IE51698B1 - Herbicidal 2-haloacetanilides - Google Patents

Abstract

A group of N- hydrocarbyloxymethyl-2- haloacetanilide compounds, herbicidal compositions containing said compounds as the active ingredient and herbicidal method of use in various crops, particularly, corn and soybeans and other crops including cotton, peanuts, rape, bush beans, wheat and sorghum. The herbicides herein are particularly effective against hard-to-kill perennial weeds such as quackgrass and nutsedges and are also effective against annual weeds.

Description

This invention pertains to the field of 2-halo-ncetani1 ides and their use in the agronomic arts, e.g., as herbicides.

The prior art relevant to this invention includes numerous disclosures of 2-haloacetanilidas which may be unsubstituted or substituted with a wide variety of substituents on the anilide nitrogen atom and/or on the anilide ring including alkyl, alkoxy, alkoxyalkyl, haloalkyl, halogen, etc., radicals.

As more relevant to the invention compounds, which are characterized by having a hydrocarbyloxymethyl radical on the anilide nitrogen, a trifluoromethyl radical in one ortho position and a methyl radical or, in specific cases, an ethyl radical or hydrogen in the other ortho position, the closest prior art known to the inventor appears to be Belgian Patent No. 810,763, corresponding to British Patent No. 1 455 474. The most relevant disclosures in the aforementioned patent are the generic disclosures of N-alkoxyethyl- or alkyl-substituted alkoxyethyi-2-chloroacetanilides which may be substituted on the anilide ring at the ortho and meta positions with one or more radicals selected from a plurality of radicals including halogen, alkyl, alkoxy 25 or tri fluoromethyl (-CF^J. In more particular, the list of compounds in Table II includes species substituted with a -CFg radical in one ortho position with no substituent in the other ortho position {Compound Numbers 37-48) and compounds having -CFg substitution in a meta position with) one ortho position unsubstituted and the other ortho position substituted with a methoxy radical (Compound Numbers 22-25) or a chlorine atom (Compound Numbers 33-36). However, there is no specific disclosure or exemplary species in the -2'763 patent of 2-haloacetanilides substituted with a -CFj radical in one ortho position and a methyl or ethyl radical in the other ortho position as in the compounds of this invention. Moreover, the compounds in the *753 patent are characterized by an alkoxyalkyl group substituted on the anilide nitrogen atom wherein the alkylene moiety must have no less than two carbon atoms between the nitrogen atom and the oxygen atom of the alkoxy moiety. Xn contrast, the compounds of this invention are further characterized, in part, by the substitution on the anilide nitrogen atom with an alkoxymethyl radical. The significance of the above distinctions between the compounds of the '753 patent and this invention will be made manifest by reference to the comparative herbicidal data herein clearly establishing tne superiority of the invention conpounds in terms of unit activity, selectivity, weed-control spectrum and crop safety.

Other pertinent prior art less relevant than the above-mentioned '753 patent includes U. S. Patent Numbers 3,954,311, and 4,152,137, German Application 2402983, British Application No. 2 013 188, which corresponds to Irish Specification No. 48057, South African Patent Number 74/0767 and British Patent No. 455 471. Although these references contain generic disclosures of substituents -CFj substitution on the anilide ring, the only disclosures of any species of such compounds in any of these references are found in said U. S. Patent 3,955,311 and South African Patent No. 74/0757. Even so, neither of the '811 nor '757 patents contain any species of ortho -CF^-substituted compounds generally or more particularly, such compounds further substituted in the other ortho position with a methyl or ethyl radical; the only -CF^-substituted species disclosed in these patents are meta-CFj-substituted compounds. Moreover, like the above '753 Belgian patent, both of the '311 U. S. patent and '757 South -3African patent require that there be no less than two carbon atoms between the anilide nitrogen and the oxygen of the alkoxy moiety, a requirement described in all the foregoing prior art references, except said '137 U. S. patent which, as mentioned above, discloses no -CFj-substituted species whatever.

