NZ196545A - 2-haloacetanilides and herbicidal compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 96545 V 196545 Priority Dat^s): ;?P. jo • -2 Of CompJsta Specification FHsd: Coict031 PloiNZljaa Glass. ••••••«• ■ • • ■ • • ■ • /jiv • P.O. JontmaS, Wo: . ■ • M5V '' -'J £K £3 NEW ZEALAND PATI-NTS ACT, 1453 No.: Date: COMPLETE SPECIFICATION 1HERBICIDAL 2-HALOACETANILIDES' fc/We, MONSANTO COMPANY, a corporation of the State of Delaware, United States of America, now residing at 800 North Lindberg Boulevard, St. Louis, Missouri 6 3166, the United States of America, hereby declare the invention for which ~i~/ we pray that a patent may be granted to f«e-/us, and the method by which it is to be performed, to be particularly described in and by the following statement: (followed by page la) 1 — <rttG—12«. J— HERBICIDAL 2-HALQACETANILIDES Background of the Invention Field o£ the Invention This invention pertains to the field of 5 2-haloacetanil ides and their use in the agronomic arts, e.g., as herbicides.

Description of che Prior Art The prior art relevant to this invention includes numerous disclosures of 2-haioacetanilides 10 which may be unsubstituted or substituted with a wide variety of substituents on the anilide nitrogen acorn and on the anilide ring including alkyl, alkoxy, alkoxyalkyl, halogen, etc., radicals.

As relevant to the invention compounds, which 15 are characterized by having a methyl or ethyl radical on the anilide nitrogen, an alkoxy radical in one ortho position and a methyl radical in the other ortho position, the closest prior art known to the inventor are U. 3. Patent Numbers 3,26b, 584, 3,442,945, 20 3,773,492 and 4,152,137. The '492 and "137 patents disclose generic formulae for herbicidal compounds which broadly emcompass the invention compounds.

However, the only N-aj.kyl-substituteo 2-haloacetaniiicie compound specifically disclosed by either of the '492 25 or '137 patents is propachlor, i.e., N-isopropy1-2- chioroacetanilide, a well-known commercial heroicide; neither patent discloses any heroicidal data relative to propachlor. U.S. Patent Number 2,863,752 (Re 26,961) discloses compounds of a class encompassiny 30 propachlor (not specifically named) and homologs and analogs thereof. Of the compounds within the scope of the '752 patent, propachlor was found to be the most herbicidaliy efficacious, hence, was developed as a commercial herbicide. Said '752 patent discloses that 35 the compounds therein may be used at rates as low as 1.0 lb/A (1.12 kg/ha); however, as shown in Example IV the experimental data presented therein is limited to application rates of 5 lb/A (5.6 kg/ha) and 25 ib/n (2b ly 6545 — J kg/'ha ) . Additionally , N-ethyi-2-cnioroacecanix ide is a named species in said '752 patent; yet, U.S. Patent Wo. 4,137,070 discloses that that compound (Example 406 in the '070 patent) is an antidote for the herbicide EPTC. In contrast to the foregoing '7 52 compounds, the compounds of this invention are highly effective selective herbicides against exceedingly hard-to-control weed species at application rates well below 1.0 lb/A, e.g., ranging to below one-sixteenth (1/16) lb/A (0.07 kg/ha).

More structurally relevant to the invention compounds than propachlor or related compounds, perhaps, are compounds disclosed in said '584 and '9 45 patents. In particular, Example 13 of said '584 patent discloses the compound N-tert-butyl-2'-methoxy-2-chloroacetanilide and Example 67 of said '945 patent discloses the compound 21-metnoxy-61-tert-butyl-2-chloroacetanilide. Thus, propachlor differs from the invention compounds in the type of substituent radicals in two positions, i.e., both ortho positions of the molecule, as weil as tne particular alkyl radical attached to the nitrogen atom. Said Example 13 in saio '584 patent differs in the type of substituent in one ortho position, the particular alkoxy radical in the other ortho position and the particular alkyl radical attached to the nitrogen atom and said Example 67 in said '945 patent differs from the invention compounds in the type of substituent attached to the nitrogen atom and the particular alkyl and alkoxy raaicals, respectively, attached to the ortho positions of the anilide molecule.

U.S. Patent No. 4,146,387 discloses 2-haloacetaniiide compounds which may be substituted with aikyl radicals on the nitrogen atom anu in botn ortho positions. The compounds of the '387 patent are described as known herbicides of tne type disclosed, e.g., in the above-mentioned '945 and '752 patents, including propachioi:. 1S654S — 3— AG-i 22 J The above '584 patent contains some herbicidal data relative to the above-mentioned compound having a chemical configuration most closely related to the invention compounds, and some data are presented for other homologous ana anaioyous compounds less-closely related in chemical structure. More particularly, these most relevant references, while disclosing herbicidal activity on a variety of weeds, do not disclose any data for any compounds which are shown to additionally and/or simultaneously control the hard-to-kill annual weeds such as Texas panicum, itchgrass (raoulgrass), wild proso miliet, alexandergrass, red rice, shattercane and seedling johnsongrass, while also controlling or suppressing a broad spectrum of other noxious perennial ana annual weeds, e.g, yellow nutsedge, smartweed, lambsquarter, pigweed, foxtails, large crabgrass and barnyardgrass.

A highly useful and desirable property of herbicides is the ability to maintain weed control over an extended period of time, the longer the better during each crop season. With many prior art herbicides, weed control is adequate only for 2 or 3 weeks, or, in some superior cases, perhaps up to 4-6 weeks, before the chemical loses its effective phytotoxic properties. Accordingly, one disaavantage of most prior art herbicides is their relatively short soil longevity.

Another disadvantage of some prior art herbicides, somewhat related to soil longevity under normal weather conditions, is tneir susceptibility to leaching into the soii, hence, the lack of weed control persistence under heavy rainfall which inactivates many nerbic ides.

A further disadvantage of many prior art herbicides is limitation of their use in specified types of soil, i.e., while some herbicides are effective in soils having small amounts of organic matter, they are ineffective in other sons higti in 1965 aG-122-> organic matter or vice-vtrsa. It is, therefore, advantageous that a herbiciae be useful in all types of soil ranging from light organic to heavy clay and -ruuek.

Yet another disadvantage of many prior art herbicides is the limitation to a particular effective mode of application, i.e., as a preemergence surface application or as a preplant soii incorporation mode of application. It is highly desirable to be able to apply a herbicide in any mode of application, whether by surface application or preplant incorporated.

And, finally, a diisadvantage in seme herbicides is the necessity to adopt and maintain special handling procedures due to the toxic nature thereof. Hence, a further desideratum is that a herbicide be safe to handle.

It is, therefore, an object of .lis invention to provide a group of herbicidal compounds which overcome tne above-mentioned disadvantages of the prior art and provide a multiplicity of advantages in a single group of herbicides.

It is an object of this invention to provide herbicides which selectively control hard-to-kill annual weeds such as Texas panicum, raoulgrass, wild proso millet, alexandergrass, red rice, shattercane ana seedling johnsongrass, while also controlling or suppressing a broad spectrum of less-resistant perennial and annual weeds such as mentionec above, while maintaining crop safety in a plurality of crops including soybeans, cotton, peanuts, rape, oush beans, alfalfa and/or vegetable crops.

It is a further object of this invention to provide herbicidal effectiveness in the soil for extended periods ranging up to at least 12 weeks.

Yet another object of this invention is to provide herbicides which resist leaching and dilution due to high moisture conditions, e.g., as heavy rainfall. 19 6545 -5- AG-i 2 2J Still another object of this invention is the provision of herbicides wnich are effective over a wiae range of soils, e.g., ranging from 1iyht-meuium organic to heavy clay and muck.

Another advantage of the herbicides of this invention is the flexibility available in the mode of application, i.e., by preemergence surface application and by preplant soil incorporation.

Finally, it is an advantage of the herbicides 10 of this invention that they are safe and require no special handling procedures.

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

Summary of the Invention The present invention relates to herbicidally active compounds, herbicidal compositions containing these compounds as active ingredients and herbicidal method of use of said compositions in various crops. 2q It has now been found that a selective group of 2-haloacetanilides characterized by specific combinations of alkyl radicals on the anilide nitrogen atom and in one ortho position and specific alkoxy radicals in the other ortho position possess 25 unexpectedly superior ana outstanding herbicidal properties vis-a-vis prior art herbicides, including the rnost-closely-related compounds of the most relevant prior art.

A primary feature of the herbicidal 30 compositions of this invention is their ability to control a wide spectrum of weeas, including weeas controllable by current herbicides and, additionally, a plurality of weeds which, inci iv iduaiiy and/or collectively, have heretofore escaped control by a 35 single class of known herbicides, while maintaining crop safety with respect to a plurality of crops including, particularly, soybeans, cotuon, peanuts, rape, bush beans (snap beans), alfalfa and others as 196545 AG--L 2. '2. well. Whiie prior art herbicides are useful for controlling a variety of weeds, including on occasion certain resistant weeas, the unique herbicides of this invention have been found to be capable of controlling 5 or greatly suppressing a plurality of resistant weeds, most notably annual weeds, such as Texas panicum, itchgrass, wild proso millet (Panicum miliaceum), alexandergrass, red rice, shattercane and seedling johnsongrass, while controlling and/or suppressing 10 other less-resistant perennial and annual weeds- The compounds of this invention are characterized by the formula II C1CH-C R \ / N R wherein R is methyl or ethyl; R^ is a C-^_g alkyl radical, preferably alkyls; R2 is methyl, ethyl or t-butyl, preferably methyl, and is hydrogen or methyl in a meta position, 20 preferably hydrogen; provided that: When R is ethyi, R^ is n-butyl, R2 is methyl and R^ is hydrogen; When R^ is methyl, R ana R£ are a.lso methyl 25 and Rj^ is isopropyl or n-butyl; When R^ is hydrogen ana R and are both methyl, ri is etny1' n-propyi, isopropyl, n-butyl, isobutyi, sec-butyl, n-pentyi, isopentyl, 2-methylbutyi, 1-methylpentyi, 2-methylpentyl or 30 1,3-dimethyibuty!; 7 19 G 5 4 5 When 1*2 is ethyl, R is methyl and R^ is isopropyl and When R2 is t-butyl, R and R^ are both methyl. Preferred species of this invention are as follows: N-methyl-2'-isopentyloxy-6'-methyl-2-ch.loro-acetanilide.

