CA1131661A - Ortho-alkoxy-substituted 2-haloacetanilides, their method of preparation and their use as herbicides - Google Patents

Abstract

Abstract of the Disclosure The disclosure herein relates to a new class of herbicidal compounds comprising 2-haloacetanilides, herbi-cidal compositions containing same, their method of prepara-tion and use to selectively control undesired vegetation in agricultural crops, e.g., monocotyledons such as wheat, sorghum and rice and dicotyledons such as sugarbeets and soybeans.

Description

~ 3~ AG-1161 NOVEL ORTHO-ALKOXY-SUBSTITUTED 2-HALOACETANILIDES, HEIR M~ OF_~EPARATION AND THEIR USE AS HERBICIDES

Background of the Invention The invention herein pertains to the field of 2-haloacetanilides, their preparation, herbicidal composi-tions containing same as active ingredient and method of usethereof~ In more particular, the herbicidal compositions herein have particular application in the control of un-desired plants associated with monocotyledons such as wheat, sorghum and rice and dicotyledons such as sugarbeets and soybeans.

Description of the Prior Art .
It is known in the prior art to prepare 2-haloacet-anilides having a variety of substituents on the-phenyl ring and on the anilide nitrogen atom.

As more or less relevant to the compounds of this invention the prior art discloses various 2-haloacetanilides which may be substituted with alkyl, alkoxy and/or alkoxyalkyl radicals or other substituents on the phenyl ring and on the nitrogen atom. See, for example, German Patent Application Numbers 2,402,983 and 2,405,183 and U. S. Patent Numbers 3,966,811 and 3,976,471.
Said '983 German patent application discloses herbi-cidal compounds which may be substituted with alkyl and/or alkoxyalkyl radicals in the 2' and 6' positions and with an alkoxyalkyl radical on the nitrogen atom. EIowever, the alkoxyalkyl radical on the nitrogen atom in said '983 patent must have no less than two carbon atoms separating the nitro-gen and oxygen atoms as distinguished from alkoxymethyl-sub-stituted 2-haloacetanilides. Moreover, said '983 German patent application does not disclose any examples whatever of any 2-haloacetanilides having alkoxyalkyl radicals on the anilide ring or, further, any process for preparing such com-pounds.
The '183 German application and the '811 and '471 `. ~

2- AG-1161 1~3~
U. S. patents disclose 2-haloacetanilide compounds which may be substituted with alkoxyalkyl radicals on the phenyl ring, but not in either of the ortho (2' and 6') positions as required in the present invention. Moreover, the nitrogen substituents in the '811 and '471 patents are distinct from those herein; that in '811 patent being a 2,2-dialkoxyethyl radical and that in the '471 patent being an alkylideneamino-oxymethyl radical.
Other less relevant prior art compounds include 2-haloacetanilides which may be substituted with alkoxyalkyl or dialkoxyalkyl radicals on the nitrogen atom, but not on the phenyl ring which may have other substituents thereon; typical of such compounds are those described in U. S. Patent Numbers

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 processes for producing analogous compounds as those described and claimed herein, the closest prior art appears to be the processes described in the above-mentioned patents. Illustrative prior art processes involve the haloacetylation of the appropriately-substituted aniline, e.g., secondary aromatic amines wherein the phenyl ring and nitrogen have their substituents affixed-prior to haloacetyla-tion. Another process involves the reaction of the appropri-ately-substituted aniline with haloalkanols, e.g., 2-halo-propanol to introduce the hydroxyalkyl chain on the nitrogenatom, followed by chloroacetylation and, finally, by etheri-fication of the hydroxyalkyl group with an alcohol to obtain the corresponding N-alkoxyalkyl compound.
An earlier process involves the haloacetylation of the appropriately-substituted-phenylazomethine to obtain the N-halom~thyl adduct thereof which is then reacted with an alcohol to obtain the corresponding N-alkoxyalkyl compound.
Alternatively, the N-halomethyl adduct is reacted with an appropriately-substituted salt of an o~ime to obtain the corresponding product (3,976,471 above).

-3- ~ AG-1161 As relevant to one embodiment of this invention described below, i.e., wherein silver or other heavy metal tetrafluoroborate is used as catalyst, J~ C. Sheehan et al (JOI~E1 ~merican Ch~m. SO~r 89.;2, pages 362 et se~., esp. 364 and 368, January 18, 1967), describe a neopentyl rearrangement of 2-bromo-3,3-dimethyl-N-_-butylbutyramide by use of silver tetra-fluoroborate. However, that process is described as a dehydro-bromination resulting in the removal of the 2-halogen atom.
~ccordingly, the process described by Sheehan et al teaches the labiliky o the 2-halogen atom in the presence of silver tetrafluoroborate.
The prior art is devoid of disclosure of a process for producing 2-haloacetanilides by reacting an alcohol with ortho-benzylic halide lntermediates to produce the corresponding ether derivative.
Summary of the Invention The present invention xelates to a new ~lass of herbicidal 2-haloacetanilide compounds, process for preparing these compounds, herbicidal compositions containing said com-pounds as active ingredient and herbicidal method of use, particularly- to control noxious weeds in soybeans, sugarbeets, wheat, rice and sorghum.
In more particular, the compounds of this invention are those having the formula o N

1 ) ~30R4 wherein X is halogen, R and Rl are independently hydrogen, Cl_10 alkyl, alkoxymethyl or alkoxymethyl substituted with Cl 4 alkyl groups, R2 and R3 are independently hydrogen, Cl 4 alkyl or alkoxy groups, R4 is hydrogen, Cl 10 alkyl or alkenyl, phenyl or phenyl substituted with Cl 5 alkyl or alkoxy, halogen or nitro groups and n i5 an integer from 0-4 inclusive.
The novel process herein involves the preparation of compounds within the scope of Formula I which comprises reacting a compound having the formula R C-CH X

II l R2 1 ~ ~C-X
(Rl)n ~ R3 with a compound of the formula wherein the R-R4 groups are de~ined above and Xl is a chloro, bromo or iodo atom, preerably in the presence of heavy metal cations, e.g., silver, lead, mercury, etc., or other Lewis Acids, e.g., AlCl3, SnC14, ZnC12, etc. The cations are de-rived from compounds such as acetates, oxides, nitrates, tetra-fluoroborates and the like. Alternatively, when Xl is bromo or iodo, alkali metal and alkaline earth Cl 10 alkoxides, e.g., the methoxides, ethoxides, propoxides, butoxides, etc., of sodium, potassium, rubidium, magnesium, zinc, cadmium and mercury, may be used in lieu of the compound of Formula III.
The discovery of the above process is unexpected because of the known lability of the 2-halogen on the N-acetyl radical. Thus, with compounds having halogen sites with essen-tially the same or relatively similar reactivities, a problem was created with respect ko differentially replacing the halogen on haloalkyl-substituted aryl moieties, e~g., benzylic or xylylic halogens, while preserving the halogen at the 2-acetyl position to produce desired deri~atives. For example, prior attempts by the inventor to react either I- or OCH3- anions with one or both of the benzylic haloalkyl moieties on the compound 2',6~-bis (chloromethyl)-N-(methoxymethyl)-2-chloroacetanilide resulted in the partial displacement of chlorine at all three halogen sites. Thus, the simple replacement of chlorine by nucleophiles in such systems was clearly inadequate.