Of the above-mentioned most relevant prior art, oniy said Belgian Patent No. 810,763 and South African Patent No. 74/0757 disclose any herbicidal data χθ relative to N-alkoxyalkyl-2-haloacetanilides having -CFj substitution on the anilide ring. Even so, such disclosures are vague, indefinite and incomplete. For example, said '753 patent discloses limited herbicidal data for only one -CF^-substituted compound, viz., X5 Compound No. 37 (which is the same compound as in Example 2), i.e., 2-trifluoromethyl-N(2’-methoxyethyl)-2-chloro-acetanilide. In Table 3 of said '753 patent, Compound No. 37 is shown to destroy or seriously injure certain unidentified species of 2o Cuperus”, Setaria, Digitaria and Echinochloa, with little injury to the weeds Avena fatua and an unidentified species of Lolium in certain crops. The lack of specific identity of five of the six weeds tested precludes a meaningful evaluation of the herbicidal efficacy of said Compound 37.

Similarly, said '767 South African patent discloses limited herbicidal data for only one -CFjsubstituted compound, viz., Compound No. 78, i.e., 2,5dimethyl-3-tri fluoromethyl-N-(2'-methoxyethyl)—N-230 chloroacetanilide. The only herbicidal data disclosed for Compound No. 73 is in Example 5 wherein Compound No. 78 is said to exhibit very strong growth inhibition of four species of grass weeds. However, there is no laboratory or field data disclosed in said '767 patent relative to the effect of Compound No. 78 on any crop or whether that conpound exhibits selective control of any weed in any crop, thus rendering any meaningful -4evaluation of tnat compound based on such limited data impossible. Still further, the above most relevant references, while disclosing herbicidal activity on a variety of weeds, do not disclose any data for any -CF^-substituted-N-alkoxy-alkyl compounds which are shown to additionally and/or simultaneously control or suppress in one or more crops the hard-to-kill perennial weeds, quackgrass, yellow and purple nutsedgss and a broad spectrum of annual weeds including such hard-to-kill annual grass weeds such as seedling johnsongrass, shattercane, alexandergrass (Brachiaria plantaginea), panicums (Texas and wild proso millet), red rice and itchgrass (Raoulgrass), while also controlling or suppressing other noxious perennial and annual weeds, e.g, fall panicum, smartweed, lambsquarters, pigweed, foxtails (e.g., giant and yellow), crabgrass, barnyardgrass, morningglory, velvetleaf, cocklebur, purslane, hemp sesbania, prickly sida, etc.

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 herbiciies, weed control is adequate only for 2 or 3 weeks, or, in some superior cases, perhaps up to 4-5 weeks, before the chemical loses its effective phytotoxic properties. Accordingly, one disadvantage 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 /eather conditions, is the lack of weed control persistence under heavy rainfall which .inactivates many herbicides.

A further disadvantage of many prior art herbicides is limitation of their use in specified types of soil, i.e,, while some herbicides are 516 9 8 -5effective in soils having small amounts of organic matter, they are ineffective in other soils high in organic matter or vice-versa. Xt is, therefore, advantageous that a herbicide be useful in all types of soil ranging from light organic to heavy clay and muck.

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 soil incorporation, pre- and/or post-plant mode of application. It is highly desirable to be able to apply a herbicide in any mode of application, whether by surface application or soil i ncorpo ration.

And, finally, a disadvantage in some 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 this invention 2o to provide a group of herbicidal conpounds which overcome the above-mentioned disadvantages of the prior art and provide a multiplicity of advantages heretofore unachieved in a single group of herbicides.

It is an object of this invention to provide herbicides which control and/or suppress hard-to-kill perennial and annual weeds such as described above, while maintaining crop safety in a plurality of crops, particularly corn and soybeans, and others including cotton, peanuts, rape, bush beans, wheat and/or 3q sorghum.

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

Yet another object of this invention is to 35 provide herbicides which resist leaching and dilution due to high moisture conditions, e.g., as heavy rainfall. -6Still another object of this invention is the provision of herbicides which are effective over a wide range of soils, e.g., ranging from light-medium 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 preemergenca surface application and by soil incorporation.

Finally, it is an advantage of the herbicides 10 °f 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.

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 particular croos.

It has now been found that a selective group of 2-haloacetanilides characterized by specific combinations of specific hydrocarbyloxymethyl radicals on the anilide nitrogen atom, a tri fluoroniethyl (-CFj) radical in one ortho position and a methyl or ethyl radical or hydrogen atom in the other ortho position possess unexpectedly superior and outstanding herbicidal properties vis-a-vis prior art herbicides, including homologous compounds of the most relevant prior art.