N-methyl-2'-n-propoxy-6'-methyl-2-chloro-acetanilide.

N-methyl-2'-n-butoxy-61-methyl-2-chloroacet-anilide.

N-methyl-21-sec-butoxy-61-methyl-2-chloro-acetanilide.

N - ethyl-2'-n-butoxy-61-methyl-2-chloroacet-anilide.

N-methyl-21-isopropoxy-61-methyl-2-chloro-acetanilide.

N-methyl-21-isobutoxy-61-methyl-2-chloroacet-anilide.

N-methyl-21-isopropoxy-6'-ethyl-2-chloroacet-anilide.

The utility of the compounds of this invention as the active ingredient in herbicidal compositions formulated therewith and the method of use thereof will be described below.

Detailed Description of the Invention The compounds of this invention may be made in a variety of ways. For example, these compounds may be prepared by a process involving the N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent under basic conditions. The N-alkylation process is described in Examples 1 and 2 herein. _ PATEN7" UJUM983 RECEIw / 19Go45 AG-1223 Example 1 This example describes the preparation of one preferred species, N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide. In this example dimethyl sulfate is used as the alkylating agent to prepare the N-alkyl-2-chloroacetanilide from the corresponding sec-amide anion. 2'-n-butoxy-61-methyl-2-chloroacetanilide, 4.9 gms (0.02 mol), dimethyl sulfate, 2.6 gms (0.02 mol) and 2.0 gms of triethyl benzyl ammonium bromide were mixed in 250 ml of CI^CI^ under cooling. Fifty (50) ml of 50% NaOH were then added all at once at 15°C and the mixture stirred for two hours. Water (100 ml) was added and the resultant layers separated. The organic layer was washed with water, dried over MgSO^ and evaporated by Kugelrohr. A clear liquid, b.p. 135°C at 0.07 mm Hg was obtained in 78% yield (4.2 gms) and recrystallized upon standing to a colorless solid m.p. 41-42.5°C.

Anal. Calc'd for C14H2QCIN02 (%): C, 62.33; H, 7.47; Cl, 13.14.

Found: C, 62.34; H, 7.49; Cl, 13.16.

The product was identified as N-methyl-21-n-butoxy6'-methyl-2-chloroacetanilide.

Example 2 To a chilled (15°C) mixture of 2'-n-butoxy-6'-methyl-2-chloroacetanilide, 5.6 g (0.022 mol), diethyl sulfate, 4.0 g (0.024 mol), and 2.2 g of triethyl benzyl ammonium bromide in 250 ml of methylene chloride, was added all at once 50 ml of 50% NaOH and the mixture was stirred for 5.0 minutes. Water (150 ml) was added, and the resulting layers separated: the organic layer was washed with water, dried with MgSO^, then evaporated by Kugelrohr to give 4.lg |(66% yield) of a clear liquid, b.p. 114°C at 0.05 mm Hg. 196545 —9~ AG—l2^J Anal. Caic'd for C^^H22C^N02 ^' 63.48; H, 7.81; Cl, 12.49.

Found: C, 63.50; H, 7.85; Cl, 12.48.

The product was identified as N-ethyl-2 1 -n-butoxy-6 1 -methyl-2-chloroacetanilide.

Examples 3-19 Following substantially the same procedures, quantities of reactants and general conditions 10 described in Examples 1 and 2, but substituting the appropriate sec-anilide to obtain the corresponding N-alkylated end product, other N-methyl-2-haloacetani-lides according to the above formula were prepared; these compounds are identified in Table X.

TABLE I Example Empirical No. Compound Formula 3 N-methyl-21-isopentoxy-6'-methyl-2-chloroacet-anilide 4 N-methyl-2'-n-propoxy-61-methyl-2-chloroacet-anilide N-methyl-2'-sec-butoxy-6'-methyl-2-chloroacet-anilide 6 N-methyl-2'-isopropoxy-61-methyl-2-chloroacet-anilide 7 N-methyl-21-isopropoxy-6'-ethyl-2-chloroacet-anilide 8 N-methyl-2'-isobutoxy-6'-methyl-2-chloroacet-anilide 9 N-methyl-2'-methoxy-61-t-butyl-2-chloroacet-anilide N-methyl-2'-ethoxy- 6'-methyl-2-chloroacet-anilide B.P. °C Analysis (mm Hg) Element Calculated Found 120 C 63.48 63.38 (0.05) H 7.81 7.80 Cl 12.49 12.44 130 C 61.05 60.88 (0.15) H 7.09 7.12 Cl 13.86 13.70 C 62.33 62.16 H 7.47 7.50 Cl 13.14 13.10 127 C 61.05 61.05 (0.03) H 7.09 7.09 Cl 13.86 13.83 105 C 62 .33 62.40 (0.01) H 7.47 7.52 Cl 13.14 13.03 115 C 62.33 62.32 (0.03) H 7.47 7.49 Cl 13.14 13.12 99-100 C 62.33 62.25 (m.p.) H 7.47 7.51 Cl 13.14 13.14 57-58 C 59.63 59.63 (m.p.) H 6.67 6.71 Cl 14 .67 14.67 c15H22C1N02 C13H18C1N02 C14H20C1NO2 c13H18C1N02 C14H20C1NO2 C14H20C1NO2 C14H20C1NO2 c12H16C1N02 <1 TABLE I (Cont'd) Example No.

Compound Empirical Formula B.P. °C (mm Hg) Element Analysis Calculated Found 11 N-methyl-2(1-methyl- pentoxy)-6'-methyl-2-chloroacetanilide C, .ClN0o 16 24 2 120 (0.08) c h Cl 64 .53 8 .12 11.90 64 .42 8 .15 11.89 12 N-methyl-21-n-pentoxy-6'-methyl-2-chloroacet-anilide c15h22cino2 125 (0.12) c h Cl 63.48 7.81 12 .49 63.36 7.81 12.50 . J. P. & s.>r H mathyl 2' n pi'opoitymothyl C« .ii»,,ClM0,v 120 160 n I .1 _n 11. I LS—2\J ± / n n C n -62.33 -61.59- .tM.. n J. P. & \io ¥7 n Or*—Hie Lhyj:—2 anilide -ihluiuat:eL~ N-methyl-2'-isopropoxy-5',6' -dimethyl-2-chloroacet-anilide N-methyl-2 *-n-butoxy-3', 6 ' -dimethyl-2-chloroacet-anilide -h N-methyl-2 L-butoxy- ',6 1-dimetnyl-2-chloroace t- anilide N-methyl-2'-(2-methyl-pentoxy)-6'-methyl-2-chloroacetanilide N-methyl-2'-(2-methyl-butoxy)-61-methyl-2-chlor6acetanilide C14H2 0C1N°2 C15H22C1N02 C-, ,-H„0ClN00 lb 22 2 C16H24C1N02 (:15H22C1N02 (0.05 0.1) 121 (0.01) 108 (0.07) 46-47 (m.p. ) 116 (0.03) 120 (0.06) -U- 7 .47 7 .51 C h Cl C h Cl C h Cl C h Cl C h Cl .19 62.33 7.47 13.14 63.48 7.81 12.49 63 .48 7 .81 12.49 64 .53 8 .12 11.90 63.48 7 .81 12.49 62.65 6.84 13.17 63.54 7.80 12.48 63.56 7.82 12 .52 64 .59 8.11 11.96 63.53 7 .85 12.45 • • TABLE I at Example No.

, J. P. & S.

If Compound N-methyl-21 -(1,3-dimethyl-butoxy-61-methyl-2-chloro-acetanilide Empirical Formula C16H23C1N02 (Cont'd) B.P. °C Analysis ys (mm Hg) Element Calculated Found 128 C 64.53 64.49 (0.15) H 8.12 8.14 Cl 11.90 11.89 > 0 1 1—1 fo to OJ Cn 196545 -13- AG-122J The seconoary anixiues usee as starting materials in the above N-alkyiation process are prepared by known methods, e.g., naioacetylation of the corresponding aniline. For example, the starting 5 sec-anilide used in Example 1 was prepared as follows: 2-n-butoxy-6-mechylaniline, 27.4 g (0.0153 mol), in 250 mi of methylene chloride was stirred vigorously with a 10% sodium hydroxide solution (0.25 mol)) while a solution of chioroacetyl chloride, 17.4 10 gm (0.0154 mol), in methylene chloride was added over minutes keeping the temperature between 15-25°C with external cooling. The reaction mixture was stirred for a further 60 minutes. After the addition was complete, the layers separated and the methylene chloride layer 15 washed with water, dried and evaporated in vacuo to obtain 28.3 g of a white solid, m.p. 127-128°c.

Anal. Caic'd for C^-H^CINC^ (%): C, 61.05; H, 7.09; Cl, 13.86.

Found: C, 61.04; H, 7.0b; 20 Cl, 13.86.

The product was identified as 2'-n-butoxy-b'-methyl-2-chioroacetaniliae. c The secondary anilides used as starting materials in Examples 3-yS were prepared in a similar 25 manner.

The primary amines used to prepare the above-mentioned secondary anilides may be prepared by known means, e.g., by catalytic reduction of the corresponding 2-alkoxy-6-alkyl-nitrobenzene in etnanol 30 using platinum oxide catalyst.