5 ~3~6~1 AG~

It was discovered by this inventor that the halogen on halomethyl-substituted aryl molecules, e.g., benzylic halo-gens, xylylic halogens, etc., could be selectively activated without activating the otherwise equally labile 2-acetyl halo-gen by use of silver tetrafluoroborate (AgBF4). Moreover, asnoted above, in alternative embodiments,in some cases, e.g., when the o-positions are iodoal~yl or bromoalkyl radicals, -these radicals can be etherified in excess alcohol with an equiva-lent of alkali metal or alkaline earth alkoxide,e.g., sodium alkoxide.
The process conditions are not critical although best conducted at temperatures within the range of from about -80 to 180C, preferably from 0 125C and still more preferably from 25-100C, although higher and lower temperatures may also be used for sufficient reaction times and pressures (which may be subatmospheric or superatmosphere) as to assure complete re-action. In like manner, concentrations o reactants are not critical, but it will be understood by those skilled in the art that the ratios of reactants will be appropriately selected following the detailed description and working embodiments herein.
As used herein, the term "alkyl" and combined forms thereof as in "alkoxymethyl" is understood to include primary, secondary and tertiary alkyl radicals.
The preferred compounds herein for use in herbicidal compositions are those in which (having reference to Formula I) X is chlorine, bromine or iodine and, especially chlorine; R
and R4 are lower alkyl groups, particularly methyl; R is an Cl 10 alkyl or alkoxymethyl radical, particularly Cl 5 alkyl or alkoxymethyl radical and R2 and ~3 are hydrogen atoms.
Representative compounds of the present invention in-clude those in which the R-R4 groups of the above formula in-- clude methyl, ethyl, propyl, isopropyl, n-butyl, primary isobutyl, secondary isobutyl and tertiary butyl radicals and the R, R
and R4 radicals further include n-amyl, branch chain amyls, the normal and branched hexyls, heptyls, octyls, nonyls, and decyls and corresponding R4 C2 10 alkenyl groups, preferably C2 4 alkenyl groups, particularly the allyl radical.
In one aspect of this invention, preferred compounds 3~ AG-ll61 - are N, 2'-bis or N, 2',6'-tris ~alkox~methyl)-2-haloacetanilides wherein the alkoxymethyl radicals have the same alkyl radical in the alkoxy moiety. These compounds are prepared by using silver tetrafluoroborate catalyst dissolved in an alcohol sol-vent of Formula III wherein R4 is the same alkyl radical as thatin ~he alkoxy moiety of R in Formula II. In such case, etheri-fication occurs selectively at the 2' and/or 6'-haloalkyl posi-tion(s), as exemplified in Example 18 below. On the other hand, ~hen the R4 alkyl radical o~ Formula III is different from that in the alko~y moiety in the alkoxymethyl radical R of Formula II, transetherification can occur between the R4 and R groups result-ing in N,2'-bis or N,2',6'-tris (alkoxymethyl) compounds having the same R4 alkyl radical in the alkoxymethyl positions.
Another aspect of this invention concerns 2-haloacet-15 anilid~ compounds having different alkoxymethyl radicals on theN atom and in the 2' and/or 6' positions (i.e., the ortho posi-tions relative to the anilide nitrogen atom). Compounds of this type are prepared by reacting N,2'-bis or N,2',6'-tris (alkoxy-methyl)-2-haloacetanilides of Formula I with an alcohol of Formula III wherein R4 is dif~erent from and usually larger than the alkyl moiety in the N and 2' and/or 6' positions in the presence of an organic sulfonic acid such as methyl sulfonic acid. In such case, transetherification occurs selectively between the R4 and alkoxymethyl radical on the nitrogen atom; the preparation of compounds of this type is exemplified in Example 22 below.
The transetheri~ic~tion process discussed in this paragraph is the subject of a separate invention by a dif~erent inventorship entity in the assignee's laboratories.
Alternatively, the foregoing compounds having the same or different alkoxyme~hyl radicals in N and 2' and/or 6' positions may be prepared by the N-alkylation o the anion o~ a secondary 2-haloacetamide having one or more o-alkoxymethyl su~stituents with an alkylating agent such as a haloalkyl alkyl ether, e.g., chloromethyl methyl ether;
Example 23 below exemplifies this N-alkylation pro-cess to prepare N~2'~-bis(alkoxymethyl)-2-haloacetanilides~ Com-pounds of the type discussed in this and the preceding paragraph may also be prepared ~y reaction of metal salts of the alcohols of Formula III, e.g., R40M wnere M is an alkali~ne earth) metal, 7- ~t316~1 AG-1161 with compounds of Formula II wherein R is alkox~methyl, X i5 chlorine and Xl is bromo or iodo.
The herbicidal compositions herein are useful as selective herbicides by applying them to the locus of undesir-able plants to be controlled and desirable plants to be protected.
The invention will be more clearly understood byreference to the following detailed description.
Detailed Description of the Invention The compounds of this invention are derived from intermediate compounds characterized in relevant part by having halomethyl substituents in one or both ortho-positions of the anilide ring. These intermediate compounds are themselves novel and the subject of another invention by the inventor herein who has discovered a plurality of methods for the production of the intermediates. Among these methods may be mentioned the frae radical halogenation, preferably in the presence of ultraviolet light, of 2-haloacetanilides. Chlori-nation readily occurs to give mono-chlorination at the N-methyl and/or o-alkyl position, but no reaction at the alpha or nuclear centers. Bromination, with elemental bromine, but more particularly with N-bromosuccinimide, is selective, giving only o-alkyl mono-bromination, even in the presence of an N-methyl moiety. Exemplary processes for preparing the intermediates used in this will be described in examples which follow; all temperature readings are degrees Centigrade.
Example 1 This example describes alternative methods for the preparation of the intermediate starting material, N-(methoxy~
methyl)-2',6'-bis(chloromethyl)-2-chloroacetanilide used to prepare an invention compound.
l(a). 2-Chloro-N,2',6'-trimethylacetanilide (21.1 g, 0.1 mol) was placed in 200 ml CCl~ and an internal 0.2 amp UV
source illuminated within the 500 ml flask. Chlorine (0.1 mol, 7 g) was introduced subsurface with stirring, The reac-tion was mildly exothermic, with temperature climbing from20 to 40. After all chlorine had been added, an essentially colorless soLution was obtained, while nmr showed an obvious mixture with both the -CH3 group on both the ring and the N

8- ~3~ AG~1161 atom undergoing substitution. Neither ClCH2C(O) norring H
moieties were affected. The mixture was cooled to ca 5 and another 0.1 mol chlorine added with nmr still indicating a mixture of mono-chlorinated N-CH3 and ring -CH3. Finally, a third molar equivalent of chlorine was added, with a good deal of spectral simplification. The material was permitted to stand over the weekend, then solvent removed to give vis-cous oil. Portions of this were recrystallized from pentane-ether to give crystals, mp 70~75. Carbon dissulfide also was a good solvent for recrystallization. This material, on the basis of nmr (and its further reactions) was assigned the structure, 2-chloro-N, 2'~6'-tris(chloromethyl) acetanilide.

The b~lk of the viscous oil (7 g) was heated in 250 ml methanol on a steam bath for 10 minut~s, let cool gradually, then stripped of all but ca 50 ml methanol. White crystals developed, and 5 g of these were filtered off, mp 111-114.
Recrystallization from carbon tetrachloride, mp 117-118.
Analysis: Calc'd for C12H14C13NO2(%): C, ~6.40; H, 4.54, N, 4.51;
Cl, 34.24 Found: C, 44.48; H, 4.33; ~, 4.64;
Cl, 34.96.
The product was identified as the above-mentioned intermediate.
l(b). It was also demonstrated that said intermediate could be prapared from the preformed N-chloromethyl compound (derived from chloroacetyl chloride and azomethi~e of 2,6-xylidine). 2-Chloro-N-(chloromethyl)-2',6'-acetoxylidide (10 g, 0.04 mol) in 200 ml CC14 was reacted with 0.081 mol (5.8 g) chlorine at 40-45. Additional 1.4 g C12 was added to make up losses from chlorine volatility. Solvent was removed and the residue boiled with ca 300 ml methanol for lt2 hour, then two-thirds of this volume was removed, the contents scratched, filtered to give 6.4 g.

