

Example VI

2'-bromomethyl-6 * -t-buty1-N-methyl-1-2-30 chloroacetanilide (5 g, 0.015 mol) was dissolved in 250 ml ethanol and 3.3 g of a clear solution of 3.3 g AgBF2 in 50 ml of ethanol was added thereto at room temperature. Immediate precipitation of yellow AgBr occurred. The material was left in the dark overnight, then AgBr was filtered off and the ethanol removed in vacuo. The residue was taken up in methylene chloride, washed with 150 ml of 10% ^ 2 ((where 8001735 τ 12 was added to a small amount of NaCl). After the filtration of the two liquid phases, the organic layer was separated, again with water washed and the solvent removed in vacuo The residue was recrystallized from heptane and a second recrystallization from ethanol yielded 3.0 g, mp = 77-78 ° C.

Analysis: Calculated for 0 ^^^ 01 ^ 2: C 64.52, H 8.12, N 4.70%

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 VII

• 2? - (bromomethyl) -6'-t-butyl-N-methyl-2-chloroacetanilide (1.7 g, 0.005 mol) was charged in ethylene-15 dichloride and added to a solution consisting of 0.7 g p-cresol and 1.0 g AgBF4 in ethylene dichloride. An instant theoretical precipitation of AgBr occurred. After standing for no longer than 30 minutes, the solution was treated with NaCl solution and filtered to remove the last residues of silver ion. The ethylene dichloride solution was then washed with 5% NaOH to remove phenol. It is then washed, CH2CI2 added and the organic solution finally washed again with water. After drying over MgSO4, filtration and treatment in vacuo to remove the solvent, the residue was recrystallized from isopropanol and then again to give 0.3 g of a white solid product; melting point = 148-152 ° C. Analysis: Calculated for ^ ^ 2 ^ 01 ^ 2: C 70.08, 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, -t-butyl-N-methyl-2-chloroacetanilide.

Example VIII

2 (bromomethyl) -6'-t-butyl-N-methyl-2-chloroacetanilide (1.6 g, 0.005 mol) was brought in methanol and a methanol solution of 0.95 g of sodium p-nitrophenate was added . The material was heated at reflux for 2 hours, cooled and scratched to yield 0.8 g of solid precipitate 8001735 I 4 13; melting point = 185-1860C. A portion was recrystallized from acetonitrile to give white crystals; melting point = 186-187 ° C.

Analysis: Calculated for: 5 C 61.46, H 5.93, Cl 9.07, N 7.17%.

Found: C 61.37, H 6.01, Cl 9.12, N 7.09%.

The product was identified as 2 - (p-nitrophenoxymethyl) -6, -t-butyl-N-methyl-2-chloroacetanilide. Example IX

2 '- (chloromethyl) -6'-t-butyl-N-methyl-2-chloroacetanilide (0.01 mol) was added in about 75 ml of t-butanol containing 2.4 g (0.012 mol) of AgBF4. After standing overnight in the dark, the mixture was filtered to recover AgCl, stripped of solvent, taken up in 15 pure CHgCl 2, washed with an aqueous solution of NaCl and 2 2 2 and dried over MgSO 2. After filtration and drying, the material was treated in vacuo to remove the solvent and the residue recrystallized and / or distilled in vacuo. Analysis: Calculated for C 8 H 22 ClNO 2: C 66.34, H 8.66, N 4.30%.

Found: C 65.21, H 8.49, N 4.41%.

The product, melting point = 65-67 ° C, obtained in a yield of 46%, was identified as 2 * - (t-butoxynethyl) -6, -t-butyl-N-methyl-2-chloroacetanilide.

Example X.

The same procedure as described in Example IX was followed, but n-propanol was replaced with t-butanol. The product, a white solid, mp = 53-54 ° C, was obtained in 64% yield and had the elemental analysis indicated below.

Calculated for C11 H14 CINO: C 65.47, H 8.40, N 4.49%, C 64.42, H 8.15, N 4.63%.

The product was identified as 21 - (n-propoxymethyl) -O-t-butyl-N-methyl-2-chloroacetanilide. Example XI

According to the procedure described in Example VI, wherein methanol is replaced by ethanol, 300 1 7 35 14, a white solid, recrystallized from methanol having a melting point of 74-75 ° C, was obtained in a yield of 70% .

Analysis: Calculated for C 63.48, H 7.81, N 4.94%

Found: C 63.47, H 7.83, N 4.97%.