As noted above, the compounds of this invention have been found to be effective as herbicides, particularly as pre-emergence herbicides, although post-emergence activity has aiso been snown. 35 The pre-emergence tests referred to herein include both greenhouse ana field tests. In the greennouse tests, the herbicide is applied either as a surface application after planting the seeds or vegetative 196545 -14- AG—122_> propagules or by incorporation into a quantity of soil to be applied as a cover layer over the test seeds in pre-seeded test containers. In tne field tests, the herbicide is pre-plant incorporated ("P.P.I.") into the 5 soil, i.e., the herbicide is applied to the surface of the soil, then incorporated therein by mixing means followed by planting of the crop seeds.

The surface application test method used in the greenhouse is performed as follows: Containers, e.g. , aluminum pans typically 9.5" x 5.25" x 2.75" (24.13 cm x 13.34 cm x 6. 9 9 cm) or plastic pots 3.75" x 3.75" x 3" (9.53 cm x 9.53 cm x 7.62 cm) having drain holes in the bottom, are level-filled with Ray silt loam soil then compacted to X5 a level 0.5 inch (1.27 cm) from tne top of the pots.

The pots are then seeded with piant species to be tested, then covered with a 0.5 inch layer of the test soil. The herbicide is then applied to the surface of the soil with a belt sprayer at 20 gal/A, 30 psi (187 2 1/ha, 2.11 kg/cm ). Each pot receives 0.25 inch (0.64 cm) water as overhead irrigation and the pots are then placed on greenhouse benches for subsequent sub-irrigation as neeoea. As an alternative proceaure, the overhead irrigation may be omitted. Observations 25 of herbicidal effects are made about three weeks after-treatment.

The herbicide treatment by soil incorporation used in greenhouse tests are as follows: A good graae of top soil is piacea in 30 aluminum pans and compacted to a depth of three-eights to one-half.inch from the top of the pan. On the top of the soil is placed a predetermined number of seeds or vegetative propagules of various plant species. The soil required to level fill the pans after seeding or 35 adding vegetative propagules is weigheo into a pan.

The soil and a known amount of the active ingredient applied in a solvent or as a wettabie powocr suspension are thoroughly mixed, and used to cover the prepared 19 6545 AG— i 2 3 pans. After treatment, the pans are given an initial overhead irrigation of water, equivalent to one-fourth inch (0.64 cm) rainfall, then watered by subirrigation as needed to give adequate moisture for germination and growtn. As an alternative procedure, the overhead irrigation may be omitted. Observations are made about 2-3 weeks after seeding and treating.

Tables II and III summarize results of tests conducted to determine the pre-emergence herbicidal activity of the compounds of this invention; in these tests, the herbicides were applied by soil incorporation and sub-irrigation watering only; a dash (-) means that the indicated plant was not tested. 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 1 2 3 0-24 25-4 9 50-74 75-iUO The plant species utilized in one set of tests, the data for which are shown in Table II, are identified by letter in accordance with the following legend: Canada Thistle E Lambsquarters I Johnsongrass B Cockiebur C Velvetleaf F Smartweed J G Yellow Nutsedge K Downy Brorne Barnyardgrass D Morninggiory Id Quackgrass 19 65 40 Table II Pre-Emergenr G— X 2 2 - I. P. & s.

M? J. P. & s. "26- 7-?? Compound of Example No. kg/h ri B c D E F G H i J K 1 11. 2 3 3 3 3 3 3 3 3 3 3 3 . fa 3 2 2 3 3 3 3 3 3 3 3 2 11. 2 J 1 1 2 3 3 — 3 3 3 3 .6 3 Q 1 I 3 3 — 3 1 3 3 3 11. 2 3 2 3 3 3 3 3 3 3 3 3 .6 3 1 3 2 3 3 3 3 2 3 3 4 11. 2 3 2 3 3 3 3 3 3 3 3 3 . 6 2 1 3 2 3 3 3 3 j 3 3 11.2 -v J 2 j 3 3 3 3 3 3 3 3 .6 3 2 3 3 J 3 3 3 3 3 3 6 11. 2 3 2 2 3 3 3 3 3 3 3 3 . 6 "i J 2 2 3 3 3 3 3 2 3 3 7 11. 2 3 3 3 3 "i J 3 3 3 3 3 3 .6 J 1 2 3 3 3 3 3 3 3 j 8 11.2 3 2 3 3 3 3 3 3 1 3 3 . 6 3 2 2 2 3 3 3 3 3 3 3 9 11. 2 3 0 3 3 3 3 3 3 3 3 3 .6 J 0 2 3 3 3 -5 3 3 3 3 1. 12 2 0 2 3 3 I 2 3 1 3 J 11. 2 2 2 3 3 3 ■-> 3 -i 3 3 3 J . 6 3 1 3 2 3 2 2 3 2 3 3 11 11.2 3 2 2 3 3 3 3 3 3 J 3 . 6 2 2 2 2 3 2 3 3 3 3 3 12 11. 2 3 2 2 3 3 3 j 3 3 3 j . 6 i i -> 3 1 1 3 3 2 3 3 2 3 3 -L O Hi il C £ 1 - <- 1 - —dr- .J •n J I —e— *3 X ± X _> J j "S~ n 11. 2 3 1 3 3 3 O 3 3 3 3 J . fa (j 0 2 3 3 2 j 3 1 3 3 li. 2 1 l 2 3 3 3 3 3 J J 3 .6 2 0 1 2 2 I 3 2 0 3 J li. 2 3 1 i 2 3 3 J J 3 J J .6 2 0 0 0 3 2 "j 3 3 3 3 196545 —2. 7 — AG—I<^2j Table II (Cont'u) Pre-Emergent Plant Species Compound of Example No. kg/ ha A B C D E F G H I J K yjih 11. 2 3 1 1 0 2 3 3 3 3 3 3 . o 3 0 2 2 3 2 3 3 3 3 3 11. 2 3 2 3 3 3 3 3 3 3 3 3 \< .6 3 2 2 3 3 j 3 3 3 3 11.2 3 1 2 2 3 3 3 3 2 3 3 . 6 3 0 2 2 3 3 3 3 1 3 3 The compounds were further tested by utiii zing the above procedure on the following plant species: L Soybean R Hemp Sesbania M Sugarbeet E Lambsquarters N Wheat F Smartweea 0 Rice C Velvetleaf P Sorghum J Downy Brome B Cocklebur S Panicum Spp.

Q Wild Buckwheat K Barnyaragrass D Morningglory T Crabgrass The results are summarized in Table III. 1&&S45 Compound of Table III Pre-Emergent Plant Species Example No. k y / i i a L M N 0 P B Q D R E F c J S K iTl X 1 .6 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1.12 2 3 2 3 3 1 2 2 3 3 3 _L 3 n J J 3 0. 28 0 2 1 3 "3 J 1 2 1 2 j -> J 0 3 3 3 3 0. 0 6 0 1 1 1 3 1 2 0 1 2 2 •o 3 3 3 3 0.01 0 0 0 0 0 0 1 0 1 1 i 0 0 1 3 3 0.006 0 0 0 0 0 - 0 0 1 1 0 0 0 2 3 2 2 .6 1 2 3 3 3 1 1 2 3 3 3 1 3 3 3 _ 1.12 0 2 3 3 3 0 1 0 3 3 3 0 3 3 3 - 0.2 a 0 1 2 2 2 0 0 0 3 1 1 0 3 3 3 - 0.0 6 0 0 0 2 0 0 0 0 3 0 0 0 1 1 3 - 0.01 0 0 0 1 0 0 0 0 1 0 0 0 0 0 1 - 3 .6 2 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1.12 1 3 3 3 3 2 2 0 2 3 3 2 3 3 3 3 0. 28 1 2 2 3 3 0 1 0 0 3 3 0 3 3 3 3 0.06 0 1 1 1 0 0 0 0 0 3 1 0 0 -■> j 3 3 0.01 0 0 0 0 3 0 1 0 0 0 0 0 2 3 "i J 3 0.006 0 0 0 0 0 0 0 0 0 1 1 0 0 0 1 1 4 .6 2 3 3 3 3 3 0 3 3 3 3 2 3 3 3 J 1.12 0 2 2 3 3 1 3 2 3 3 2 2 3 3 3 3 0. 2-8 0 2 3 3 3 - 1 3 3 3 1 1 3 3 3 3 0.06 0 1 1 1 3 - 0 0 1 0 0 0 3 3 3 3 0.01 0 0 0 0 0 0 0 - 0 0 0 0 0 X 2 3 .6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1.12 2 3 3 3 3 1 3 3 3 3 3 2 3 3 3 .j 0. 28 0 2 2 2 3 1 1 1 3 3 3 2 •-> 3 3 3 0.06 0 1 1 2 2 0 0 0 3 3 1 2 3 3 3 0.01 0 0 0 0 0 0 0 0 1 1 1 0 0 1 3 3 O.OOo 0 1 0 0 0 0 0 0 2 1 1 0 0 0 1 2 6 . 6 3 3 3 3 3 2 3 2 3 3 3 3 3 3 3 1. 12 2 3 O 3 3 1 2 2 2 3 3 2 3 3 3 - 0.28 0 2 1 3 3 0 1 1 2 3 2 2 3 3 3 - U. 06 0 1 0 0 0 0 0 0 1 3 1 0 j 3 3 — 0.01 0 0 0 1 0 0 1 0 1 1 0 0 2 0 3 - 7 .6 1 3 3 3 3 1 3 3 J 3 3 3 3 3 3 J 1.12 0 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3 0. 2b 0 2 2 2 0 2 2 2 3 2 1 3 3 3 3 0.06 0 2 1 1 1 1 0 3 2 2 1 1 1 3 3 3 0.01 1 1 0 1 0 0 0 1 1 0 U 0 1 0 2 j 0.006 0 0 0 0 0 0 0 i 2 0 0 0 1 0 2 2 196545 Compound of .. J. P. & S. *b~I-*! MA.

P. 8s. S.

Mol .