Example 2 Two grams (0.0065 mol) of the compound of Example 1, i.e., N-(methoxymethyl)-2',6'-bis(chloromethyl)-2-chloroacet-anilide was placed in 25 ml methanol, warmed to dissolve, and 0.0135 mol (2.7 g) silver tetrafluoroborate (AgBF4) dissolved in 10 ml methanol was added. Material stirred with heating at 35-40. Only 0.8 g Ag Cl collected on filtering. Small-scale investigation revealed that little more precipitate could be collected from this filtrate on heating, but more precipitate resulted on heating if more AyBF4 was added.
Therefore 2.5 g additional AgBF4 was added and the material actually heated at reflux three minutes, and kept above 55 for 10 minutes more. The filtrate was boiled once again in the filtering flask on a hot plate, then filtered to give 0.1 g (total AgCl precipitate 1.6 g). The filtered solution was placed in the refrigerator overnite. Then 2.0 g more AgBF4 was added and material boiled ca 5 minutes, to give 0.1 g more AgCl (total 7.2 g AgBF4). The methanol solution was reduced to 1/5 its volume, then added to 5~ NaHC03 solution.
There was an immediate precipitate Ag2O (3.1 g). This was filtered off and salt (NaCl) added with CH2Cl2. The aqueous salt solution was extracted several times with CH2C12. After drying, organic solution was vacuum treated to give 1.2 g light yellow oil.
Analysis: Calc'd for C H2 ClNO4(%): 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 Upon repeating the procedure a second time using 3.1 g of said intermediate 2.1 g yield of final product was obtained.
The product was identified as N,2',6'-tris(methoxy-methyl)-2-chloroacetanilide by NMR.
Example 3 N-(methoxymethyl~-2',6'-bis(chloromethyl)-2-chloro-acetanilide (2.5 g, 0.0081) was placed in 100 ml isopropanol -1 o- 1~31~1 AG-1161 with 8.6 g AgBF4, then refluxed l hour, cooled. AgCl (2.3 y~
was recovered. The material was treated with 5~ NaHCO3 solu-tion, then extracted with CH2Cl2 with salt being added to in-sure complete Ag~ removal and ether-amide recovery. The S mixture was ~iltered, organic solution separated and material vacuum treated to remove solvent to give 2.3 g oil which by nmr showed no CH30; and three-isopropoxy groupings. The crude (1.7 g) was distilled at 200-210 (0.05 mm) in a Kugel-rohr to give 1.3 g amber oil distilled; nmr unchanged.
Anal. Calc~d for C20H3~ClNO4(%): 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 4 2',6'-bis(l-chloroethyl)-N-me~hyl-2-bromoacetani-lide (0.01 mol) was placed in ca. 75 ml methanol which con-tains 2.4 g (0.012 mol) AgBF4. After standing overnite in the dark, the mixture is filtered to recover AgCl, stripped of solvent, taken up in pure methylene chloride washed with aqueous solution of NaCl and Na2CO3, and dried over Mg504.
After filtering and drying, material vacuum treated to remove solvent, and residue recrystallized and/or vacuum sublimed.
Anal- Calc'd ~or C15H22BrN3(~) C, 52-33; Br~ 23-21; N~ 4.07 Found: C, 49.75; Br, 25.57; N, 3.98 The product, m.p. 86-95C obtained in 19% yield was identified as 2',6'-(bis-1-methoxyethyl)-N-methyl-2-bromoacetanilide.
Example 5 . .
2'-(Bromomethyl)-6'-t-butyl-N-methyl-2-bromoacetanilide (3.7 g, 0.01 mol) was placed in 150 ml methanol, and 2.4 g AgBF4 in 50 ml methanol was added. Material was permitted to stand three hours, 1.6 g AgBr filtered off; further standing overnite gave 0.1 g more AgBr (theory 1.9 g). The material was vacuum treated to remove solvent, and the residue treated with the usual mixture of CH2C12/NaCl/10% Na2CO3. After filtering (canvas filter), the filtrate stripped to give oil which crystallized on standing. Recrystallization from hexane, mp 55-60, 2.1 y. Second recrystallizatian from heptane gave a white solid, mp 72-74.
Anal. Calc'd for C15H22BrNO2(%): 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 6 2'-Bromomethyl-6'-t-butyl-N-methyl-2-chloroacetanilide (5 g, 0.015 mol) was dissolved in 250 ml ethanol and 3.3 g of a clear solution of 3.3 g AgBF4 in 50 ml ethanol added at room temperature thereto. There was an instantaneous precipitate of yellow AgBr. Material permitted to stand in the dark over-night, then AgBr filtered off and ethanol removed under vacuum.
The residue taken up in methylene chloride, washed with 150 ml 10% Na2CO3 (to which some NaCl had been added). After filtering the two liquid phases, the organic layer was sepa-rated, washed once more with water, then solvent removed in vacuo. The residue was recrystallized from heptane, and a second recrystallization from ethanol to give 3.0 g yield, m.p. 77-78C.
Anal. Calc'd for C16H24ClNO2(%): C, 64.52; H, 8.12; N, 4.70 Found: C, 63.50; H, 7.81; N, 4.82 The product ~as identified as 2l~ethoxymethyl)-6'-t-butyl-N-methyl-2-chloroacetanilide.

-12- ~131~ AG-1161 ~xample 7 2'-(Bromomethyl)-6'-t-butyl-N-methyl-2-chloroacet-anilide ~1.7 g, 0.005 mol) was placed in ethylene dichloride and added to a solution consisting of 0.7 g p-cresol and 1.0 g AgBF4 in ethylenedichloride. There was an instant, theory precipitate of AgBr. After standing no more than 1/2 hour, solution treated with NaCl solution and filtered to remove last vestiges o~ silver ion. The ethylene dichloride solution was then washed with 5% NaOH to remove phenol. After these washed, CH2C12 added and organic solution given a final water wash. After drying over MgS04, filtering and vacuum treat-ment to remove solvent the residue was recrystallized from isopropanol, then once again to give 0.3 g white solid product, m.p. 148-152C.
Anal. Calc'd for C H ClNO (%): 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'~ tolyloxymethyl)-6'-_-butyl-N-methyl-2-chloroacetanilide.
Example 8 2'-(Bromomethyl)~6'-t-butyl-N-methyl-2-chloroacetani-lide (1.6 g, 0.005 mol) was placed in methanol and a methanol solution of 0.95 g sodium p-nitrophenate was added. The material was refluxed 2 hours, cooled, scxatched, 0.8 g solid precipitate, mp 185-186. Portion recrystallized from aceto-nitrile, to obtain whitç crystals, mp 186-187C.
Anal. Calc'd for C20H23ClN2O4(~): C, 61-46; H, 5.93; Cl, 9.07i N, 7.17 Found: C~ 61.37; H, 6.01; Cl, 9.12;
N, 7.09 The product was identified as 2'~ nitrophenoxymethyl)-6'-t-butyl-N-methyl-2-chloroacetanilide.

-13- 1131~ AÇ-1161 Example 9 2'-fchloromethyl)-6'-t-butyl-N-methyl-2-chloroacetani-lide (0.01 mol) was placed in about 75 ml t-butanol containing 2.4 g (0.012 mol) ~gBF4. After standing overnight in the dark, the mixture was filtered to recover AgCl, stripped of solvent, taken up in pure CH2C12, washed with aqueous solution of NaCl and Na2CO3 and dried over MgSO4. After filtering and drying, the material was vacuum treated to remove solvent and the residue recrystallized and/or vacuum distilled.
Anal. Calc'd for C18 H28ClNO2(~): C, 66.34; H, 8.66; N, 4.30 Found: C, 65.21; H, 8.49; N, 4.41 The product, mp 65-67C, obtained in 46~ yield was identified as 2'~ butoxymethyl)-6'-t-butyl-N-methyl-2-chloroacetanilide.
Example 10 The same procedure in Example 9 was followed, but suhstituting n-propanol for t butanol. The product, a white solid, mp 53-54C, was obtained in 64% yield and had the following elemental analysis:
Calc'd for C17H26ClNO2(%): C, 65.47; H, 8-40; N~ 4-49 C, 64.42; H, 8.15; N, 4.63 The product wasidentified as 2'-(n-propoxymethyl)-6'-t-butyl-N-methyl-2-chloroacetanilide.
Example 11 Following the identical procedure in Example 6, but substituting methanol for ethanol, a white solid recrystallized from methanol having mp 74-75C was obtained in 70~ yield.
Anal. Calc d for C15H22ClNO2(%): 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~

-14~ 6~ AG-1161 Example 12 2'-(Bromomethyl)-6'-_-butyl-2-chloroacetanilide (1.6 g, 0.005 mol) was placed in 25 ml methanol, and 1 g (ca 0.005 mol) AgBF4 added in 20 ml methanol. There was an instant precipitate of theory AgBr. Without further delay, the filtered methanol solution was vacuum treated to remove solvent and 10% Na2CO3 solution added to the residue, along with methylene chloride solution and NaC1. After filtering through a sintered glass funnel with minimum suction, the methylene chloride layer was separated, then vacuum treated to remove solvent. The solid residue, mp 70-90, 0.8 g re-crystallized from variety of solvents the best being cold, aqueous methanol. For analytical sample, the material, a white solid, was vacuum sublimed, oil bath 100-110 (0.05 mm), mp 101-102~
Anal- Calc d for Cl4H20clNo2(%) C, 62.33; H, 7.47; Cl, 13.1~;
N, 5.19 Found: C, 61.45; E, 7.40; Cl, 12.82;
N, 5.01 The product was identified as 2'-~methoxymethyl)-6'-t-butyl-2-chloroacetanilide.
The above product could alternatively be prepared by reacting 3.2 g of the above 2'-bromomethyl starting material in methanol with 0.01 mol sodium methoxide (7.0 ml, 1.48M
NaOCH3 in CH30HI. Reaction heated at 50-60, cooled, let stand, stripped, water/CH2C12 added. CH2C12 solution stripped off and solid recrystallized methylcyclohexane to give product identical with that described above.