A primary feature of the herbicidal compositions of this invention is their ability to control a wide spectrum of weeds, including weeds controllable by current herbicides and, additionally, a plurality of weeds which, individually and/or collectively, have heretofore escaped control by a single class of known herbicides, while maintaining crop safety with respect to one or more of a plurality -Ιοί crops including, particularly, corn and soybeans, but others such as cotton, peanuts, rape, sorghum, wheat and snap beans. While prior art herbicides are useful for controlling a variety of weeds, including on occasion certain resistant weeds, the unique herbicides of this invention have been found to be capable of controlling or greatly suppressing a plurality of resistant perennial and annual weeds, such as the perennials quackgrass, yellow and purple nutsedges, annual broadleafs such as prickly sida, hemp sesbania, smartweed, lambsquarters, pigweed and annual grasses such as seedling johnsongrass, shattercane, alexandergrass, Texas panicum, wild proso millet, red rice, itchgrass and other noxious weeds such as fall panicum, foxtails, barnyardgrass, crabgrass, etc. Weed stand reduction has also been achieved in resistant weeds such as ragweed, velvetleaf, morningglory, cocklebur, purslane, etc.

The compounds of this invention are 2o characterized by the formula II wherein R is C1_g alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and R^ is hydrogen, methyl or ethyl; provided that: When R^ is hydrogen, R is isopropyl and when R^ is ethyl, R is ethyl, n-propyl or i sopropyl, Preferred compounds of this invention are 30 compounds wherein R^ in the above formula is methyl or -8‘.thyl and R is a alkyl radical. Individual preferred compounds of this invention are as follows: N- (cthoxymethyl) - 2 trifluoromethyl-C ' - .. thyl^.chloroacetanil ide.

N- (n-propoxymethyl)-2,-t.rifluoromethyl-5'-methyl-2chloroacetanilide.

N-(i ;opropoxynothyl)-2'-trifluoromethyl-5'-methyl-2chloroacetanilide.

N-(ilobutox/methyl)-2'-tr i f1uoromethy1-5'-methyJ-2chloroacctanilide.

N- (ethoxyne* hyl)-2 ’-1r i f 1 uoromcthy] -5 '-( t.hyl-2chloroacef; - il ide.

N-(n-propoxymethyl)-2 '-tr ifluoromethyl-51-ethyl-2chloroacetariil ide.

N-(: sopropoxymethyl)-2'-trif1uoromethy1-5'-uthyl-2chloroacetcnilide.

Other compounds of this invention will be described below.

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

The compounds of this invention may be made by the N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent under basic conditions as exemplified in Example 1 herein. Modification of said N-alkylation process involves the in-situ preparation of halomethyl alkyl ethers used as starting materials in said N-alkylation process and is described in Example 2 for preparing another compound of the invention. -9Example 1 This example describes the preparation of N-(ethoxymethyl)-2'-trifluoromethyl-5'-methyl-2-chloroacetanilide. 2'-Tr i fluoromethyl-5'-metnyl-2-chloroacetanilide, 4.02 gm (0.015 mol), chloromethyl ethyl ether, 3.02 gm (0.032 mol) and benzyl triethylammonium bromide, 2.0 g, (phase transfer catalyst) were mixed in 75 ml of methylene chloride in a 500 ml round bottom flask equipped with mechanical stirrer and thermometer.

Sodium hydroxide (50%), 15 ml, were added all at once with vigorous stirring giving rise to an exotherm to 2o°C. After about 5 minutes gas chromatography indicated that the reaction was complete. After 15 minutes, ic» and water were added, the layers separated and the organic layer washed with 2.5% sodium chloride, dried, filtered and stripped. The dark-colored residue was distilled on a Kugelrohr and 3.Λ g of a yellow oil fraction boiling at 110-115°C at 0.1 mm collected.

This fraction was taken up in cyclohexane and purified by HPLC using 20% ethyl acetate in cyclohexane.

Further distillation of peak fraction by Kugelrohr yielded 3.2 gm (55% yield) of colorless oil, b.p. 130-110°C at 0.1 mm Hg; on standing a white solid, m.i 25 41°C-43° C crystallized out. Anal, for ^CIF^NO,(%) Element Theory Found C 50.41 50.02 H 4.83 4.31 N 4.52 4.38 30 Example 2 This example illustrates the use of an improved alternative process by which the compounds of this invention may be prepared. A feature of the -10process of this example is that in-situ formation of the alkylating agent, thus effecting a more efficient, economical and simple operation.