Table III (Cont'd) Pre-Emergent iiG—- Plant Species Example No. kg/ ha L 14 N Q P B Q D R E F C J S K m X 8 .6 2 3 3 3 3 1 2 3 3 3 3 3 3 3 3 3 1.12 0 2 2 3 -i 0 2 2 2 3 2 1 —i J 3 3 3 0.28 0 2 2 3 3 0 1 0 2 3 2 0 j 3 3 3 0.06 0 1 0 2 3 0 1 0 0 1 0 0 1 2 3 3 0. 01 0 1 0 0 0 0 0 0 1 3 2 0 0 1 3 3 9 .6 3 3 3 3 3 2 3 J> 3 3 3 3 3 3 3 3 1.12 1 2 3 3 3 1 2 2 2 3 1 1 3 3 3 3 0.28 0 1 2 n 2 0 1 3 2 3 2 1 2 2 3 3 0.06 0 1 2 1 1 0 0 0 2 0 2 0 0 2 3 3 0. 01 0 1 2 0 0 0 0 0 2 1 1 0 0 0 2 3 .6 2 2 3 3 3 0 3 3 3 3 2 3 3 3 3 3 1.12 0 2 2 3 3 1 1 2 3 3 2 2 3 3 3 3 0.28 0 2 1 3 3 0 2 2 2 3 0 2 3 3 3 3 0.06 0 1 0 1 2 0 0 0 3 2 0 2 3 3 3 3 0. 01 0 1 0 0 0 0 0 0 1 0 0 1 0 0 0 3 11 .6 1 3 3 3 3 1 3 3 3 3 3 1 3 3 3 3 1.12 0 1 2 3 3 0 2 2 2 3 3 0 3 3 3 3 0. 28 0 1 2 3 3 - 0 1 1 3 3 0 3 3 3 j 0.06 0 0 1 2 1 0 0 0 2 3 2 0 2 2 3 3 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 l 3 12 .6 2 2 3 3 3 1 3 1 o J 3 3 1 3 3 3 3 1. 12 0 2 3 3 3 1 3 2 3 3 3 1 3 3 'i 3 0. 28 0 2 3 3 3 0 0 0 1 3 2 0 3 3 3 3 0.06 0 0 2 3 3 0 2 0 0 1 2 0 3 3 3 3 0.01 0 0 0 0 0 U 0 0 2 0 0 0 1 0 3 3 ■4.3r <- ( 1 . 1 . "5 .. _ -> Zi • 0 ± z.

J 4lL •j j" *s j j -J- 1.12 0 2 2 3 3 1 2 2^ j 1 3 3 3 - 0.28 0 2 2 j. 1 2 3 2 0 2 3 3 — 0. 06 n 1 - j \ 0 n 0 0 0 1 (\ , 2 n 1 0 0 3 3 - i _ — U u ■j u U u U 0 u U 1 -t7- —±~ 1 u 1 .6 3 3 j •"1 3 1 3 3 3 3 3 2 3 3 3 3 1. 12 2 j 2 3 3 u o 3 J 3 3 2 3 3 3 j 0.28 2 2 2 2 3 0 2 3 2 2 2 1 3 3 3 3 0. 06 0 2 ■\ X 2 1 0 j. 2 1 2 2 0 2 2 3 3 0. 01 0 1 1 1 0 0 1 1 1 1 0 0 0 0 2 3 1 / / 0. 006 0 1 0 1 0 0 1 1 1 1 0 0 0 0 1 3 'T 4r5- ' .6 2 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 1. i2 U L. 3 3 3 1 2 1 -L 3 2 0 3 3 3 3 0.28 0 1 1 1 1 0 1 0 0 1 1 0 3 3 3 0.06 u 1 0 0 0 0 0 u U 1 u 0 0 2 3 3 0.01 0 0 0 0 0 0 0 0 0 1 1 0 0 0 2 2 196545 AG-1223 Table III (Cont'd) Pre-Emergent \.,J. P. & S.

UM/Vl .

Compound of Plant species Example No, kg/ha L M N 0 P a Q D R E F C J S K T .6 1 3 3 3 3 l 2 2 3 3 3 1 3 3 3 __ 1.12 0 2 2 j 3 0 2 1 2 2 • > O 0 3 3 3 - 0.28 0 2 1 3 3 0 0 0 1 3 3 0 2 3 3 - 0.06 0 1 0 1 0 0 0 0 3 1 0 0 3 2 3 - / 0.01 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 — .6 0 3 3 3 3 0 1 1 3 3 3 1 3 3 3 — 1.12 0 2 2 3 3 0 1 0 2 2 2 0 3 3 3 - 0.28 0 2 1 3 2 0 0 0 1 0 1 0 3 3 3 — 0.06 0 0 0 r 0 0 0 0 1 1 0 0 1 1 3 - 0.01 0 0 0 0 0 - 0 0 0 0 0 0 G 0 1 - .6 3 3 3 3 3 3 3 3 3 3 3 2 3 3 3 j 1.12 0 3 3 3 3 0 3 3 3 3 j 2 3 3 3 3 0.28 0 2 2 3 3 0 2 0 2 3 2 1 3 3 3 3 0.06 0 2 0 0 2 0 2 0 0 2 3 0 3 -) -> 3 0.01 0 2 0 0 0 0 0 0 0 0 — 0 0 0 3 3 196545 ~ 21~ hG-^^J The herbiciues of this invention have been found to possess unexpectedly superior properties as pre-emergence herbicides, most particularly in the selective control of the hard-to-kill annual weeds, Texas panicum, seedling johnsongrass, shattercane, alexandergrass, wild proso millet, red rice and itchgrass, while also controlling or suppressing many other less-resistant perennial and annual weeds.

Selective control and incre^jid suppression of the above-mentioned weeds with the invention herbicides have been found in a variety of crops including soybeans, cotton, peanuts, rape and snap beans (bush beans). Selectivity has been shown in some tests at varying rates of application in sugarbeets ana garden peas; however, some crops, particularly grass crops, are usually less tolerant to tne invention herbicides than are the foregoing crops.

In order to illustrate the unexpectedly superior properties of the compounds of this invention both on an absolute basis and on a relative basis, comparative tests were conducteu in the greenhouse with compounds of the prior art most closely related in chemical structure to the invention compounds. The prior art compounds are identified as follows: A. N-tert-butyi-2-raethoxy-2-ciiIoroacetanil ide. (Example 13, U.S. Patent No. 3,268,5b4) B. 2'-t-butyl-6'-methoxy-2-chloroacetanilide.

(Example 67, U.S. Patent No. 3,442,945) C. N-isopropyl-2-chioroacetaniiiae (common name "propachlor"). U.S. Patent No. 2,863,752 (Re Patent No. 26,961); Propachlor is referenced in the above-mentioned U.S. Patent Nos. 3,773,492 and 4,i52,137 and is the active ingredient in the commercial herbiciue "Ramrod®", a registered traaemark of Monsanto Company.

In the discussion of data beiow, reference is 1965 — 2.2™ iiCj*—x made to herbicide appl icacion rates symbol izeci as "GR-^s" and "GR85"; these rates are given in kilograms per hectare (kg/ha) which are convertible into pounds per acre (lbs/A) by dividing the kg/ha rate by 1.12. ^15 "e£ines the maximum rate of herbicide required to produce 15% or less crop injury, and GR^ defines the minimum rate required to achieve 85% inhibition of weeds. The GR-^ and GRg^ rates are used as a measure of potential commercial performance, it being 10 understood, of course, that suitable commercial herbicides may exhibit greater or lesser plant injuries within reasonable limits.

A further guide to the effectiveness of a chemical as a selective herbicide is the "selectivity 15 factor" ("SF") for a herbicide in given crops and weeds. The selectivity factor is a measure of the relative degree of crop safety and weed injury and is expressed in terms of the GR^/GRg^ ratio, i.e., the GRis rate for the crop divided by the GR^ rate for the 20 weed, both rates in kg/ha (lb/A). In the tables below, selectivity factors are shown in parenthesis following the GRg^ rate for each weed; the symbol "NS" indicates "non-selective." Marginal or questionable selectivity is indicated by a dash (-); a blank space means that 25 the indicated plant was not in tne test or that the plant failed to germinate.

Since crop tolerance and weea control are inter-related, a brief discussion of this relationship in terms of selectivity factors is meaningful. In 30 general, it is desirable that crop safety factors, i.e., herbicide tolerance values, be nigh, since higher concentrations of herbicide are frequently desired for one reason or another. Conversely, ic is desirable that weed control rates be smail, i.e.,- the herbicide 35 possesses high unit activity, for economical ana possibly ecological reasons. However, small rates of application of a herbicide may not be adequate to control certain weeds and a larger rate may be _23- ULfL* required. Hence the best herbicides are those which control the greatest number of weeds with the least amount of herbicide and provide the greatest degree of crop safety, i.e., crop tolerance. Accordingly, use is 5 made of "selectivity factors" (defined above) to quantify the relationship between crop safety and weea control. With reference to the selectivity factors listed in the tables, the higher the numerical value, the greater selectivity of the herbicide for weed 10 control in a given crop.

In a first comparative test, greenhouse preemergence herbicidal activity data are presented in Table IV comparing the relative efficacy of the compound of Example 1, representative compounds of this 15 invention, with relevant compounds of the prior art, viz., Compounds A, B and C, as selective herbicides against particular weeds commonly associated with soybeans. The test data in Table IV for all compounds was obtained under identical test conditions, i.e., 20 soil incorporation with an initial overhead irrigation; the data represent the averages of two replicate runs for each compound; two different samples of the compound of Example 1 were usee and the data in the table represent the average from both test samples. 25 The weeds used in the tests herein have the following abbreviations in the tables: Texas panicum (TP), seedling joimsongrass (SJG), shattercane (SC), alexandergrass (AG), wild proso millet (WPM), fall panicum (FP), red rice (RR) and itchgrass (IG).