Example 13 Following the same procedure in Example 12 but using ethanol as the alcohol, a white ~olid recrystalliæed from hep-tane, was obtained in 55% yield, mp 110-112C.
Anal. Calc'd ~or C15H22ClN2(%) C, 61-87; H, 8-16; N~ 5-L5 Found: C, 61.02; E, 7.55; N, 5.07 -15- ~131~ AG-1161 The product was identified as 2l-(ethoxymethyl)-6~-t-butyl-2 chloroacetanilide.
Example 14 Following -the same procedure in Example 13, but substituting isopropanol as the alcohol, a greyish solid, mp 98-100C, was obtained in 50% yield.
Anal. Calc'd for C16H2~ClNO2(%): C, 64.53; H, 8.12; N, 4.70 Found: C, 64.35; H, 8.09; N, 4.72 The product was identified as 2'-(isopropoxymethyl)-6'-t-10 ~utyl-2-chloroacf~tanilide.

Following the same procedure as in Example 13, but substituting n-butanol as the alcohol, 2'-(n-butoxymethyl)-

6'-t-butyl-2-chloroacetanilide, mp 75-77C, was obtained in lS 45% yield.
Anal. Calc'd for C H26ClNO2(~): C, 65.47; H, 8.40; N, 4.49 Found: C, 65.53; H, 8.41; N, 4.54 Example 16 In similar manner as described in Example 4, but using n-propanol as the alcohol, 2'-(n-propoxymethyl~-6'-t-butyl-2-chloroacetanilide, mp 40C, was obtained in 40~ yield.
Anal. Calc'd for C16H24ClNO2(~): C, 64.52; H, 8.12; N, 4.70 Foundo C, 63.33; H, 7.89; N, 4.73 Example 17 2'-(Bromomethyl)-6'-t-butyl-2-chloroacetanilide (3.2 g, 0.01 mol) was dissolved in 75 ml of allyl alcohol, then 2.4 g (0~012 mol) of silver tetrafluoroborate dissolved in 75 ml allyl alcohol was added. The mixture was allowed to stand ~31~ AG-1161 overnight in the dark. Filtered and stripped of solvent.
The resultant oil was dissolved in CH2C12 and washed once with NaCl solution, then twice with water. The organic layer was dried over MgSO4 and stripped to leave an oil which was crystallized from pentane. Yield 1.7 g, mp 65-67C.
Anal- Calc'd for C16H22ClN2(~ C, ~4-96; H~ 7.50; N~ 4-74 Found: C, 63.85; H, 7.21; N, 4.~8 The product was identified as 2'-(allyloxymethyl)-6'-t-butyl-2-chloroacetanilide.
Example 18 2'-(Bromomethyl)-6'- t-butyl-N-(methoxymethyl)-2-chloroacetanilide (4.2 g, 0.0113'mol) was placed in 250 ml methanol and 50 ml of solution of 3.3 g AgBF4 in 50 ml metha-nol was added. There was an instant precipitate of AgBr, but the mixture was allowed to stand overnite in the dark, then filtered rom 89% theory AgBr. After methanol had been re-moved, the residue was treated in methylene chloride to a mixture of sodium chloride and 10% sodium hydroxide. The liquid phases were filtered and the organic phase separated from the filtrate. After solvent removal, 3.0 g of oil remain-ed which gave consistent nmr structure. The material was dis-tilled in kugelrohr at 200~206 (0.1 mm) to give 2.0 g nearly colorless oil in 59% yield.
in Calc'd ~or Cl6H24ClNO3(%): C, 61i24, H, 7.71; N, 4.46;
_ _ _ __ Found. C, 60.95; Hz 7,.77; N, ,4.~5 Cl, 11~44 ------------~m~e- p-roaucF-was identi~ied as 2'-(mëthoxymethyl)-6l-t-butyl-N-_ ~methoxymethyl~- -chl,,o,r,o,ace~ta~ilide.
Example 19 Following the procedure in the preceding examples, but using as starting materials 2'-(bromomethyl)-6'-t-butyl-W-(ethoxymethyl)-2-chloroacetanilide and ethanol, a white -17- ~131~6~ AG-1161 solid, mp 114-116 was obtained.
Anal. Calc d for C18H28ClNO3(%): C, 63.24; H, 8.26; N, 4.10 Found: C, 62.64; H, 7.90; N, 4.87 The product was identified as 2'-(ethoxymethyl)-6'-t-~utyl-N-(ethoxymethyl)-2-chloroacetanilide~
Example 20 Two grams of 2'-formyl-6'-t-butyl-2-chloroacetani-lide was dissolved in 10 ml methanol and 10 g (CH30)3CH, few drops of SOC12 added to form catalytic amount of HCl.
Material was refluxed on the steam bath 45 minutes, after having stood overnite at room temperature (not necessary).
A few drops o~ 50~ caustic was added to neutralize acid, and cooled solution vacuum stripped to give semi-solid residue (pH ca. 8-9). pH adiusted to 12-14, by adding caustic and water.
The resulting solid filtered, washed on filter cake with water, dried in oven at 60 for 2-3 hours to give 2.1 g. (87% yield) o~
white solid, mp 127-132C. Anal. sample from isopropanol.
Calc'd for C15H22ClNO3(%): 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'-(dimethox~methyl)-6'-t-butyl-2-chloroacetanilide.

Example 21 Five grams (0.012 mol) of 2~,3~-bis-(bromomethyl)-6~-t-butyl-2-chloroa~etanilide was placed in 175 ml methanol, then mixed~ with 7.0 AgBF4 dissolved in the same solvent.
Material let stand overnite in the dark, with AgBr iltered off. Methanol evaporated, CH2C12 added, treated with NaCl/
N~2CO3, filtered through clay, washed once again with water.
After stripping solvent after drying, solid recrystalIized from ether. Anal. sample vacuum sublimed, mp 115-117.
Calc'd for C16H24ClNO3(%~: 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 greyish solid obtained in 50% yield, was identi-fied as 2',3'- bis-(methoxymethyl)-6'-_-butyl-2-chloroacetanilide.

-18~ 16~1 AG-1151 The acetanilide starting material of this example was prepared as follows:
In a 1 liter flask lS g (0.059 mol) of 2',3'-dimethyl-6'-t-butyl-2'-chloroacetanilide was dissolved in 600 ml CC14.
Reaction provided with two white flood lites. The reaction mixtuxe was heated to reflux, then sparged with nitrogen.
Bromine (9.44 g, 0.059 mol) in 50 ml CC14 was added dropwise.
During bromine addition, nmr monitoring revealed that reaction did not proceed stepwise, but rather both arylmethyl groups 10 were brominated at nearly the same rate. Total of two molar equivalents of molecular bromine was added, and nmr o reaction mixture at this stage showed clean reaction in good yield.
After standing over weekend, reaction mixture filtered, mp 180-182, recrystallized gave 187-189. Vacuum sublimation for lS elemental analysis gave mp 195-197. Yield 50%.
Anal. Calc'd for C14H18Br2ClNO(~): C, 40.85; H, 4.41; N, 3.40 ~ound: C, 40.~0; ~, 4.37; N, 3.40 This product was identified as in the lead sentence of this example.
Example 22 This example illustrates the preparation of compounds having different alkyl radicals in the alkoxy moiety of the alkoxymethyl radicals attached to the N- and o-positions.
Three (3) grams of 6'-methyl-N,2'-bis(methoxymethyl)-25 2-chloroacetanilide were mixed with 75 ml of n-butanol and 5 microdrops of methyl sulfonic acid; the mixture was refluxed over soxhlet filled with 3 A mol sieve. The reaction, by GLC, was completed in about one hour. The material was stripped, leaving some butanol, taken up in benzene, washed once with 30 NaHCO3, evaporated to 75C (0.4 mm) to give 3.0 g (87% yield) by GLC of an oil.
Anal- Calcld for C16H24ClNO3 (%): C, 61.12; H, 7.71; N, 4.46 Eound: C, 62.12; H, 8.01; N, 4.29 The product was identified as 2'-(methoxymethyl)-6l-methyl-N-35 (n-butoxymethyl)-2-chloroacetanilide by Nmr.
Example 23 Twenty-six (26) grams of 2'-methyl-6'-(methoxymetnyl)-2-~hloro-acetanilide dissolved in about 200 ml of an 80:20 diethyl ether:

-19- ~3~ AG-1161 tetrahydrofuran mixture was treated with well-rinsed KH; theory H2 evolved. Excess chloromethyl methyl ether was added. After reaction and aqueous washes, crude material showed GLC assay nearly equivalent to a distilled heart cut,26 g yield (84%).
The material chromatographed through Florisil to give 19 g oil, b.p. 180C (0.05 mm).
~nal- Calc'd or C13H18ClN3 (%): 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)-10 2-chloroacetanilide.
The process used in this example may be modified by use of a starting acetanilide having a different alkoxymethyl radical in the o-positions from that placed on the N atom by the halomethyl alkyl ether.

Examples 24-28 In similar manner as described in the above examples, other compounds corresponding to Formula I above wer-e prepared;
these compounds are identified in Table I together with certain physical properties.

-20~ AG-1161 i6~

O et~ D Q t`

U~
Ul a~
~1 ~ t` O ~ ~ O n ~r ~ o ~1 ~o ~D O O 1~
,~ ~ r o ~ ~I CO O a~ ~ ~D Lr) ~ ~ ~D

C~

~ ~ $ æ c~ x z c~ ~: z c~ æ c~ ~ z ~1 w c~ ^ r co I ~
. o ~ l ~1 ~ ~1_ ~ ~ ~3 ~ l ~1 1 ~D .
H. ' E3 ~1 a~ ~1 0 ~ O
~~ m--~ ~ o ~ ~_ ZO Z Z o Z
O ~1 ~D ~r o ~ ~
s~ e m :~ m ::c m rl s~ ~ ~I ~ O U~
e ~ c~
~, I
~1 rl I
I ~ ~_ _,, .,,I ,_, I a~
I ~ d w ~ ~~ :~
--~dI ~I ~ a) II x ~
,~ O ~:5 a)~ u C~ 1 ~~ o X
~~ o~ s~~ o o~ o oo ~X OX--o X ~~--o~5)oIoI~ oa)oI~
~Z o ~ ~~Z o I~ I ~
I I ~~1 0 O OO ~1 0 --o~ ~ ~

a) O
~C Z t~

~3~

.
Examples 29-62 Yet other compounds corresponding to Formula I
herein and contemplated as within the scope of this invention . are shown in Table II. In the examples, the individual compounds are those whose members are identified by Formula S ~.

. .

, .

. . .
.

.
. .

. .
. .
...... .

. . .
:-.
.,, . .

... .

'~ ~

x I ~ m m c~ o m H c~ m c) c~ ~ c) c) m c~ m c~ ~ H O m m ~1 r~ ~ X ~ r ~ o r. ~ x ~ N

~1 x r~ c x ~ x x ~: r~
a~
~~1 F!:; x 5: ~ x ~ : x ~ x m ~

H
H ~: ¦ O ~1 ~ I ~1 ~ ~ ~1 ~ ~1 ~1 0 ~1 ~ ~1 ~) ~r ~1 0 ~1 ') Q u) ~ 0 r~r~ r ~r~: X ~ X ~ m ~ x _` U~ Lf y u~ ~
o o ~ ~ .
,~ ~ ~ ~ ~Y7 ~ ~ ~ ~1 ,~, tc ~ r~ r~ ~ ~ r~ ~ h ~ Q ~ R~ ~ r~ r~

o o ,1l 1 1 mm o ~
ll :: ~: X ~ : X ~ r ~ $r~ $~
s~
a) Q~Q ~ Q O O O
U~ I I I

X ~ ~ o ~ ~ ~ ~ ~ ~ o ~ ~ ~ u~ ~ 1` 0~ ~ O

.....
.

~3~

X I t) c) C~ C.) U C~

~ ~1 ~ ~ ~ ~ ~1 ~1 $ ~ ~ ~ 0~ m ~ .~
o ~ a~ ~ a o I
i ~1 1 a ~r ~

x ~ $ m m ~ m --oP~
s: ~ ~ m ~ P: m ::: m o o m ~ I ,~ ~ ,1 ~1 ~1 ,1 ,1 ~1 ~1 0 0 H
: _ ~ C~
O O
~ $ x m P::q m m ~ m ~_ ~ C~
~a o ~
.,, U~
~ ~, u~
~1 ~ ~ ~ m - ~ ~ ~c m ~ x Q~ U :q Q R C ) _ Q ~ ~ Y Z-l ~1 ~ m I ~ U C~ C~ V
~ I J ' ' ' _, ~ ~ o ~ m p ~ ' I
~; o ~ o ~ o o o o o ~ ~I o o o ~ o x ~ m ~:
I ~ I I I I I ~ ~ I I
a) I
I ~ ~ ~ ~ ~n ~ 1~ ~0 cn o ,~ ~

~3~6~ AG-1161 As noted above, compounds according to this inven-tion have been found to be effective as herbicides in the partial or total inhibition of undesirable vegetation. Tables IIIA and IVA summarize results of tests conducted to determine the pre-emergent herbicidal activity and Tables IIIB and IVB
the post-emergent herbicidal activity of representative com-pounds.
The pre-emergent test was conducted as follows:
A good grade of top soil was placed in aluminum pans and compacted to a depth of three-eighths to one-half inch from the top of the pan. On the top of the soil was placed a predetermined number of seeds or vegetative propagules of various plant species. The soil required to level fill the pans after seeding or adding vegetative propagules was weighed into a pan. A known amount of the active ingredient applied in a solvent or as a wettable powder and the soil were thoroughly mixed, and used as a cover layer for prepared pans. After treatment, the pans were moved into a greenhouse bench where they were watered from below as needed to give adequate moisture for germinatîon and growth.
Unless noted otherwise, approximately 2 weeks after seeding and treating, the plants were observed and the results recorded. Tables IIIA and IVA below, summarize such results.
The herbicidal rating was obtained by means of a fixed scale based on the percent injury of each plant species. The ratings are defined as follows:
% Control Rating 0-24 o The post-emergent tests were conducted as follows:
The active ingredients are applied in spray form to two or three week old specimens of various plant species. The -25~ t~ AG-1161 spray, a solution or wettable powder suspension containing the appropriate rate of active ingredient to give the desired test rate and a surfactant, is applied to the plants. The treated plants are placed in a greenhouse and unless other-wise noted approximately two weeks later the effects ranging from no response to total inhibition are observed and recorded.
The results are shown in Tables IIIB and IVB in which the post-emergent herbicidal activity index is as follows:
~ Control Rat g lO0 4 The plant species utilized in these tests are identified by letter in accordance with the following legend:

A Canada Thistle E Lambsquarters I Johnsongrass B Cocklebur F Smartweed J Downy Brome C Velvetleaf G Nutsedge K Barnyardgrass 20 D MorninggloryH Quackgrass 66~L
~~5~ AG-1161 Table IIIA

Plant Species Compound of E~ample No. Lb/A (Rg/Ha) ~ B C D E F G H I J K
2 5.0(5.6) 0 0 1 0 0 1 2 1 0 3 3 3 5.0(5.6) 0 0 0 0 1 0 0 0 3 1 3 4 10.0(11~2) 0 0 0 1 0 0 1 0 0 0 0 5.0(S.6) 0 0 0 1 0 0 0 0 0 1 1 5.0(5.6) 0 0 1 1 3 3 0 0 0 3 3 6 5.0(5.6) 1 1 1 1 3 2 3 3 1 2 3