A slurry of ethylene glycol monomethyl ether 7.3 gm (0.096 mol) and paraformaldehyde, 1.44 gm (0.043 mol) in 100 ml of methylene chloride solvent was cooled in an ice water bath and 5.9 gm (0.048 mol) of acetyl·' bromide added. After stirring for about 45 minutes, 4.03 gm (0.015 mol) of 2'-trifluoromethyl5'-methyl-2-chloro-acetanilide and 2.0 gm of benzyl triethylemmonium chloride were added. Fifty milliliters of 50% NaOH were added all at once. Gas chromatography indicated complete reaction after about 5 minutes. Ice and water were added to the mixture to effect phase separation and the organic phase was then separated, dried, filtered and stripped. The residue was vacuum distilled on a short path still to yield 4.2 gm (77% yield) of clear, colorless oil, b.p. 150- -159°c at 0.05 mm Hg. Anal, for C, .H._C1F^VO_ - 14 1/ 33 (%, Element Theory Found c 49.49 49.33 H 5.04 5.04 N 4.12 4.08 The product was identified as N- (2-methoxyethoxymethyl)-2’-trifluoromethyl5'-methyl-2-chloroacetanilide.

If the N-alkylation process is allowed to develop too high or too low temperatures, various impurities may be generated, e.g., sec-anilide, corresponding imidate,e<-alkoxyamide or diketopiperazines. Such impurities may be removed by washing the organic layer with a dilute aqueous salt of acid solution, e.g., 2-3% NaCl or 5% HCl.