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

Example XII

2 '- (bromomethyl) -6'-t-butyl-2-chloroacetanilide (1.6 g, 0.005 mol) was placed in 25 ml of methanol and 1 g of 10 (about 0.005 mol) AgBF4 were added in 20 ml methanol. Immediate precipitation of the theoretical amount of AgBr occurred. Without further delay, the filtered methanol solution was treated in vacuo to remove the solvent and 10% Na 2 CO 2 solution was added to the residue along with 15 methylene chloride solution and NaCl. After filtration through a sintered glass funnel with minimal suction, the methylene chloride layer was separated and then treated in vacuo to remove the solvent. The solid residue, melting point = 70-90 ° C, 0.8 g, could be recrystallized from a wide variety of solvents, the best being found to be cold aqueous methanol. To obtain an analytical sample, the material, a white solid, was sublimed in vacuo on an oil bath of 100-110 ° C (0.05 mm); melting point = 101-102 ° C.

Analysis: Calculated for C 25 ^ E ^ q CIM ^ J 25 C 62.33, H 7.47, Cl 13.14, N 5.19%

Found: C 61.45, H 7.40, Cl 12.82, N 5.01%

The product was identified as 2'- (methoxymethyl) -6, -t-butyl-2-chloroacetanilide.

The above product, on the other hand, could be prepared by reacting 3.2 g of the above 2'-bromo-methyl starting material in methanol with 0.01 mole sodium methoxide (7.0 ml, 1.48 M NaOCH2 in CH2 OH ). The reaction mixture was heated to 50-60 ° C, cooled and, after being allowed to stand, stripped, then water / C 1 -C 2 was added. The C 1 -C 2 solution was stripped and the solid recrystallized from methylcyclohexane to yield a product identical to the product described above.

Example XIII

Following the same procedure as described in Example XII, but using ethanol as the alcohol, a white solid, recrystallized from heptane, was obtained in 55 Z yield; melting point = 110-112 ° C.

Analysis; Calculated for Cji-E ^ CINC ^: C 61.87, H 8.16, N 5.15%

Found: C 61.02, H 7.55, N 5.07%.

The product was identified as 10 2 (ethoxymethyl) -O-t-butyl-2-chloroacetanilide.

Example XIV

Following the same procedure as described. In Example XIII, but using isopropanol as the alcohol, a greyish solid, melting point = 98-100 ° C, was obtained in 50% yield.

Analysis: Calculated for Cjg ^ ^ ClETC ^ i C 64.53, H 8.12, N 4.70%

Found it ; C 64.35, H 8.09, N 4.72%.

The product was identified as 2 - (isopropoxymethyl) -6, -t-butyl-2-chloroacetanilide.

Example XV

Following the same procedure as in Example XIII, but using n-butanol as the alcohol, 2 '- (n-butoxymethyl) -6, -t-butyl-2-chloroacetanilide, mp = 75-77 ° C, was obtained in a yield of 45%.

25 Analysis: Calculated for C ^^ gCll! ^: C 65.47, H 8.40, N 4.49%

Found: C 65.53, H 8.41, N 4.54%.

Example XVI

In an analogous manner as described in Example IV, but using n-propanol as the alcohol, 2 '- (n-propoxymethyl) -6'-t-butyl-2-chloroacetanilide, melting point = 40 ° C, was obtained in a yield of 40%.

Analysis: Calculated for C 64.52, H 8.12, N 4.70%

Found: C 63.33, H 7.89, N 4.73%.

Example XVII

35 2 '- (bromomethyl) -6, -t-butyl-2-chloroacetanilide (3.2 g, 0.01 mol) was dissolved in 75 ml of allyl alcohol 8001735 16 and then 2.4 g (0.012 mol) silver tetrafluoroborate, dissolved in 75 ml of allyl alcohol, is added. The mixture was left in the dark overnight. The mixture was then filtered off and the solvent removed by stripping. The resulting oil was dissolved in Cl 2 Clg and washed once with NaCl solution and then twice with water. The organic layer was dried over MgSO 2 and stripped to leave an oil which was crystallized from pentane; yield 1.7 g; melting point = 65-67 ° C.

Analysis: Calculated for cj6H22C ^ N ° 2: ^ ^ 4.96, H 7.50, N 4.74%

Found: C 63.85, H 7.21, N 4.88%.

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

Example XVIII

2 '- (bromomethyl) -61-t-butyl-N- (methoxy-methyl) -2-chloroacetanilide (4.2 g, 0.0113 mol) was brought in 250 ml of methanol and 50 ml of a solution of 3 .3 g of AgBF4 in 50 ml of methanol were added. Immediate precipitation of AgBr occurred, but the mixture was left to stand overnight in the dark, after which AgBr was filtered off in an amount of 89% of the theoretical amount. After the methanol was removed, the residue was treated in methylene chloride with a mixture of sodium chloride and 10% sodium hydroxide. The liquid phases were filtered off and the organic phase was separated from the filtrate. After the removal of the solvent, 3.0 g of oil remained, which gave a constant nmr structure. The material was distilled in a kugelrohr at 200-206 ° C (0.1 mm) to obtain 2.0 g of a substantially colorless oil in 59% yield.