7 10.0(11.2) 3 0 1 0 3 2 1 1 0 3 3

8 10.0 (11.. 2) 1 0 0 1 0 0 0 0 0 3 3 5.0(5.6) 1 0 0 1 0 0 1 0 0 1 1

9 5.0(5.6) o 0 0 0 2 0 3 2 0 2 3 5.0(5.6) 0 0 0 0 3 1 2 1 0 3 3 11 5.0(5.6) 0 0 0 1 3 1 2 0 0 1 3 12 5.0 (5-6) 0 0 1 2 3 1 2 1 0 2 3 13 5.0(5.6) 0 0 1 0 2 1 2 1 0 2 3 14 5.0(5.6) 0 0 1 1 3 0 3 1 1 3 3 5.0(5.6) 1 0 1 0 2 2 3 3 0 3 3 16 10.0(11.2) 0 0 1 0 3 1 3 3 1 2 3 5.0(5.6) 0 0 1 0 1 0 2 2 1 2 3 17 10.0(11.2) 0 1 1 1 2 1 1 2 0 2 3 5.0(5.6) 0 0 1 0 3 0 1 1 0 0 3 1~ 5.0(506) 0 0 1 1 3 1 1 2 1 3 3 1~ 10.0(11.2) 0 0 1 1 2 0 2 2 1 3 3 5.0~5.6) 0 0 1 0 2 0 1 2 1 1 2 lOoO(11.2) 1 0 1 1 3 1 1 1 0 1 3 5.0(5.6) 0 0 0 0 2 0 1 0 0 0 2 22 10.0(11.2) 1 1 1 1 1 1 2 3 1 3 3 5.0(5.6) 1 1 1 1 1 0 1 3 1 2 3 23 5.0(5.6) 0 0 0 0 2 0 0 0 0 0 1 24 5.0(5.6) 1 1 2 2 3 3 2 0 0 3 3 5.0(5.6) 3 0 0 Q 1 2 0 1 0 1 3 26 10.0(11~2) 3 2 2 2 3 3 3 2 0 3 3 5.0(5.6) 3 1 1 2 3 3 2 1 0 3 3 27 lQ.Q(11.2) 0 0 Q 0 0 0 0 0 0 0 3 5.0(5.6) 0 0 0 0 0 0 0 0 0 0 3 ':

~L~3~;6~

Table IIIA (Cont'd) Pre-Em~ent Plant Species Compound of Example No. Lb/A (K~/Ha) A B C D E F G H I J K
.
28 10.0(11.2) 3 2 1 3 3 3 3 2 0 3 3 5.0(5.6) 2 2 1 2 3 1 3 2 0 3 3 Table IIIB
Post-Emergent Plant Species Compound of Example No. Lb/A (K~/Ha) A B C D E F G H I J K
2 5.0(5.6) 0 1 0 1 0 0 0 0 - 0 4 10.0(11.2) 0 1 0 1 4 1 0 l 0 0 0

10.0(11.2) 0 1 1 2 1 0 0 0 0 0 0 6 10.0(11.2) 1 1 l 1 2 1 0 1 0 0 2 7 10.0(11.2) 0 l 0 0 1 1 0 0 0 0 8 lO.0(11.2) 1 l 0 0 0 0 0 0 0 0 0 9 10.0(11.2) l 1 0 1 4 4 0 0 0 1 2 10.0(11.2) 1 1 l 1 1 1 1 1 1 0 2

11 10.0(11.2) 0 1 0 l l 0 0 0 0

12 10.0(11.2) 0 l 0 l 0 0 0 0 0 0 0

13 10.0(11.2) 1 1 0 l 1 1 0 0 0 0

14 lO.0(11.2) 0 0 0 1 l 0 0 0 0 0 10.0(11.2) 1 1 0 1 l 1 0 0 0 0 16 10.0(11.2) 1 1 1 1 2 1 1 1 0 0 2 17 10.0(11.2) Q 1 0 1 1 0 1 0 0 0 2 18 10.0(11.2) 1 1 0 1 1 1 0 0 :- 0 2 10.0(11.2) 0 0 1 1 0 0 l 1 0 0 0 23 lO.0(11.2~ 0 0 1 0 0 0 0 0 0 0 0 - 24 10.0(11.2) 0 1 0 1 0 2 0 0 0 0 2 10.0(11.2) 0 l 0 1 0 0 0 0 0 0 2 26 10.0(11.2) 0 1 0 l - 1 1 0 0 0 2 28 10.0(11.~) 0 1 1 l 0 0 1 l 0 ` -28- ~3~6~ 1161 The compounds were further tested by utilizing the above procedure on the following plant species:

L Soybean R Hemp Sesbania M Sugarbeet E Lambsquarters N Wheat F Smartweed O Rice C Velvetleaf P Sorghum J Bromus tectorum (Downy brome) B Cocklebur S Panicum Spp.
Q Wild Buck-. K Barnyardgrass wheat D Morning- T Crabgrass glory The results axe summarized in Tables IVA and IVB.

13~6~

Table IVA
Pre-Emergent Plant S~ecies Compound of Example No. Lb/A (I;~/Ha) L M N O P ~ Q D R E F C J S K T
2 5.0 (5.6) 0 l 1 0 l 0 0 1 1 2 1 0 0 3 3 3 1.0 (1.12) 0 1 0 1 2 0 0 0 1 0 1 0 2 3 3 3 0.?5 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 3 0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 3 1.0 (1.12) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0.05 (0.061 0 0 - 0 0 0 0 0 0 0 0 0 0 l.0 (1.12) 1 0 0 2 3 0 1 0 1 1 1 0 0 2 3 3 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 3 0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 6 5.0 (5.6) 1 2 2 3 3 0 1 0 1 1 l 0 2 3 3 3 l.0 (1.12) 0 l l l 2 0 0 0 0 1 0 0 l 2 3 3 0.25 (0.28) 0 0 0 0 2 0 0 0 0 1 0 0 l 2 2 2 0.05 (0.06) ~0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 7 5.0 (5.6) 0 1 0 1 0 0 0 0 1 0 1 0 0 2 3 3 1.0 (1.12) 0 0 0 1 0 0 0 0 0 0 1 0 0 l 3 3 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 Z
8 5.0 (5.6) 1 2 0 0 0 0 0 0 l 0 0 0 0 0 3 2 1.0 (1.12) 0 l 0 0 0 0 0 0 0 0 0 0 0 0 l l 9 1.0 (1.12) 3 1 1 1 2 3 l 0 1 2 l l 1 2 3 3 0.25 (0.2~) 3 1 0 1 1 3 0 0 1 l 0~1 0 1 2 2 0.05 (0.06) 3 0 0 0 0 3 0 0 0 o 0 0 0 0 0 0 . .