TABLE IV GR-j^ Rate gr85 Oom- (Kg/Ha) _ (K2/^) _ pound Soybean TP SJG SC _AG WEW FP RR IG A >1.12 >1.12(-) >1.12(-) >1.12 {-) >1.12(-) >1.12(-) >1.12(-) >1.12(-) >1.12(-) B >1.12 >1.12(-) >1.12(-) >1.12(-) >1.12(-) >1.12(-) >1.12(-) >1.12<-) >1.12(-) C >1.12 >1.12(-) >1.12(-) >1.12(-) >1.12(-) >1.12(-) 0.12(>9.3) >1.12(-) >1.12(-) Ex. 1 0.71 0.11(6.5) <0.07(>10.2)<0.07(>10.2) 0.07(10.2) 0.14(5.1) <0.07(>10.2) 0.18(3.9) 0.07(10.2) i NJ 4> i Cn 19654a -25- AG-X22J Reference to the data in Table IV will snow that with respect to weed control, none of the prior art compounds exhibited positive selective weec control against any weed in soybeans at the maximum rate of application, i.e., 1.12 kg/ha, but for the sole exception of Compound C against fali panicum, and even there, the selectivity factor was one-foio iess than that for the compound of Example 1. In marked contrast, the compound of Example 1 selectively controlled every weed in the test at extremely low rates of application, while maintaining soybean safety up to 0.71 kg/ha. Of particular note is the fact that the compound of Example 1 controlled seedling johnsongrass, shattercane, alexandergrass, fall panicum and itchgrass; at 0.07 kg/ha (the minimum rate used) or less and also controlled the remaining weeds, i.e., Texas panicum, wild proso millet ana red rice at rates of only 0.10, 0.14 and 0.18 kg/ha, respectively.

Additional tests were conducted in the greenhouse in order to compare the relative herbicidal efficacy of prior art compgunas A-C with the compounds of Examples 1, 3-5 and 8->T, representative of the invention compounds. The tests were conducted by soil incorporation of the herbicide at application rates within the range of from 0.07 to 1.12 kg/ha (0.0625-1.0 lb/A) ana an initial overhead irrigation followed by subsequent subirrigation watering as needeo. Observations were made 19 days after treatment. The data from the additional tests are shown in Table V; the names of the weeds are abbreviated as in Table IV ana selectivity factors are shown in parentheses after the GRgcj rates for each weed.

TABLE V GR^ Rate GRg5 Rate Compound Soybean TP SJG SC AG WPM FP RR A >1.12 >1.12(-) >1.12 (-) >1.12(-) >1.12(-) >1.12(-) >1.12 (-) >1.12 (-) B >1.12 >1.12(~) >1.12(-) >1.12(-) 1.00(>1.0) >1.12(-) 1.00(>1.0) >1.12 (-) C >1.12. 1.12(>1.0) >1.12 (-) >1.12(-) 1.12 (>1.0) >1.12(-) 0.28(>4.0) 1.12 (>1.0) Ex. 1 >1.12 <0.07(>16.0) <0.07(>16.0) <0.07(>16.0) 0.07(>16.0) <0.14(>8.0) <0.07(>16.0) 0.38(>3.0) Ex. 3 >1.12 0.07(>16.0) <0.07(>16.0) 0.14(>8.0) 0.07(>16.0) 0.14 (>8.0) <0.07(>16.0) 0.25 (>4.5) Ex. 4 >1.12 0.09(>12.0) <0.07 (>16.0) 0.07(>16.0) 0.07(>16.0) 0.28(>4.0) <0.07(>16.0) 0.13 (>8.6) Ex. >1.12 0.07(>16.0) <0.07 (>16.0) <0.07 (>16.0) <0.07 (>16.0) 0.14(>8.0) <0.07(>16.0) 0.14(>8.0) Ex. 8 >1.12 0.14(>8.0) 0.07(>16.0) 0.09(>12.0) 0.14(>8.0) 0.28(>4.0) <0.07(>16.0) 1.12 (>1.0) Ex. 9 1.12 0.28(4.0) 0.14(8.0) 0.50(2.2) 0.28(4.0) 1.12(1.0) <0.07(16.0) >1.12 (NS) EX. >1.12 0.56(>2.0) 0.07(>16.0) 0.28(>4.0) 0.09(>12.0) 0.28(>4.0) <0.07(>16.0) 0.50 (>2.2) Ex. 11 >1.12 0.28(>4.0) <0.07(>16.0) 0.28(>4.0) 0.09(>12.0) 0.56(>2.0) <0.07(>16.0) 0.56 (>2.0) .J. P. & s.Ex*. 12 ■±3— >1.12 1-1.12 0.28(>4.0) ■ 0.28(4.0) 0.07(>16.0) —0.14(8.0) 0.20(>5.6) &ra0(4.0) - 0.14 (>8.0) 0.28(>4.0) —0^-28-{4T9)— <0.07(>16.0) <0.07(>1C.0) 0.48 (>2.3) —0.50(2.2) ^ as. i N> CT> I Ex. A4^ 0.56 0.14(4.0) <0.07(8.0) 0.14(4.0) 0.28(2.0) 0.56(1.0) <0.07(8.0) 0.07(8.0) to. 0 o- a _ o w o iif uQjl Ex. 25~ >1.12 0.56 (>2.0) 0.19(>5.9) 1.12 (>1.0) 0.56(>2.0) 0.56(>2.0) <0.07(>16.0) 0.28(>4.0) Cn TABLE V (Cont'd) GR15 Rate GRg5 Rate (Kg/Ha) (Kg/Ha) Compound Soybean TP SJG SC AG WPM FP RR " Ex. *6^ 1.12 0.28(4.0 <0.07(16.0) 0.14(8.0) 0.09(12.0) 0.28(4.0) <0.07(>16.0) 0.28(4.0) . ib Ex. >1.12 0.56(>2.0) 0.28(>4.0) 0.14(>8.0) 0.12(>9.3) 0.56(>2.0) <0.07(>16.0) 0.75(>1.5) i N> I | C- u> Cn 196545 -28- AG—x 22_) Referring to the data in Table V, it will be noted that within the limits of the herbicide test rates, Compound A did not selectively control any of test weeds in soybeans; Compound B only marginally selectively controlled fali panicum (not a particularly-resistant weed) and Compound C selectively controlled only fali panicum and, marginally, Texas panicum, alexandergrass and red rice. But for the sole exceptions of Compound C against fail panicum IGR^ of 0.28 kg/ha) and Compound B against alexandergrass ana fall panicum (GRg^ of i.00 kg/ha), none of the prior art compounds controlled any of the weeds in the test at less than 1.12 kg/ha (1.0 lb/A).

In sharp contrast, but for isolated instances against certain weeds, all of the invention compounds exhibited outstanding positive selective control of every weed in soybeans. In only a few instances was the selective control marginal, e.g., that of the compounds or Examples 8 and Jcl against red rice; Example 9 against wild proso millet and red rice; Example against wild proso millet and Example Jr5" against shattercane. Moreover, in contrast with-the prior art compounds and again with the noted exceptions, all of the invention compounds controlled ail of the weeds at extremexy low rates of application, ranging from no greater than 0.56 kg/ha (0.5 lb/A) downwardly to less than 0.07 kg/ha (0.0625 lb/A), a remarkable performance in absolute terms in view of the highly-resistant nature of the weeds tested (excepting fail panicum) and particularly relative to the inability of the most relevant compounds of the prior art to control any of the test weeds, except as noteu above.

Preferred compounds of this invention were further tested in the field to determine their selective preemergence herbicidal activity and soil longevity against the annual weeds Texas panicum, bristly scarbur ana Florida pusiey in peanuts 1965 -29- aG—X22 (Florunner). Observations were i.iade at 4, 3 ana 12 weeks after treatment (WAT) by surface application of the herbicides; soil type was a Dothan sandy loam with 1.3% organic matter; the results are shown in Table VI TABLE VI Percent Inhibition Rate Peanuts Texas Panicum Bristly Starbur Florida Pusley Ccrrpound kg/ha 4 WAT 8 WAT 12 WAT 4 WAT 8 WAT 12 WAT 4 WAT 8 WAT 12 WAT 4 WAT 8 WAT 12 WAT Ex. 1 1.12 0 0 0 85 60 52 80 85 95 2.24 12 0 93 83 83 - 90 95 95 90 95 3.36 22 13 0 95 97 87 - 97 95 98 98 4.48 40 27 21 100 95 98 95 100 98 100 98 98 Ex. 2 1.12 0 0 0 82 58 62 — 80 80 90 — 2.24 3 3 0 90 88 87 95 95 90 95 95 100 3.36 8 0 95 95 92 - 90 95 - 97 95 4.48 98 100 100 - 100 100 — 98 95 Ex. 3 1.12 0 0 78 78 43 — 85 — — 85 70 2.24 0 92 87 70 3.36 27 13 0 95 93 88 - 95 95 >- 98 95 4.48 37 27 13 100 97 90 - 97 95 - 98 100 a. Average of three replications i u> 0 1 to to u> Cn Ca 19 6545 -31- AG- i22J The data in Tab±e VI show that; tne compound of Example 2 selectively controlled all three weeas in peanuts at rates within the range of 2.24 to 4.4b kg/ha for up to 12 WAT. Selective control of one or more of the test weeds was also exhibited by the compounds of Examples 1 and 3 at lesser rates for up to 12 WAT, indicating that of the three test compounds, the compound of Example 2 nad the highest safety factor in peanuts under conditions of this test.

Yet other tests were conducted in the field to determine the relative efficacy of the compounds of Examples 1, 3 and 4 agstinst wild proso millet in soybeans for a period up to 12 weeks after treatment when applied either as surface applications (SA) or pre-piant incorporated (PPI). The soil was a sandy loam with 1.7% organic matter; a 2.5 inch (6.35 cm) rainfall occurred 2 days after treatment; the results of this test are shown in Table VII.