Analysis: Calculated for C 21 H 14 ClNO 4: C 61.24, H 7.71, N 4.46, Cl 11.38%

Found: C 60.95, H 7.77, N 4.55, Cl 11.44%. The product was identified as 2 '- (methoxymethyl) -6 * -t-butyl-N- (mthoxymethyl) -2-chloroacetanilide . Example XIX

According to the procedure of the previous examples, but using as starting materials of 8001735 17 21- (bromomethyl) -6 * -t-butyl-N- (ethoxymethyl) -2-chloroacetanilide and ethanol, a white solid with melting point of 114-116 ° C.

Analysis; Calculated for C 12 H 14 ClNO 3: C 63.24, H 8.26, N 4.10%. 5 Found: C 62.64, H 7.90, N 4.87%

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

2 g of 2'-formyl-6'-t-butyl-2-chloroacet-10 anilide were dissolved in 10 ml of methanol and 10 g (CHgO) gCH, a few drops of SOC2 were added to form a catalytic amount of HCl. The material was refluxed on a steam bath for 45 minutes after standing overnight at room temperature (not necessary). Some drops of 50% caustic soda were added to neutralize the acid and the cooled solution was evaporated in vacuo. stripped to give a semi-solid residue (pH about 8-9). The pH was adjusted to 12-14 by addition of sodium hydroxide and water.

The resulting solid was filtered off, the filter cake was washed with water, and oven dried for 2-3 hours at 60 ° C, yielding 2.1 g (87% yield) of a white solid, melting point = 127- 132 ° G, were obtained. An analytical sample was prepared from isopropanol.

Calculated for C 1 H 14 ClNOg: C 60.10, H 7.40, N 4.67%. Found: C 58.92, H 7.12, N 4.77%.

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

Example XXI

5 g (0.012 mol) 2'3T-bis- (bromomethyl) -30 6'-t-butyl-2-chloroacetanilide were placed in 175 ml methanol and then mixed with 7.0 g AgBF4 dissolved in the same solvent . The material was left in the dark overnight, after which AgBr was filtered off. The methanol was evaporated, added and then the mixture was treated with NaCl / 35 Na 2 CO 2, filtered through clay, and washed again with water. After drying, the solvent was stripped and the solid recrystallized from ether. An analytical sample was obtained by sublimation in vacuo; melting point = 115-117 ° C. Calculated for C 1 H 14 ClNCy C 61.24, H 7.71, Cl 11.30, N 4.46%. Found: C 58.05, H 7.42, Cl 10.64, N 4.24%.

The product, a grayish solid, obtained in a 50% yield, was identified as 2,3'-bis- (methoxymethyl) -6'-t-butyl-2-chloroacetanilide.

The acetanilide starting material of this example was prepared in the following manner.

In a 1 liter flask, 15 g (0.059 mol) of 2'-3, -dimethyl-6'-t-butyl-2, -chloroacetanilide were dissolved in 600 ml of CCl 2. The reaction was accomplished with two white grazing lights. The reaction mixture was heated to reflux and then purged with nitrogen. Bromine (9.44 g, 0.059 mol) in 50 ml CCl 4 was added dropwise. During the bromine addition, it was observed when monitoring the nmr that the reaction did not proceed stepwise, but that the two arylmethyl groups were brominated almost simultaneously. A total of 2 molar equivalents of molecular bromine were added and the nmr of the reaction mixture at this stage showed a clean reaction, the product being formed in good yield. After standing during the weekend, the reaction mixture was filtered off; melting point = 180-182 ° C, after recrystallization 187-189 ° C. Sublimation in vacuo for the elemental analysis gave a sample with a melting point of 195-197 ° C. 25 Yield 50%.

Analysis: Calculated for Cj ^ HjgB ^ ClNO: C 40.85, H 4.41, N 3.40%

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

This product was identified as the compound indicated at the beginning of this example.

30 Example XXII

This example illustrates the preparation of compounds with different alkyl radicals in the alkoxy portion of the alkoxymethyl radicals attached at the N and o positions.

3 g of methyl-N 2 (bis-bis-ethoxymethyl) -35 2-chloroacetanilide were mixed with 75 ml of n-butanol and 5 micro-drops of methyl sulfonic acid; the mixture was heated under reflux over a Soxhlet, filled with a 3 l molecular sieve. The reaction was completed in about 1 hour by GLC. The material was stripped to leave a small amount of butanol, taken up in benzene, washed once with NaHCO 2 and evaporated to 75 ° C (0.4 mm), yielding 3.0 g (87% yield) by GLC of an oil was obtained.