5.0 (5.6) 1 3 2 3 3 0 0 1 2 3 3 l 3 3 3 3 l.0 (1.12) 1 2 2 2 3 0 0 0 0 1 1 0 2 3 3 3 0.25 (0.28) 1 l l 1 2 0 0 0 0 0 1 0 2 2 3 3 0.05 (0.06) 0 0 0 1 0 0 0 0 0 0 1 0 0 1 l 2 11 5,0 (5-6) 2 3 l 2 3 0 0 0 1 2 2 l 2 3 3 3 1.0 (1.12) 1 2 0 0 1 0 0 0 1 2 1 0 l 3 3 3 0.25 (0.~8) 1 1 0 0 1 0 0 0 0 2 0 0 0 2 3 2 0.05 (0.06) 1 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 ~- ~13~
~30- AG-1161 Table I~IA
Pre-E~er~ent Plant Species Compound of Example No. L~/A (K~/Ha) L M N O P B Q D R E F C J S K T
12 1.0 (1.12) 2133300111003333 0. '5 (0.28) 1 0 0 1 1 0 0 0 1 0 0 0 2 2 2 3 0.05 (0.06) 0 0 0 0 0 Q 0 0 0 0 0 0 0 0 0 1 13 5.0 (5.6) 3333332333313333 1.0 (1.12) 21223302 2 2 0 1 2 333 0.25 (0.28) 1 1 0 1 1 0 0 310001333 0~05 (0.06) 0 0 0 1 1 0 0 0 1 0 0 0 0 0 1 1 0.01 (0.011) 0000030000000000 14 5.0 (5.6) 2 2 333102 2 3 2 33333 1.0 (1.12) 2 1 2 33 0 0 1 2 2 1 1 3 333 0.25 (0.28) 1 0 0 0 1 0 0 0 0 0 0 0 0 1 3 3 0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0.01 (0.11) 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 0 5.0 (5.6) 2 3 3 3 3 1 0 1 3 3213333 1.0 (1.12) 1 2 2 3 2 0 0 0 2 1 1 0 2 2 3 3 0.25 (0.28) 010100000000112 2 16 5.0 (5.6) 1 2 1 3310123 2 1 333 3 1.0 (1.12) 0101100011102 3 3 3 0.25 (0.28) 0001000011001223 0.05 (0.06~ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 17 5.0 (5.6) 2 2 3 2302111103 3 3 3 1.0 (1.12) 1010100000001133 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 2 18 5.0 (5.6) 2 222302223 2 1 3333 1.0 (1.12) 1 1 1 1 2 0 1 2 2 2 1 0 2 333 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 2 0.05 (0.06) 0 0 0 1 0 0 0 1 0 0 0 0 0 0 1 2 19 5.0 (5.6) 1 2 3 3 3 0 0 2 1 2 2 0 3333 1.0 (1.12~ 1 1 0 1 300111103333 0.25 (0.28) 0 1 0 0 1 0 0 0 1 1 0 0 2 2 2 2 5.0 (5.6) 2 1 2 2 301111113333 1.0 (1.0) 0 0 0 0 0 0 0 0 1 0 0 0 1 1 2 2 :' ' : , .: . , 66~
-31~ AG-1161 Table IVA (Cont '~) Plant Species Compound of Example No. L_ (Kg/Ha) L M N O P B Q D R E F C J S K T
22 5.0 (5.6) 0 0 1 1 2 0 0 1 1 1 0 1 3 33 3 1.0 (1.12) 0 0 0 1 1 0 0 0 0 1 0 0 2 2 33 0.25 (0.28) 0 1 0 0 0 0 0 0 0 1 0 0 0 0 1 2 0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 24 5.0 (5.6) 0 2 0 1 3 2 3 2 2 3 3 2 1 3 3 3 1.0 (1.12) 0 1 0 0 2 0 0 1 1 1 1 0 0 3 33 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 1 0 0 3 33 0.05 (0.06) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 5.0 (5.6) 0 1 1 0 31 3 1 1 2 3 0 1 3 3 3 1.0 (1.12) 0 - 0 0 1 0 2 0 0 3 2 0 2 3 3 3 0.25 (0.~8) 0 1 2 0 0 0 0 0 0 0 ~ 0 1 3 3 3 0.05 (0.06) 0001000000000032 0.01 (0.11) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 26 5.0 (5.6) 1 2 2 33 3 2 3 3 - 313333 1.0 (1.1;~) 0 3 1 331313 - 3 03333 0.25 (0.28) 0 2 1 2 3 0 0 0 2 - 2 0 1 3 33 0.05 (0.06) 0 0 0 0 0 0 0 0 0 - 1 0 0 1 3 3 0.01 (0.11) 000001000 - 20003 2 27 5.0 (5.6) 0 0 0 0 0 0 1 0 1 3300033 1.0 (1.12) 00000000 - 31000 2 3 0.25 (0.28) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 28 5.0 (5.6) 0 323323333303333 1.0 (1.12) 0 2 0 2 3 1 3223303333 0.25 (0.28) 0 1 0 0 1 0 0 0 0 3 300333 0.05 (0.-06) 0000001003200022 ,~ . .

6~;~

Table IVB
Post-Emergent Plant S ecie~
Compound of P
Example No. Lb/A (Kg/Ha) L M N O P B Q D R E F C J S K T
9 5.0 (5~6) 2 1 0 1 1 1 1 2 1 2 1 1 0 1 3 3 1.0 (1.12) 1 0 0 0 0 0 1 1 1 1 0 1 0 0 2 2 0.25 (0.28) 1 0 0 0 0 0 1 1 1 0 0 0 0 0 1 1 0.05 (0.06) 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ~33- ~ ~ 3~ 6~ ~ AG-1161 The herbicidal compositions of this invention in-cluding concentrates which require dilution prior to appli-cation contain at least one active ingredient and an adju-vant in li~uid or solid form. The compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particu-late solids, ~ranules, pellets, solutions, dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsi-fying agent or any suitable combination of these.
The compositions of this invention, particularly liquids and wettable powders, preferably contain as a con-ditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into the compositions greatly enhances their efficacy.
By the term "surface-active agent" it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Anionic, cationic and non-ionic agents can be used with equal facility.
Preferred wetting agents are alkyl 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 vegetable oils, ditertiary acetyleni~ glycols, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g., sorbitan~. Preferred dis-persants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl, naphthalene sulfonates, sodium naphthalene sulfonate, and the polymethylene bisnaphtha-lene sulfonate.
Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid 6~L
-34~ ~G-1161 extender and one or more wetting and dispersing agents. The inert solid extenders are usually of mineral origin such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powders compositions of this invention usually contain from about 0.5 to 95 parts (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 95 parts (preferably 5-50 parts) of inert solid extender, all parts being by weight of the total composition. Where re-quired, from about 0.1 to 2~0 paxts of the solid inert extender can be replaced by a corrosion inhibitor of anti-foaming `agent or both.
Aqueous suspensions may be prepared by mixing to-gether and grinding an aqueous slurry o water-insoluble active ingredient in the presence of dispersing agents to obtain a concentrated slurry of very inely-divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted and sprayed, coverage is very uni~orm.
Emulsifiable oils are usually solutions o active ingredient in water-immiscible or partially water-immiscible solvents together with a surface active agent. Suitable solvents for the active ingredient o this invention include hydrocarbons and water-immiscible ethers, esters or ketones.
The aqueous suspensions and emulsifiable oil compo-sitions ge~erally contain from about 5 to 95 parts (preferably 5-50 parts) active ingredient, about 0.25 to 50 parts (preer-ably 1-25 parts) surace active agent and where required about 4 to 94 parts solventj alI parts being by weight based on the total weight of emulsifiable oil.
Granules are physically stable particulate composi-tions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate ~3~
~35~ AG-1161 extender. In order to aid leaching of the active ingredient from the particulate, a surface active agent such as those listed hereinbefore can be present in the composition.
Natural clays, pyrophyllites, illite and vermicuiite are examples o~ operable classes o~ particulate mineral extenders.
The pre~erred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate atta-pulgite or heat expanded, particulate vermiculi~e, and the finely-divided clays such as kaolin clays, hydrated attapul-gite or bentonitic clays. These extenders are sprayed orblended with the active ingredient to form the herbicidal granules.
The granular compositions of this invention general-ly contain ~rom about 5 parts to about 30 parts by weight of active ingredient per 100 parts by weight of clay and O to about 5 parts by weight of surface active agent per lOO parts by weight of particulate clay. The preferred granu-lar compositions contain from about 10 parts to about 25 parts by weight o~ active ingredient per 100 parts by weight of ~ claY.
The compositions of this invention can also contain other additaments, for example, fertilizers, other herbicides, other pesticides, safeners and the like used as adjuvants or in combination with any of the above-described adjuvants.
Chemicals useful in combination with the active ingredients o~ this invention include, ~or example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like such as:
3-amino-2,5-dichlorobenzoic acid 3-amino-1,2,4-triazole 5-amino-4-chloro-2-phenyl-3(2H~-pyridaæinone 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-N,N-diallylacetamide 2-chloroallyl diethyldithiocarbamate N'-(4-chlorophenoxy) phenyl-N,N-dimethylurea 131~