Soybean Rate 3 WAT 8 WAT Compound Kg/Ha SA PPI SA PPI Ex. 1 1.12 32 0 22 2.24 33 0 33 3.36 32 13 32 4 .48 33 50 Ex. 2 1.12 0 27 0 8 2 .24 37 0 3.36 22 40 7 27 4.48 60 13 47 Ex. 3 1.12 8 2.24 22 7 18 3.36 22 18 4.48 22 43 33 a. Average of three replicate tests TABLE VII a Percent Inhibition W.iPtoao Millet 12 WAT 3 WAT 8 WAT 12 WAT SA PPI SA PPI SA PPI SA PPI 0 0 85 82 40 43 18 0 0 92 78 78 48 77 50 0 95 85 90 60 85 60 8 23 98 92 85 78 78 70 0 0 85 73 60 57 0 92 75 68 53 72 43 0 0 95 87 88 70 85 63 7 8 92 88 88 70 83 62 0 0 95 85 68 55 63 0 0 95 85 80 67 58 47 0 0 95 80 82 50 82 42 0 95 90 90 78 85 58 i u> ro I left mOi Cn 196 AG—j. 22 The oata in Table VII show that a 3.36 kg/ha rate of each compound selectively controlled wild proso millet in soybeans for 3, 8 and 12 WAT in the surface applications. Thus, certain treatments of the crop with 5 the invention compounds provided season long control of wild proso millet, since germination and emergence of th species increases progressively with the growing season. The greater degree of injury to soybeans in the PPI treatments was deemed to be due to excessively deep and ]_q uneven incorporation by the disc harrow and the rainfall occurring 2 days after treatment. In this test, the surface application treatments provided superior weed control and crop safety.

Examples 1, 3 and 4 were tested for their herbicidal activity on the very resistant annual weed seedling johnsongrass with both surface application and pre-plant incorporation herbicide treatments. This field test was conducted in a clay soil (58% clay and 3.1% organic 20 matter). Observations were made at 4 and 8 weeks after treatment; the results are shown in Table VIII.

In yet another field test, the compounds of TABLE VIII Percent Inhibitiona Soybean Seedling Johnsongrass Rate 4 WAT 8 WAT 4 WAT 8 WAT Compound K g/Ha PPI SA PPI SA PPI SA PPI SA Ex. 1 1.12 2.24 3.36 4.43 13 23 30 3 12 15 18 12 28 22 38 3 10 17 22 7 75 78 80 23 67 85 85 85 87 93 80 80 78 Ex. 3 1.12 2. 24 3.36 4.48 22 28 32 3 13 18 22 13 13 22 32 7 15 23 17 47 70 78 67 82 78 0 70 85 90 23 60 78 68 Ex. 4 1.12 2.24 3.36 4.43 13 23 22 0 13 12 17 8 8 20 28 0 12 13 15 7 60 73 75 23 68 82 85 33 85 87 88 8 78 38 85 a. Average of 3 replicate trials 1965 -35- AG-12 23 The compound of Example 4 selectively controlled seedling johnsongrass in soybeans at the 2.24 kg/ha for as long as 8 weeks after treatment unaer PPI conditions and at the 3.36 and 4.48 kg/ha rates 5 under surface application conditions. The compound of Example 1 selectively controlled seedling johnsongrass at the 3.3b kg/ha rate for at least 4 weeks after treatment under surface application conditions.

As indicated by data in the above tables, 10 compounds according to this invention are suitable used under either surface application or soil incorporation treatments, the preferred treatment depending upon various factors such as soil, climate, etc. Generally, however, surface application of the herbicides are 15 preferred over soil incorporation.

In laboratory tests to determine the resistance of the herbicide to leaching into the soil and resulting herbicidal efficacy, the compound of Example 1 was formulated in acetone and then sprayed at 20 different concentrations onto a weighed amount of Ray silt loam contained in pots having filter paper covering drainage holes in the pot bottoms. The pots containing the treated soil were subjected to leaching by placing on a turntable which rotated under two 25 nozzle tips of a water container calibrated to deliver one inch (2.5 cm) of water per hour simulating rainfall. Leaching rates were adjusted by varying the amount of time on the turntable. Water was delivered to the soil in the pots and allowed to percolate 30 through the filter paper and drainage holes. The pots were then allowed to sit for three days at ambient room temperature. The treated soil in the pots was then removed, crumbled ana placed as a surface layer on top of other pots containing Ray silt loam soil seeded with 35 barnyardgrass seeds. The pots were then placed on greenhouse benches, sub-irrigated and allowed to grow for 2-3 weeks. Visusj. ratings of percent growth inhibition compared to control (untreated) pots ana 196545 AG-12 2 j fresh weights for Darnyardgrass were made io days after treatment and recorded; the data from three replications of these tests are shown in Tabie IX.

Table IX Barnyardgrass Compound of Ex. 1 40 Rate (Kg/Ha 2. 24 0. 56 0.14 Percent Fresh Percen Rain Inhibition Weight of (Cm) (Avg. of 3 replications) Control: 0 100 0 0 0. 64 100 0 0 1. 27 100 0 0 2. 54 100 0 0 . 08 100 0 0 . 16 95 0 0 0 100 0 0 0. 64 100 0 0 1. 27 100 0 0 2. 54 100 0 0 . 08 95 0 0 . lb 95 0 0 0 100 0 0 0.64 . 100 0 0 1. 27 100 0 0 2. 54 95 0 0 .08 95 0. 20 3 . 3 . 16 90 0.83 14. 1 The data in Table IX indicate that the compound of Example 1, representative of the invention compounds, was quite resistant to leaching into the soil under conditions of heavy rainfall and exhibited no less than 90% control of barnyardgrass at application rates as low as 0.14 kg/ha (0.125 ib/a) under 10.16 cm of rainfall.

A distinct advantage of a heroicioe is its ability to function in a wide variety of soil types. Accordingly, data is presented in Table X snowing the herbicidal effect o£ the compounds of Examples 1 and 3 on alexandergrass (AG) and barnyardgrass (BYG) in soybeans in a wide variety of soil types and organic matter content. The heroicioe treatments were applied by surface application with overhead irrigation as 196545 ~ 3 7 ~ ALj - x 2 2 j described above; selectivity factors for the weeas are shown in parentheses after the GRy5 rates for the weeas.

Table X [H7 9-3-84] Soil Type and Compound Ray silt loam Ex. 1 Ex. 3 Sarpy clay loam Ex. 1 Ex. 3 Drummer silty Clay loam Ex. 1 Ex. 3 Florida sand Ex. 1 Ex. 3 Florida muck Ex. 1 Ex. 3 Brazilian (Sao Paulo) Sandy clay loam Ex. 1 Ex. 3 O.M. %_ 1.0 2.3 6.0 6.8 22.1 17.6 Clay _% 9.6 37.0 1.8 .0 GR._ Rate Id (Kg/Ha) Soybeans 1.12 1.12 <2.24 <2.24 2.24 <2.24 1.12 1.12 2.24 2 .:2 4 1.12 1.12 GRQ5 Rate (Kg/Ha) AG <0.14 (>8.0) <0.14 (>8.0) 0.28 (>8.0) 0.21(>10.7) <0.14(>16.0) <0.14(>16.0 <0.14 (>8.0) 0.28 (4.0) 1.12 ( 2.0) 2.24 ( 1.0) <0.14 (>8.0) 0.14 (8.0) BYG 0.14 (8.0) <0.14 (>8.0) 0.96 (>2.3) 0.42 (>5.3) 0.24 (>9.3) 0.28 (>8.0) 1.12 ( 1.0) 2.24 ( NS ) 2.24 ( 1.0) <2.24 ( NS ) 0.14 ( 8.0) 0.14 ( 8.0) a. Data represent averages of 13 days after treatment. two replications. Observations made i u> 00 1 CP Ski « 196545 -39- AG-a22j The data in Table X show that the invention compounds were largely insensitive to soil type. In more particular, the compound of Example i exhibited positive selective control of alexandergrass and 5 barnyardgrass in soybeans in all soild in the test containing organic matter ranging from 1.0% O.M. content in Ray silt loam to 22.1% O.M. in Fioriua muck soil. Similarly, the compound of Example 3 exhibited positive selective control of the weeds in test in 10 soybeans in all soil types,except against barnyardgrass in Florida sand (b.8% O.M.) and Flonoa muck. Since the compound of Example 3 did selectively control both alexandergrass and barnyarcigrass in Drumiaer silty clay loam soil having approximately the same organic 15 matter content as Florida sand, but a much higher clay content (37.0%) and in soils, having higher O.M. and clay content as in Brazilian sandy clay loam, it is believed that the low clay content (1.8%) in the Florida sand contributed to non-selective control of 20 barnyardgrass in that soil.

The compounds of this invention have their most important application in soybeans and peanuts. However, selective weed control has been established in a variety of other crops as indicated in Table III 25 above. In yet other tests, the compound of Example 1 was also shown to be useful in snap beans and garden peas at rates up to 1.0 lb/a, in cotton, rape, carrot and red beet up to 0.5 lb/a or more and in alfalfa, flax and cabbage on the order of 0.25-0.5 lb/a. 30 Toxicology studies on the compounds of Examples 1, 3 and 4 have indicated the following properties: 196545 1 2 2 J Toxicology OLD50, Mg/Kg DLD, Mg/Kg. Eye irritation Skin irritation Compouna of Example No. 3370 >2GQU siight none 2300 >1000<1260 severe corrosive 4 2400 >3100<50i0 moderate corrosive The corrosive nature of the compound of Example 3 may be due to a contaminant, dimethyl sulfate, found in the preparation of the sample on which toxicology studies were conducted. It is apparent that the above compounds may be safely used with the normal degree of care required for compounds having the indicated toxicological properties. The indicated relative degree of safe handling characteristics for the compounds of the respective examples appears to be: Example 1 > Example 4 > Example 3.