Analysis: Calculated for Cj ^^^ ClNO ^: C 61.12, H 7.71, N 4.46%

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

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

Example XXIII

26 g of 2-methyl-6- (methoxymethyl) -2-chloroacetanilide dissolved in about 200 ml of an 80:20 diethyl ether: tetrahydrofuran mixture were treated with well rinsed KH; the theoretical amount of hydrogen was developed. An excess of chloromethyl methyl ether was added. After the reaction and the aqueous washings, the crude material exhibited a GLC value substantially equal to a distilled heart-20 fraction; yield 26 g (84%). The material was chromatographed on Florisil to give 19 g of oil, lookpoint = 180 ° C (0.05 mm).

Analysis: Calculated for C 8 H 9 ClNO 3: C 57.46, H 6.68, N 5.15%

Found: C 57.32, H 6.72, N 5.13%.

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

The process used in this example can be modified by using a starting acetanilide having an alkoxymethyl residue at the o-positions other than that applied to the N atom through the halomethylalkyl ether. Examples XXIV-XXVIII

In an analogous manner as described in the above examples, other compounds of the general formula 1 were prepared; these compounds, along with certain physical properties, are listed in Table A below.

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8001735 22

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As noted above, the compounds of the invention have been shown to act as herbicides for the partial or total inhibition of unwanted vegetation. Tables C (A) and D (A) give the results of tests carried out to determine the herbicidal activity upon application for the emergence of the plants, and Tables C (B) and D (B) show the results of tests carried out for determining the herbicidal activity in post-emergence application of representative compounds of the invention.

The plant emergence test was performed in the following manner.

A good quality topsoil was placed in aluminum pans and compressed to a depth of 3/8 to 1/2 inch from the top of the pan. A predetermined number of seeds or vegetative propagules of varying plant species was placed on top of the soil. The soil needed to fill the pans at an equal level after sowing or adding the vegetative propagules was weighed into a pan. A known amount of the active ingredient, present in a solvent or as a wettable powder, and the soil were intimately mixed and used as a coating for the topped pans. After the treatment, the pans were placed in a greenhouse bank, where they were watered from below in an amount to obtain the appropriate amount of moisture for germination and growth.

Unless otherwise indicated, the plants were observed approximately 2 weeks after sowing and treatment and the results recorded. Tables C (A) and D (A) below list the results. The herbicidal rating was obtained on an established scale based on the percentage damage of each plant species. The valuations are indicated below.

% Control Rating 0-24 0 25-49 1 35 50-74 2 75-100 3 8001735 25

The post-emergence agent application test was performed in the following manner.

The active ingredients were applied in the form of a spray to two or three week old samples from different plant species. The spray, a solution or wettable powder suspension, containing the appropriate amount of active ingredient to provide the desired amount to be tested, and a surfactant, is applied to the plants. The treated plants are placed in a greenhouse and about two weeks later, effects ranging from no response to total inhibition are observed and recorded, unless otherwise indicated. The results obtained are shown in Tables C (B), where the herbicidal activity index on application after the emergence of the plants is shown below.

% Control Rating 0-24 0 25-49 1 50-74 2 20 75-99 3 100 4

The plant species used in these experiments are indicated by a letter according to the scheme shown below.

25 A Canadian thistle G Nut sedge B Burdock H Cultivated grass C Mallow I Johnson grass D Dayblood J Gentle swab E Loosestrife K Cepine 30 F Water pepper 800 1 7 35 26

Table C (A)

For the emergence of the plants

Plant Species Connection from

image Kg / Ha ABCDEFGHIJK

II 5.6 0 0 10 0 12 1 0 3 3 III 5.6 00001000313 IV 11.2 00010010000 5.6 00010000011 V 5.6 0 0 1 1 3 3 0 0 0 3 3 VI 5.6 11113233123 VII 11.2 3 0 10 3 2 110 3 3 VIII 11.2 10010000033 5.6 10010010011 IX 5.6 00002032023 X 5.6 00003121033 XI 5.6 0 0 0 13 1 2 0 0 1 3 XII 5.6 0 0 1 2 3 1 2 1 0 2 3 XIII 5.6 00102121023 XIV 5.6 0 0 113 0 3 113 3 XV 5.6 10102233033 XVI 11.2 00103133123 5.6 00101022123 XVII 11.2 01112112023 5.6 00103011003 XVIII 5.6 0 0 113 112 1 3 3.

XIX 11.2 0 0 112 0 2 2 13 3 5.6 0 0 10 2 0 12 11 2 XX 11.2 10113111013 5.6 00002010002 XXII 11.2 11111123133 5.6 11111013123 XXIII 5.6 00002000001 XXIV 5.6 11223320033 XXV 5.6 30001201013 8001735 27

Continued from Table C (A)

For the emergence of the plants.