N,N-dimethyl-N~(3-chloro-4-methylphenyl) urea S-(.4-chlorobenzyl).N~N-diethylthiolc~rbamate isopropyl N-(3-chlorophenyl) carbamate 2,2-dichloropropionic acid S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate 2-methoxy-3,6-dichlorobenzoic acid 2,6-dichlorobenzonitrile N,N-dimethyl-2,2-diphenylacetamide 6,7-dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt 3-(3,4-dichlorophenyl)-1,1-dimethylurea 4,6-dinitro-o-sec-butylphenol 1,3-dimethyl-3-t2-benzothiazolyl) urea ethyl N,N-dipropylthiolcarbamate 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-(~-chlorophenyl)-1,1-dimethylurea l-butyl 3-(3,4-dichlorophenyl)-1-methylurea N-l-naphthylphthalamic acid 1,1'-dimethyl-4,4'-bipyridinium salt 2-chloro-4,6-bis~isopropylamino)-s-triazine 2-chloro-4,6-bis(ethylamino)-s-triazine 2,4-dichlorophenyl-4-nitrophenyl ether alpha, alpha, alpha~trifluorc-2,6-dinitro-N,N-dipropyl-p-toluidine S-propyl dipropylthiolcarbamate 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 : : monosodium acid:methanearsonate disodium methanearsonate N-(l,l-dimethylpropynyl)-3,5-dichlorobenzamide 2-chloro-~,~,a-trifluoro-p-tolyl-3-ethoxy-4-nitro-dinhenyl ethe~
Sodium 5-f2-chloro-4-ttrifluoromethyl)phenoxy]-2 nitrobenzoate Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate 4-amino-6-t-butyl-3-methylthio-1,2,4-triazin-5-one N-~2,4-dimethyl-5-~[(tri~luoromethyl)sulfonyl]amino~
phenyl~ acetamide 3-isopropyl~lH-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 Cl 6 monoalkyl amine and alkali metal salts and combinations thereof in ratios of 1-4 lb/acre (1.12-4.48 kg/ha) to 1-10 lb/acre of compounds of this inverltion-Fertilizers useful in combination with the active in-gredients include for example ammonium nitrate, urea, potash and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost manure, humus, sand and the like.
When operating in accordance with the present invention, effective amounts of the acetanilides of this invention are ap-plied to the soil containing the plants, or are incorporated into aquatic media in any convenient fashion. The application of liquid and particulate solid compositions to the soil can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired.
The application of an effective amount of the compounds of this invention to the locus of undesired weeds is essential and critical for the practice of the present invention. The exact amount of active ingredient to be employed is dependent upon various factors, including the plant species and stage of development thereo~, the type and condition of soil, the amount of rainfall and the speci~ic acetanilide employed. In selective preemergence application to the plants or to the soil a dosage of from 0.02 to about 11.2 kg/ha, preferably from about 0.04 to about 5,60 kg/ha, or suitably from 1.12 to 5.6 kg/ha of acetani-lide is usually employed. Lower or highex rates may be required in some instances. One skilled in the art can readily determine from this specification, including the above example, the opti-~3~- AG-1161 mum rate to be applied in any particular case.
The term "soil" is employed in its ~roadest sense to be inclusive of all conventional "soils" as defined in Webster's New International Dictionary, Second Edition, Una-bridged (1961). Thus the term refers to any substance ormedia in which vegetation may take root and grow, and includes not only earth but also compost, manure, muck, humus, sand and the like, adapted to support plant growth.
Although the invention is described with respect to specific modifications, the details thereof are not to be con-strued as limitations except to the extent indicated in the following claims.

Claims (22)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Compounds having the formula wherein X is halogen, R and R1 are independently hydrogen, C1-10 alkyl, alkoxymethyl or alkoxymethyl substituted with one or two C1-4 alkyl groups, R2 and R3 are independently hydrogen, C1-C4 alkyl or alkoxy groups, R4 is hydrogen, C1-10 alkyl or alkenyl, phenyl or phenyl substituted with C1-5 alkyl or alkoxy, halogen or nitro groups and n is an integer from 0-4 inclusive.

2. Compounds according to Claim 1 wherein R is hydrogen.

3. Compounds according to Claim 1 wherein R is a C1-10 radical.

4. Compounds according to Claim 1 wherein R is C1-10 alkoxymethyl or alkoxymethyl substituted with one or two C1-4 alkyl groups.

5. Compounds according to any of Claims 2, 3 or 4 wherein R1 is hydrogen.

6. Compounds according to any of Claims 2, 3 or 4 wherein R1 is a C1-10 alkyl radical.

7. Compounds according to any of Claims 2, 3 or 4 wherein R1 is a C1-10 alkoxymethyl or alkoxymethyl substi-tuted with one or two C1-4 alkyl groups.

8. Compounds according to any of Claims 2, 3 or 4 wherein R4 is a C1-10 alkyl radical.

9. Compounds according to any of Claims 2,3, or 4 wherein R4 is a C2-10 alkenyl radical.

10. Compounds according to any of Claims 2, 3, or 4 wherein R4 is phenyl or phenyl substituted with C1-5 alkyl or alkoxy, halogen or nitro groups.

11. Compounds according to any of Claims 2, 3 or 4 wherein R2 and R3 are both hydrogen.

12. Compounds according to any of Claims 2, 3 or 4 wherein at least one of R2 or R3 is a C1-4 alkyl radical.

13. Compound according to Claim 1 wherein said compound is 2'-(methoxymethyl)-6'-methyl-N-(ethoxymethyl)-2-chloroacetanilide, 2'-(methoxymethyl)-6'-methyl-N-(methoxy-methyl)-2-chloroacetanilide, 2'-(methoxymethyl)-6'-methyl-N-(n-butoxymethyl)-2-chloroacetanilide, 2'-(n-propoxymethyl)-6'-?-butyl-2-chloroacetanilide or 2'-(methoxymethyl)-6'-methyl-N-(isopropoxymethyl)-2-chloroacetanilide.

14. Process for preparing compounds of the formula I wherein X is halogen, R and R1 are independently hydrogen, C1-10 alkyl, alkoxymethyl or alkoxymethyl substituted with one or two C1-4 alkyl groups, R2 and R3 are independently hydrogen, C1-4 alkyl or alkoxy groups, R4 is hydrogen, C1-10 alkyl or alkenyl, phenyl or phenyl substituted with C1-5 alkyl or alkoxy, halogen or nitro groups and n is an integer from 0-4 inclusive which comprises reacting a compound of the formula II

wherein X and said R-R3 groups are as defined above and X1 is chloro, bromo or iodo, with a compound of the formula wherein R4 is as defined above; wherein the reaction is con-ducted at temperatures within the range of about -80°C. to 180°C. and wherein the reaction is conducted in the presence of silver tetrafluoroborate.

15. Process according to claim 14 wherein the reaction is conducted in the presence of a heavy metal cation, other Lewis Acid or, when X=C1 and X' is bromo or iodo, a C1-10 alkoxide of an alkali metal or alkaline earth metal.

16. Process according to claim 15 wherein the reaction is conducted in the presence of sodium methoxide when X' is a bromo or iodo atom and X=chloro atom.

17. Process according to claim 15 wherein said compound of Formula III and silver tetrafluoroborate are present in excess amount relative to said compound of Formula II.

18. Process according to claim 15 comprising reacting 2'-(bromomethyl)-6'-?-butyl-N-(methoxymethyl)-2-chloroacetanilide with methanol to obtain 2'-(methoxymethyl)--6'-?-butyl-N-(methoxymethyl)-2-chloroacetanilide.

19. Process according to claim 15 comprising reacting 2',6'-bis(l-chloroethyl)-N-methyl-2-bromoacetanilide with n-propanol to obtain 2'-(?-propoxymethyl)-6'-?-butyl-2-chloroacetanilide.

20. Process according to claim 15 comprising reacting 2'-(bromomethyl)-6'-methyl-N-(methoxymethyl)-2-chloroacetanilide with methanol to obtain 2'-(methoxymethyl)-6'-methyl-N-(methoxymethyl)-2-chloroacetanilide.

21. A method for controlling undesirable vegetation which comprises applying to the locus thereof a herbicidal composition comprising an adjuvant and an effective amount of a compound having the formula wherein X is halogen, R and R1 are independently hydrogen, C1-10 alkyl, alkoxymethyl or alkoxymethyl substituted with one or two C1-4 alkyl groups, R2 and R3 are independently hydrogen or C1-4 alkyl groups, R4 is C1-10 alkyl or alkenyl, phenyl or phenyl substituted with C1-5 alkyl or nitro groups, and n is an integer from 0-4 inclusive.

22. Method according to claim 21 whereinsaid compound is 2'-(methoxymethyl)-6'-methyl-N-(ethoxymethyl)-2-chloroacetanilide, 2'-(methoxymethyl)-6'-methyl-N-(methoxy-methyl)-2-chloroacetanilide, 2'-(methoxymethyl)-6'-methyl-N-(n-butoxymethyl)-2-chloroacetanilide, 2'-(n-propoxymethyl)-6'-t-butyl-2-chloroacetanilide or 2'-(methoxymethyl)-6'-methyl-N-(isopropoxymethyl)-2-chloroacetanilide.

.