Therefore, it will be appreciated from the foregoing detailed description that compounds according to this invention have demonstrated unexpected and outstandingly superior herbicidal properties botii absolutely and relative to the most structurally-relevant compounds of the prior art, one of which (Compound C) is a commercial herbicide. More particularly, the compounds of this invention have proven to be outstanding selective herbicides, particularly in the control of hard-to-kill annual grasses in soybeans, peanuts and other crops. In more particular, compounds according to this invention exhibit outstanding control of the annual grasses Texas panicum, itchgrass, wild proso millet, alexandergrass, seedling johnsongrass, shattercane and red rice, while controlling and/or suppressing other less-resistant annual grasses and perennials, including those mentioned in Tables II and III above and others, such as bristly starbur, Florida pusiey, etc. 19654^ -41- AG-1223 The herbicidal compositions of tnis invention including concentrates which require dilution prior to application contain at least one active ingredient and an adjuvant in liquid or soiid form. The compositions 5 are prepared by admixing tne active ingredient'with an adjuvant including diluents, extenders, carriers ana conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, peilets, solutions, dispersions or emulsions. Thus the 10 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 emulsifying agent or any suitable combination of these.

The compositions of this invention, 15 particularly liquids and wettabie powders, preferably contain as a conditioning agent one or more surface-active agents in amounts sufficient to renoer a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into 20 the compositions greatly enhances their efficacy. By the term "surface-active agent" it is understood that wetting agents, dispersing agents, suspending agents anc emulsifying agents are included therein. Anionic, 1».M,45 cationio and non-ionic agents can be used with equax facility.

Preferred wetting ayents are aikyi benzene and alkyl naphthalene sulfonates, sulfated facty alcohols, amines or acid amiues, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetyienic 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 dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl, naphthalene sulfonates, sodium naphthalene sulfonate, and the polymethyiene bisnaphthalene sulfonate.

Wettabie powders are water-dispersibie compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents. The inert soiid extenders are usually of mineral origin such as the natural ciays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettabie powders compositions of this invention usually contain from about 0.5 to 60 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, ali parts being by weight of the total composition. Where required, from aoout U.i to 2.0 parts of the solid inert extender can be replaced by a corrosion inhibitor of anti-foaming agent or Doth.

Other formulations include dust concentrates 196545 _ Zj.3— ACj—i223 comprising from 0.1 to bu% by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range of from about 0.1-10% by weight.

Aqueous suspensions or emulsions may be prepared by stirring an aqueous mixture of a water-insoluble active ingredient and an emuisification agent until uniform and then homogenized to give' stable emulsion of very finely-divided particles. The 10 resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that when diluted ana sprayed, coverage is very uniform. Suitable concentrations of tnese formulations contain from about 0.1-60% preferably 5-50% by weight 15 of active ingredient, the upper limit being deterraincu by the solubility limit of active ingredient in the solvent.

In another form of aqueous suspensions, a water-immiscible herbicide is encapsulated to form 20 microencapsulated phase dispersed in an aqueous phase. In one embodiment, minute capsules are formed by bringing together an aqueous phase containing a lignin sulfonate emuisifier and a water-immiscible chemical and polymethyiene polyphony!isocyanate, dispersing the 25 water-immiscible phase in the aqueous phase followed by addition or a poiyfunctional amine. The isocyanate ana amine compounds react, to form a solid urea shell wali arounc particles of the water-immiscible chemical, thus forming microcapsules thereof. Generally, the 30 concentration of the microencapsulated material will range from about 430 to 700 g/1 of total composition, preferaoxy 4 c u to 600 q/l Concentrates are usually solutions of active ingredient in water-immiscible or partially water- ly bo AG-i 223 immiscible solvents together with a surface active agent. Suitable solvents for the active ingredient of this invention include aimethyiformide, dimethyisulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters or ketones.

However, other high strength liquid concentrates may be formulated by dissolving the active ingredient in a solvent then diluting, e.g., with kerosene, to spray concentration.

The concentrate compositions herein generally contain from about 0.1 to 95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50 parts (preferably 1-25 parts) surface active agent and where required about 4 to 94 parts solvent, all parts being by weight based on the total weight of emuisifiable oil.

Granules are physically stable particulate compositions comprising active, ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender. In order to aio 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, iilite and vermiculite are examples of operable classes of particulate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate attapulgite or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the herbicidal granules.

The granular compositions of this invention may contain from about 0.1 to about 30 parts preferably from about 3 to 20 parts by weight of active ingredient per 10U parts by weight of clay and 0 to about 5 parts jfc.v _v w ~ ^ -45- icftl. by weight of surface active agent per iGi) parts by weight of particulate clay.

The compositions of this invention can also contain other aduitaments, for example, fertilizers, 5 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 of this invention include, for example, triazines, ureas, 10 carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamaces, triazoles, benzoic acids, nitriles, biphenyi ethers and the like such as: Heterocyclic Nitrogen/bulfur Derivatives 2-Chloro-4-ethylamino-6-isopropylamino-^-triazine 2-Chloro-4,6-bis(isopropylamino)-s-trxazine 2-Chloro-4,6-bis(ethy1amino)-s-triazine 3-Isopropyl-lH-2,1,3-benzothiaa iaz in-4-(3H)-one 2,2 dioxide 3-Amino-1,2,4-triazole 6 , 7-Dihyurod ipyriao(i,2-a:2',l'-c)-pyraz idi inium salt -3romo-3-isopropyl-6-methy1uracil 1,1'-Dime thy1-4,41-bipyrid inium 25 Ureas N '- ("4-chlorophenoxy) phenyl-N ,N-d imethylurea N ,N-cimetliyl-N ' - ( 3-chloro-4-me thylphenyl) urea 3-13,4-dichiorophenyl)-l,1-d imethyiurea l,3-Dimethyl-3-(2-benzothiazolyi) urea 30 3-(£-Chlorophenyi)-l,1-dimethylurea l-Butyl-3-(3,4-dichiorophenyl)-1-metnylurea 19 6545 A(j — -L 2 J Carbama tes/Thioj-carbamates 2-Chioroallyl diethyldi thiocarbamate S-(4-cniotobenzyi)N, N-diethyl th iol carbamate Isopropyl N-(3-chlorophenyl) carbamate S-2,3-dicnloroallyl N,N-aiisopropylthioicarbamate Ethyl N,N-dipropylthiolcarbamate S-propyl dipropylthiolcarbamate Acetamides/Acetanil ides/Anilines/Amides 2-Chloro-N,N-diallylacetamide N,N-dimethyl-2,2-diphenylacetamide N- ( 2 , 4-dimethyl-5- [ [ (trif luoroiuethyl) sulfonyl] amino]phenyl)acetamide N-Isopropyl-2-chloroacetanilide 2',61-Diethyl-N-methoxymethyl-2-chloroacetanilide 2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-y1)-2- chloroacetanilide cx , , cC -Trifluoro-2 , 6-dinitro-N ,'N-dipropyl-p-toluidine N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamice 20 Acids/Esters/Alcohols 2, 2^Dichloropropionic acid 2-Methyi-4-chlorophenoxyacetic acid 2,4-Dicnlorophenoxyacetic acid Me thy1-2- 14-(2,4-dichlorophenoxy)phenoxy] 25 propionate 3-Amino-2,5-dichiGrobenzoic acid 2-Methoxy-3,6-dicnlorobenzoic acid 2 , 3 , 6-Trichiorophenyiacetic acid Sodium 5- [2-chioro-4-( tr if luoromethyi )phenoxy] -2-ni trobenzoate -.5 4 , 6-Dini tro-o-sec-bu tyiphenol N-(phosphonomethyl) glycine and its C, -monoalkyl amine and alkaline metal saitss and combinations thereof Ethers 2 ,4-Dichloropheny1-4-nitrophenyi ether 2-Chloro- , , -trifluoro-£-toiyi-3-ethoxy-4-nitrodiphenyl ether Miscellaneous 2,6-Dichlorobenzonitrile Monosodium acid methanearsonate Disodium methanearsonate Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate. Other useful additainents include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

Herbicidal formulations of the types described above are exemplified in several illustrative embodiments below.

I. Emuisifiable Concentrates (EC's) Weight Percent A. Compound of Example No. 1 ^ 35.6 Calcium dodecyibenzene sulfonate/' polyoxye thylene ethers blend (e.g., Atlox® 3437F) 5.0 Monochlorobenzene 29.7 Cy aromatic hydrocarbon 29.7 100.00 19 AG—1z / 3 B. Compound of Example No. 3 85. U Calcium dodecyl suifonate/ai- kylaryl polyether alcohol blend 4.0 Cg aromatic hydrocarbons solvent li.Q luO.UO C. Compound of Example No. 4 5.0 Calcium dodecylbenzene sulfonate/ polyoxyethylene ethers blend (e.g., Atiox 3437F) 1.0 Xylene 94.0 100.00 II. Liquid Concentrates Weight Percent A. Compound of Example No. 5 10.0 Xylene 90.0 100.00 B. Compound of Example No. 6 8 5.U Dimethyl sulfoxide 15.0 100.00 n A. J. P. &2o C. Compound of Example No. 50.0 N-methyipyrrolidone 50.0 100.0 "Zby'gf1 D* Compound of Example No. ^ 5.0 Ethoxyiated castor oil 20.0 Rhodamine B . 5 Dimethyi formamiue 74.5 100.00 III. Eiiiuxsions Weight Percent A. Compound of Example No. 7 40.0 Polyoxye thylene/polyoxy- propylene block, copolymer with butanol (e.g., Tergitol® XH) 4.0 Water 56.0 100.00 B. Compound of Example No. 8 5.0 10 Polyoxyethylene/polyoxy- propylene block copolymer with butanol 3.5 Water 91.5 100.00 IV. Wettabie Powaers Weight Percent A. Compound of Example No. 9 25.0 Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyi-taurate 1.0 Amorphous silica (synthetic) 71.0 100.00 B. Compound of Example No. 10 80.0 Soaium dioctyi sulfosuccinate 1.25 Calcium Iignosulfonate 2.75 Amorphous silica (synthetic) 16.00 100.00 C. Compound of Example No. 11 10.0 Sodium 1ignosulfonate 3.0 Sodium N-rnethyi-N-oleyl-taurate 1.0 Kaoiinite clay 86.0 0.0 0 1 hcj — i 2 z j V. Dusts .. J_P. & S.