Plant Species Connection from

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XXVI 11.2 32223332033 5.6 31123321033 XXVII 11.2 00000000003 5.6 00000000003 XXVIII 11.2 32133332033 5.6 2 2 12 3 1 3 2 033

Table C (B)

After the plants emerge

Connection Plant Species

from example Kg / Ha ABCDEFGHIJK

II 5.6 01010000-01 IV 11.2 01014101000 V 11.2 01 121000000 VI 11.2 11112101002 VII 11.2 01001100001 VIII 11.2 1 1000000000 IX 11.2 11014400012 X 11.2 11111111102 XI 11.2 0 1 0 1 1 0 0 0 0 1 1 XII 11.2 01010000000 XIII 11.2 11011100001 XIV 11.2 00011000001 xv 11.2 110 1110 0 0 0 1 XVI 11.2 11112111002 XVII 11.2 01011010002 XVIII 11.2 11011100- 02 XX 11.2 0 0 1 1 0 0 110 0 0 XXIII 11.2 00100000000 XXIV 11.2 01010200002 XXV 11.2 01010000002 XXVI 11.2 0101-110002 XXVIII 11.2 01110011011 8001735 28

Using the procedure described above, the compounds were further investigated for the following plant species: L Soybean R Hemp sesbania 5 M Sugar beet E Loosestrife N Wheat F Water pepper 0 Rice C Mallow P Sorghum J Bromus tectorum (soft swirl) B Burdock S Panicum Spp.

10 Q Wild buckwheat K Cinnabar D Dayflower T Blood millet.

The results are shown in Tables D (A) and D (B), 15 8001735 29

Table D (A)

For the emergence of the plants

Connection ^.

Plant species from front ---

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II 5.6 0110100112100333 1.12 0101200010102333 0.28 0000000000000233 0.06 000000000000001 0 III 1.12 000000000.0000023 0.28 000000000000001 1 0.06 000-000000000000 V 1.12 100230101 1 100233 0.28 00000000000023 0.06 000000000000001 1 .6 1223301011102333 1.12 01 1 1200001001233 0.28 0000200001001222 0.06 0000000000000010 VII 5.6 0101000010100233 1.12 0001000000100133 0.28 0000000000000022 VIII 5.6 1200000010000032 1.12 010000000000001 1 IX 1.12 31112310121100 300 300 6 1323300123313333 1.12 1222300001 102333 0.28 1 1 1 1200000102233 0.06 00010000001001 12 8001735 30

Continued from Table D (A)

For the emergence of the plants

Connection Plant species from front -

image Kg / Ha LMNOPBQDREFCJSKT

XI 5.6 2312300012212333 1.12 1200100012101333 0.28 1 100100002000232 0.06 10000000000001 1 1 XII 1.12 21333001 1 1003333 0.28 1001 100010002223 0.06 0000000000000001 XIII 5.6 3333332333313333 1.12 21223302200 031000 0.213 11011000 313 0.28 11011000 3100 0000030000000000 XIV 5.6 2233310223233333 1.12 2123300122113333 0.28 1000100000000133 0.06 000000000000001 0 0,11 0000030000000000 XV 5,6 2333310133213333 1.12 1223200021 102233 0,28 0101000000001 122 XVI 0103 313111021011 100113111020011 000000000000001 2 8001735 ί 1 31

Continued from Table D (A) Before the plants emerge

Connection Plant Species from before - '

image Kg / Ha LMNOPBQDREFCJSKT

XVII 5.6 2232302111103333 1.12 1010100000001 133 0.28 0000000000000000 122 XVIII 5.6 2222302223213333 1.12 1111201222 1 02333 0.28 000000000 00001 22 0.06 0001000100000012 XIX 5.6 1233300212203333 1.12 11013001 1 '1101333 0.2822 001 00000 2122301111113333 1.0 0 000000010001122 XXII 5.6 0011200111013333 1.12 0001 100001002233 0.28 0 1 00000001000012 0.06 0000000000000001 XXIV 5.6 0201323223321333 1.12 010020010 1 100333 0.28 00000000003333 0.06 0000000000000002 XX-00 0.28 0120000000201333 0.06 0001 000000000032 0.11 000 0 0000 C 0000010 8001735 32

Continued from Table D (A)

For the emergence of the plants

Connection Plant Species

image Kg / Ha LMNOPBQDREFCJSKT

XXVI 5.6 122333233-313333 1.12 031331313-303333 0.28 021230002-201333 0.06 000000000-100133 0.11 000001000-200032 XXVII 5.6 0000001013300033 1.12 00000000-3100023 0.28 0000000000000001 XXVIII 5.6 0323323333303333 1.1 .28 0100100003300333 0.06 0000001003200022

Table D (B)

After the plants emerge

Connection Plant species from front ---

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IX 5.6 2 10 11 112 12 110 13 3 1.12 1000001 1 1 1010022 0.28 1000001110000011 0.06 1 000000000000 0 00 8001735 f33

The herbicidal compositions of the invention, including concentrates, which require dilution before application, contain at least one active ingredient and an additive in liquid or solid form. The preparations are prepared by mixing the active ingredient with an additive, including diluents, cutters, carriers and conditioners, to provide preparations in the form of finely divided particulate solids, pellets, 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 dispersing agent, an emulsifying agent, or any suitable combination thereof.

The preparations according to the invention, in particular liquids and wettable powders, preferably contain, as conditioning agent, one or more surfactants in amounts sufficient to make a given preparation readily dispersible in water or in oil. The inclusion of a surfactant in the compositions greatly enhances its action. The term "surfactant" includes wetting agents, dispersants, suspending agents and emulsifying agents. Anionic, cationic and non-ionic agents can be used equally successfully.

Preferred humectants are alkyl-25 benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated ethylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylphenol phenylphenol phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenylene phenylphenolphenethylphenylene phenylphenylene phenylphenolphenethylphenylphenol-phenol isoctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate and the polymethylene bisnaphthalene sulfonates.

Wettable 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 obtained from silicon oxide and the like. Examples of such cutters include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the invention usually contain about 0.5-95 parts (preferably 5-20 parts) of active ingredient, about 0.25-25 parts (preferably 1-15 parts) of wetting agent, about p 25-25 parts (preferably 1.0-15 parts) of dispersant and 5 to about 95 parts (preferably 5-50 parts) of inert solid cutting agent, all parts being parts by weight based on the weight of the total composition . If necessary, about 0.1-2.0 parts of the solid inert cutting agent can be replaced by a corrosion inhibitor or anti-foaming agent or both.

Aqueous suspensions can be prepared by mixing and grinding an aqueous suspension of water-insoluble active ingredient in the presence of dispersants to form a concentrated suspension of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that the coating is very uniform after dilution and spraying.

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

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

8001735 35

Granules are physically stable particulate preparations containing the active ingredient adhered to or distributed by a base matrix material 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 those mentioned above may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of useful particulate mineral cutting agents. The preferred cutters are 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 or mixed with the active ingredient to form the herbicidal granules.

The granular compositions of the invention generally contain about 5 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 20 parts by weight of surfactant per 100 parts by weight of particulate clay. The preferred granular compositions contain about 10 to about 25 parts by weight of active ingredient per 100 parts by weight of clay.

The compositions of the invention may also contain other additives, for example, fertilizers, other herbicides, other pesticides, safeners and the like, which are used as additives or in combination with one or more of the above additives. Chemicals that are useful in combination with the active ingredients of the invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like, such as 3-amino-2,5-dichlorobenzoic acid 35 3-amino-1,2,4-triazole 5-amino-4-chloro-3-pheny1-3 (2H) -pyridazinone 8001735 36 2-chloro-4-ethylamino-6 -isopropylamino-s-triazine 2-chloro-NN-diallylacetamide 2-chloroallyldiethyldithiocarbamate N '- (4-chlorophenoxy) phenyl-NN-dimethylurea 5 NN-dimethyl-N, - (3-chloro-4-methylphenyl) urea S- ( 4-chlorobenzyl) -N, N-diethylthiolcarbamate isopropyl N- (3-chlorophenyl) carbamate 2,2-dichloropropionic acid _S-2,3-dichloroallyl-N, N-diisopropylthiolcarbamate 10 2-methyl-3,6-dichlorobenzoic acid 2,6-dichloorbenzonitri1 N, N-dimethyl-2,2-diphenylacetamide 6,7- dihydrodipyrido (1.2-a: 2'.1T-c) -pyrazidinium salt 3- (3,4-dichlorophenyl) -1,1-dimethyl urea 4.6-dinitro-o-sec-but ylphenol 1,3-dimethyl-3- (2-benzothiazolyl) urea ethyl-NN-dipropylthiol carbamate 2,3,6-trichlorophenylacetic acid 5-bromo-3-isopropyl-6-methyluracil 20 3- (3,4-dichlorophenyl) -1-methoxy-1-methyl urea 2-methyl-4-chlorophenoxyacetic acid 3- (p-chlorophenyl) -1,1-dimethylurea 1-buty1-3- (3,4-dichlorophenyl) -1-methylurea N-1-naphthylphthalamic acid 1,1-dimethyl-4.4, -bipyridinitim salt 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 2,4-dichloropheny1-4-nitrophenyl ether a, a, a-trifluoro-2,6-dinitro-NN -dipropyl-p-toluidine 30 S-propyldipropylthiol carbamate 2,4-dichlorophenoxyacetic acid N-isopropyl-2-chloroacetanilide 2'.6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl-6'-ethyl-N- (2- methoxyprop-2-yl) -2-chloroacetanilide 35 monosodium acid methanesaronate disodium methanesaronate 8001735 t37 N- (11-dimethylpropynyl) -3,5-dichlorobenzamide 2-chloro-aaa-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl 5- / 2-chloro-4- (trifluoromethyl) phenoxy / -2-nitrob enzoate methyl 2- / 4- (2,4-dichlorophenoxy) phenoxy / propionate 5 4-amino-6-t-butyl-3-methylthio-1,2,4-triazin-5-one N- {2,4-dimethyl-5- / / (trifluoromethyl) sulfonyl / amino / phenyl acetamide 3-isopropyl-1H-2.1.3-benzothiadiazin-4- (3H) -one-2,2-dioxide 3-methyl-4-amino-6-phenyl-1,2,4-triazine- 5-one N- (phosphonomethyl) glycine and its Cmonoalkylamine and alkalime-10 language salts and combinations thereof in ratios of 1-4 pounds / acre (1.12-4.48 kg / ha) to 1-10 pounds / acre of the compounds of the invention.