Mfi wv Jr :S^? weight Percent A. Compound of Example No. 12 2.0 Attapulgite 9<3. 0 100.00 • J; p- & S. 1^)-8? Guiupuund—e-fi—Example -No.—±-3- 6-0 . 0 MontmrMr-illoni Le *40 . Or <■100. 00' Xj. Compound of Example No. 13 30.0 Bentonite 70.0 ML,.... iqo.oo P., 7-*! r J/- P' & S' vA IU X* Compound of Example No. uf 1.0 Diatomaceous earth 99.0 100.00 VI. Granules J P & S i£~ Weight Percent A. Compound of Example No. 15.0 Granular attapulgite (20/40 mesh) 85.0 J, P. & S. ioo. oo lib •-) • 83 MK. & Compound of Example No. 30.0 70 . 0 £ S, Diatomaceous earth (20/40 i 0 <y 100.00 n C. Compound of Example No. -i-tf 0.5 Bentonite (20/40) 99.5 100.00 (£ D. Compound of Example No. ¥5 5.0 Pyrophyllite (20/4 0) 95.0 100.00 •51- ia ./a y AG— I 2j VII. Microcapsules A. Compound of Example No. 1 encapsulated in polyurea sneil wall 49.2 Sodium 1ignosulfonate (e.g.

Reax 83I>^ ) 0• ^ Water 49.9 100.00 B. Compound of Example No. 3 encapsulated in polyurea shell wall 10.0 Potassium 1ignosulfonate (e.g., Rexas C-21® ) .5 Water 89.5 100.00 C. Compound of Example No. 4 encapsulated in polyurea shell wall 80.0 Magnesium salt of lignosulfate (Treax 2.0 Water 18.0 0.0 0 When operating in accordance with the presen-t invention, effective amounts of the acetaniiiues of this invention are applied 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. Th compositions can also be applied from airplanes as a dust or a spray because of tneir effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by aading tne compositions to the aquatic media in the area where control of the aquatic plants is desired. riCj — 1 2 2 J> 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 thereof, tne type and condition of soil, the amount of rainfall and the specific 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 aoout 0.04 to about 5.60 kg/ha, or suitably from 1.12 to 5.6 kg/ha of acetanilide is usually employed. Lower or higher rates may be required in some instances. One skilled in the art can readily determine from this specification, including the above example, the optimum rate to be applied in any particular case.

The term "soil" is employed in its broadest sense to be inclusive of all conventional "soils" as defined in Webster's New International Dictionary, Second Edition, Unabridged (1961). Thus the term refers to any substance or media in which vegetation may take root and grow, and includes not only earth but also compost, manure, muck, humus, sand and the iike, aaapted to support plant growth.

Although the invention is described with respect to specific modifications, the details thereof are not to be construed as limitations except to the extent indicated in the following claims. 196545 -53- -AG 1223-

Claims (39)

WHAT WE CLAIM IS:

1. Compounds having the formula 0 !• cich2c _r N wherein R is methyl or ethyl; R-j_ is a C^_g alkyl radical; 5 R2 is methyl, ethyl or t-butyl and R^ is hydrogen or methyl in a meta position; provided that; when R is ethyl, R^ is n-butyl, R2 is methyl and R3 is hydrogen; 10 when R3 is methyl, R and R2 are also methyl and R^ is isopropyl or n-butyl; when R^ is hydrogen and R and R2 are both methyl, R^ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 15 . 2-methylpentyl or 1,3-dimethylbutyl; when R2 is ethyl, R is methyl and R^ is isopropyl and when R2 is t-butyl, R and R^ are both methyl.

2. Compounds according to Claim 1 wherein R^ is a C^_5 alkyl radical and R and R2 are methyl radicals.

3. Compound according to Claim 2 which is N-methyl-21-isopentyloxy-61-methyl-2-chloroacetanilide.

4. Compound according to Claim 2 which is N-methyl-2'-n-propoxy-6'-methyl-2-chloroacetanilide.

5. Compound according to Claim 2 which is N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide. ■?- c. £ J*., <?.! V< tf -54- AG 1223

6. Compound according to Claim 2 which is N-methyl-2'-sec-butoxy-61-methyl-2-chloroacetanilide.

7. Compound according to Claim 2 which is N-methyl-21-isopropoxy-61-methyl-2-chloroacetanilide.

8. Compound according to Claim 2 which is N-methyl-2'-isobutoxy-6'-methyl-2-chloroacetanilide.

9. Compound according to Claim 1 which is N- ethyl -21-n-butoxy-6'-methyl-2-chloroacetanilide.

10. Compound according to Claim 1 which is n-methyl-21-isopropoxy-6'-ethyl-2-chloroacetanilide.

11. Herbicidal composition comprising an adjuvant and a herbicidally effective amount of a compound having the formula C1CH-C R 2 \ / R2' wherein r is methyl or ethyl; Rn is a C, , alkyl radical; 1 1-b R2 is methyl, ethyl or t-butyl and is hydrogen or methyl in a meta position; provided that: when r is ethyl, r, is n-butyl, r_ is methyl and ri R^ is hydrgcm ; when r^ is methyl, r and r2 are also methyl and R^ is isopropyl or n-butyl; when r^ is hydrogen and r and r2 are both methyl, R^ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl; when r2 is ethyl, r is methyl and r^ is. isopropyl and 5.R6545, -55- AG-t2^ when R2 is t-butyl, R and R^ are both methyl.

12. Composition according to Claim 11 wherein in said compound R^ is a C3_^ alkyl radical and R and R2 are methyl radicals.

13. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-21-isopentyloxy-61 -methyl-2-chloroacetanilide.

14. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2'-n-propoxy-61-methyl-2-chloroacetanilide.

15. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-21-n-butoxy-61 -methyl-2-chloroacetanilide.

16. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2'-sec-butoxy-61-methyl-2-chloroacetanilide.

17. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2*-isopropoxy-61-methyl-2-chloroacetanilide.

18. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-21-isobutoxy-6'-methyl-2-chloroacetanilide.

19. Herbicidal composition according to Claim 11 wherein said compound is N-ethyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide.

20. Herbicidal composition according to Claim 11 wherein said compound is N-methyl-2'-isopropoxy-6'-ethyl-2-chloroacetanilide. 196545 -56- -AG 1223-

21. Method for controlling undesirable plants in crop plants which comprises applying to the locus thereof a herbicidally effective amount of a compound having the formula 0 II C1CH„C R 2 \ / N wherein R is methyl or ethyl; R^ is a C^_g alkyl radical; R2 is methyl, ethyl or t-butyl and R^ is hydrogen or methyl in a meta position; 10 provided that: when R is ethyl, R^ is n-butyl, R^ is methyl and R^ is hydrogen; when R^ is methyl, R and R2 are also methyl and R^ is isopropyl or n-butyl; 15 when R^ is hydrogen and R and R2 are both methyl, R^ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl; when R2 is ethyl, R is methyl and R^. is isopropyl 20 and when R2 is t-butyl, R and R^ are both methyl.

22. A method according to Claim 21 wherein in said compound R^ is a C^g alkyl radical and R and R2 are methyl radicals .

23. A method according to Claim 22 wherein said compound is N-methyl-2'-isopentyloxy-61-methyl-2-chloroacetanilide. _ 9 6 5 4 -57- AG-i£2r

24. A method according to Claim 22 wherein said compound is N-methyl-21-n-propoxy-61-methyl-2-chloroacetanilide.

25. A method according to Claim 22 wherein said compound is N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide.

26. A method according to Claim 22 wherein said compound is N-methyl-2'-sec-butoxy-6'-methyl-2-chloroacetanilide.

27. a method according to Claim 22 wherein said compound is N-methyl-21-isopropoxy-6'-methyl-2-chloroacetanilide.

28. A method according to Claim 22 l90bu.Ti?yij wherein said compound is N-methyl-2'-icobutyl-6'-methyl-2-chloroacetanilide.

29. a method according to Claim 21 wherein said compound is N-ethyl-2'-n-butoxy-61-methyl-2-chloroacetanilide.

30. A method according to Claim 21 wherein said compound is N-methyl-21-isopropoxy-6'-ethyl-2-chloroacetanilide.

31. Method according to Claim 21 wherein said crops are leguminous crops.

32. Method for controlling undesirable plants in soybeans, peanuts, rape, cotton, snap beans, alfalfa and vegetable crops which comprises applying to the locus thereof a herbicidally effective amount of N-methyl-2'-isopentyloxy-61-methyl-2-chloroacetanilide.

33. Method for controlling undesirable plants, in soybeans, peanuts, rape, cotton, snap beans, alfalfa and vegetable crops which comprises applying to the locus thereof a herbicidally effective amount,of N-methyl-21- -n-propoxy-6'-methyl-2-chloroacetanilide. ^ , .. * J. P. & $5 I . m 5 J. P. & s. Mil. ~JO"

34. Method for controlling undesirable plants in soybeans, peanuts, rape, cotton, snap beans, alfalfa and vegetable crops which comprises applying to the locus thereof a herbicidally effective amount of N-methyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide. p/ai^K

35. Method for controlling undesirable ^lans in soybeans, peanuts, rape, cotton, snap beans, alfalfa and vegetable crops which comprises applying to the locus thereof a herbicidally effective amount of N-methyl-2'-isobutoxy-61-methyl-2-chloroacetanilide.

36. A compound as claimed in any one of claims 1 to 10 substantially as hereinbefore described with reference to any Example thereof.

37. A composition as claimed in any one of claims 11 to 20 substantially as hereinbefore described with reference to any Example thereof.

38. A method as claimed in any one, some or all of claims 21 to 35 when performed substantially as hereinbefore described with reference to any Example thereof.

39. A method a|p claimed in any one, some or all of claims 21 to 35 and 2r7 wherein said compound is used as a composition as claimed in any one of claims 11 to 20 and 37. DATED THIS DAY OF 19*3" f A. J. PARK & SON PER yb AGENTS FOB THE APPLICANTS