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

In the practice of the method of the invention, effective amounts of the acetal anilides of the invention are applied to the soil containing the plants, or 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, machine-powered sprayers, "boom" and hand sprayers and spray sprayers. The formulations can also be applied from airplanes in the form of a puff or a spray because they work effectively in small amounts. The application of the herbicidal preparations to aquatic plants is usually carried out by adding the preparations to the aqueous media in the area in which control of the aquatic plants is desirable.

The application of an effective amount of the compounds of the invention to the site of the undesirable herbs is essential 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 stage of development, the type and condition of the soil, the amount of rainfall and the specific acetanilide used. In the selective application 5 for the emergence of the plants on the plants or on the ground, usually an amount of 0.02 to about 11.2 kg / ha, preferably about 0.04 to about 5.60 kg / ha or suitably 1.12-5.6 kg / ha acetanilide used. Smaller or larger quantities may be required in some cases. Those skilled in the art can easily deduce from this description and the above example the optimum amount to be used in each special case.

The term "soil" is used in its broadest sense and includes all the usual "soil types" as defined in Webster's New International Dictionary, Second Edition, Unabridged (1961). Thus, the term encompasses any substances or media in which a vegetation can take root and grow, including not only soil, but also compost, manure, peat, humus, sand and the like, made suitable for supporting plant growth.

8001735

Claims (26)

1. Compounds of the general formula 1, wherein X represents halogen, R and R 1 independently represent hydrogen, alkyl, alkoxymethyl or alkoxymethyl, substituted by one or two C 1-6 alkyl groups, R 2 and R 4 independently represent hydrogen, C 1-6 alkyl - or alkoxy groups, R 1 represents hydrogen, C 1-8 alkyl or alkenyl, phenyl or phenyl substituted by alkyl or alkoxy, halogen or nitro groups and n is an integer from 0-4. Compounds according to claim 1, characterized in that R represents hydrogen. Compounds according to claim 1, characterized in that R is a Cj_jq residue. Compounds according to Claim 1, 15, characterized in that R represents C 1-8 alkoxymethyl or alkoxymethyl substituted by one or two C 1-8 alkyl groups. Compounds according to claims 2, 3 or 4, characterized in that R 1 represents hydrogen. Compounds according to claims 2, 3 or 4, characterized in that R 1 is a C 1 -J 4 alkyl radical. Compounds according to claims 2, 3 or 4, characterized in that R 1 represents a C 1 -C 6 alkoxymethyl or alkoxymethyl substituted by one or two Calkyl groups. Compounds according to claims 2, 3 or 4, characterized in that R 1 is a C 1-8 alkyl radical. Compounds according to claims 2, 3 <f 4, characterized in that R 1 is an alkenyl residue. 10. Compounds according to claims 2, 3 or 4, characterized in that R 1 represents phenyl or phenyl substituted by C 1 -alkyl or alkoxy, halogen or nitro groups. Compounds according to claims 2, 3 or 4, characterized in that R 2 and R 2 both represent hydrogen. Compounds according to claims 2, 3, 35 or 4, characterized in that at least one of the groups R 2 or R 1 is a C 1-4 alkyl radical. 8001735 Compounds according to claim 1, characterized in that the compound is 2, - (methoxymethyl) -6, -methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2, - (methoxymethyl) -6'-methyl-N - (methoxymethyl) -2-chloroacetanilide, 2 '- (methoxymethyl) - 5,6-methyl-N- (n-butoxymethyl) -2-chloroacetanilide, 2' - (n-propoxy-methyl) -6'-t- butyl-2-chloroacetanilide or 2 '- (methoxymethyl) -6, -methyl-N - (isopropoxymethyl) -2-chloroacetanilide. 14. Process for the preparation of compounds of the general formula I, wherein X represents halogen, 10. and Rj independently represent hydrogen, C 1-8 alkyl, alkoxy-methyl or alkoxymethyl substituted by one or two C 1-8 alkyl groups, 11 and R independently represent hydrogen, alkyl or alkoxy groups, R 1 represents hydrogen, C 1-8 alkyl or alkenyl, phenyl or phenyl, substituted by C 1-6 alkyl or alkoxy, halo or nitro groups, and n an integer of 0- 4 is characterized in that a compound of the formula II, wherein X and the groups R @ 4 have the meanings indicated above and X1 represents chlorine, bromine or iodine, is reacted with a compound of the formula III, wherein R ^ has the meanings stated above. R 1 represents C 1-8 alkyl or alkenyl, phenyl or phenyl substituted by alkyl or nitro groups and n is an integer from 0-4. Process according to claim 14, characterized in that the reaction is carried out at temperatures between about -80 ° C and + 180 ° C. 16. Process according to claim 15, characterized in that the reaction is carried out in the presence of a heavy metal cation or another Lewis acid or, when X = Cl and X 'is bromine or iodine, a C 1-4 alkoxide of an alkali. metal or alkaline earth metal. 17. Process according to claim 16, characterized in that the reaction is carried out in the presence of silver tetrafluoroborate. 18. Process according to claim 16, characterized in that the reaction is carried out in the presence of sodium methoxide when X 'is a bromine or iodine atom and X is a chlorine atom. Process according to claim 17, characterized in that the compound of the formula 3 and silver tetra-8001735 i-fluoroborate are present in an excess with respect to the compound of the formula 2. 20. Process according to claim 17, characterized in that the compound of the formula 1 is 2, - (methoxymethyl) -6, -t-butyl-N- (methoxymethyl) -2-chloroacetanilide, 2 '- ( methoxymethyl) -6'-methyl-N- (methoxymethyl) -2-chloroacetanilide or 2i- (n-propoxymethyl) -6'-t-butyl-2-chloroacetanilide. 21. Herbicidal compositions containing an additive and an effective amount of a compound of the general formula 1 wherein X represents halogen, R and Rj independently represent hydrogen, C 1-4 alkyl, alkoxymethyl or alkoxymethyl substituted by one or two alkyl groups , R2 and R1 independently represent hydrogen or alkyl groups, Herbicidal preparations according to claim 21, characterized in that the compound is 2 '- (methoxymethyl) - 6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2 - (methoxymethyl) -20 61-methyl- N- (methoxymethyl) -2-chloroacetanilide, 2 '- (methoxy-methyl) -6'-methyl-N- (n-butoxymethyl) -2-chloroacetanilide, 2r- (n-propoxymethyl) -6, -t-butyl -2-chloroacetanilide or 2 '- (methoxy-methyl) -6 * -methyl-N- (isopropoxymethyl) -2-chloroacetanilide. 23. A method of controlling undesired vegetation, characterized in that a herbicidal composition is applied in its place, containing an additive and an effective amount of a compound of the general formula 1, wherein X represents halogen, R and Rj independently representing hydrogen, C 1-4 alkyl, alkoxymethyl or alkoxymethyl substituted by one or two C 1-4 alkyl groups, R 2 and R 3 independently representing hydrogen or C 1-4 alkyl groups, R 1 represents C 1-4 alkyl or alkenyl, phenyl or phenyl, substituted by C 1-4 alkyl or nitro groups, and n is an integer from 0-4. The method according to claim 23, 35, characterized in that the compound is 2, - (methoxymethyl) -6'-methyl-N- (ethoxymethyl) -2-chloroacetanilide, 2 '- (methoxymethyl) - 8001735 6' -methyl -N- (methoxymethyl) -2-chloroacetanilide, 2 '- (methoxy-methyl) -61-methyl-N- (n-butoxymethyl) -2-chloroacetanilide, 2' - (n-propoxymethyl) -6, -t- butyl-2-chloroacetanilide or 2 '- (methoxymethyl) -6'-methyl-N- (isopropoxymethyl) -2-chloroacetanilide. Herbicidal compositions according to claim 21 in the form of articles. 26. Compounds, methods and preparations as described in the description and / or examples. 10 8001735