Examples 3—15 Following substantially the same procedures, quantities of reactants and general reaction conditions as described in Examples 1 or 2, but substituting the -11appropriate starting sec-anilide and alkylating agent to obtain the end product, other compounds according to the above formula are prepared; these compounds are identified in Table X. 516 9 8 -12Analysis Example Empirical B.P. °C No. _Compound_ Formula (mm Hg.) Element Calculated Found CM OS kO m co •Μ’ ο τρ m o r* oo CO rH 04 r—i IA tP in cn co oi kO Ol 04 HLAtT in O’ r—i rH OkO O ro in τρ in rH 05 Ol tp oo in τρ cn ro OS Ol co H1 cn co OS 04 co tp o> in CO kO rH tp ··.* o os <* oCS <· Ti TP O' co Tp Τί Tp ΟO Tp TP in rH in Ti in rH in TP in co in tp in Tp Tp τρ CO M· CO kO rH CO in Tp in τρ ο» m CO kO rH co in tp in co r> ro CM ko rH co m τρ m τρ o· in CO kO rH ro tn tp in u ffl a U ffl ffl Q ffl 2 υ ffl ffl υ υ υ ο ο 0 rH Ο ο ο O —. οι οι τΡ rH UH ί—ι «μ rH 1 o 1 rH 1 γΗ 1 rH o · Ο · ο · Ο · o o Η Ο Η Ο CO ο rH rH rH ' ιΗ Ol CM οι 04 O Ο Ο Ο 2 ffl ffl ffl rH co co co u fc fc fc co rH rH tH fc o u Ο in O' O' OS «Η r-i »H rH ffl ffl ffl ffl CO tp Tp in rH rH iH rH u u U u 1 0 1 1 0 1 1 1 μ 0 Ή μ «μ 0 *H 0 μ β 0 β μ β β 0 Φ β φ 0 Φ rH β μ rH μ β μ μ rH φ μ Φ rH φ •Η ΜΗ 0 •μ ο μ □ μ φ •μ φ μ φ •μ φ μ ό μ ο μ 0 μ ο 1 Ή μ μ ι μ μ μ “ rH I 0 - 0 1 0 CM ·Η — rH 04 γΗ - γΗ 1 β CM β 1 β CM β — Φ ι υ ϋ I υ Η μ ,— ι Η 1 1 >1 Φ rH ΟΙ >ιΟ4 rH 04 β ϋ 1 β ι >ι 1 μ Φ β rH μ γΗ β Η Φ 0 μ >1 Φ >1 μ >, ε μ Φβ ε λ φ β > 0 ε μ μ ε μ X Η >1 Φ X Φ >1 Φ 0 β χ ε ο ε χ ε λ υ 0 ι fc 1 0 ι 0 ι Οΐ- 0 - μ - μ οι Ο so μ ko β kO fc ι μ ι fc ι β f 0 Ή fcrH 0 Η 0 Η ω > 1 > ω > ω >ι •μ β β β Φ •μ β Φ •μ β Φ μ — μ Ό μ Ό ~μ Ό ι Φ ι Φ ·μ 1 Φ ·Η 1 Φ ·Η ffl ε 2 β fH 2 ε·-Η 2 ε «η co τρ m kO U W ffl ο ε ζ ο; I o in · co o o ffl CO fc CM o ffl I I μ μ ο Φ β u ι—I Φ μ o •H JH μ o +J rH I ti - 0 Ol I I 04 I rH iH >1 >1 β Λ μ -μ Φ Φ ε ε >1 I X ο '•β ti I Φ μ rH Τ3 ω >ν«Η εΛ-« — Η-> ·Η 1 Φ β ζ ε φ ο μ β φ -η o μ φ - β 04 ϋ I 1 ~ 04 Η I S ιΗ β >1 μ β Φ μ ε φ >ι ε κ ι ο μ ko β I β Ή >1 β β μ ι Φ ε anilide N— ( sec-butoxymethyl)-2 ’-tri fluoro- C. j-H. pClF,N02 135-142°C methyl-6 1-methyl-2-chloroaoet- (0.05 ) anilide ο- oo σ» -13rt C Ο Ό C fi 0 tt tt rt tt ih Ό rt Φ CO rt c (0 rt fi υ rt CO o Ν* ΓΓ- rt CN Ν' Ν* Ν' © Ν' rt TO Ν' Μ,η* ιη ιη ιη σι ο CD m ηι oo -e σι η ιη-ι μ ιοοαι σιη,Μ „ £ ωιοΗ ,ιοη Hirw πΐιή^ ω ιή cr © in m U X 2 Ο X 2 0X2 0X2 0X2 0X2 Ο ο cr in TO r-s rt CN I O Φ rt ll rt Ort rt O ίο i—I rt I o rt rt □ rt •Η fi ll 6 •H ll α o ε tt w Φ rt CU » ε ο co 2 X tt I o li I rt Φ rH U rt io •rl 0 Ρ M rt 0 I rt - X! CN 0 I I —. CN rt | >1 rt x >% rt x φ rt ε φ >i E κ ι o <—i © > I Φ rt rt Ό rt >irt (0 X rt — rt rt Φ c ε φ CN CN CN 1 o O o O 2 2 2 2, TO TO TO tt tt tt tt ι—I «—1 i—1 rt o O o o TO rt r*. rH CN rt X X X X( Ν’ © Ν’ rt ι—1 rt o O o o i 0 1 0 1 M li 1 rt o ll rt rt x ι υ - ι CN CN I I ·—> rt rt >x x rt rt φ φ ε ε ι >1X © I rt rt >i >ι Φ TOX Ό ii rt rt <0 Φ •h3 V1 CN 1 >1 ?x rt f Φ J *W O rt M M 0 rt rt I X - 0 CN I I CN — I o TO tt S3 in θ >, Φ ί X Ό >rt rt I Φ >t >« X X rt rt φ φ >1© ct ε rt 5 έ -h O 1 Φ 0 o c ° O C X rt Ό It li co “ H <0 rt >irt cu o rt •rt 0 +> Φ X H fi φ J 1) rt rt 1 rt o 1 Η O 1 Φ c 2 Uh co 2 M-i co s ε <0 I rt li rt ι ι ™ . ι CN Γ* H +> WOO) Λ I Ό 4J - -H a) oh ε 1 -η Sc-· fi X >ιβ 0 Λ+Ι a-p ω ο ωο ί-l g (0 cu ρ o I £2 z ‘‘-o I rt — !>n Η X >+J X Φ Φ rt I Ό Q) - rt g © rt >t 1 *d « rt fi Q M CUX rt O +J 0) li Φ O cue φ ooo M It ll rt O O — firt I r-i XJ 2Ή O - 14 The secondary anilide starting materials used in the above examples to prepare the compounds of this invention are suitably prepared by conventional chloroacetylation of the appropriate primary amine as exemplified in Example 16 below.

EXAMPLE 16 This example illustrates the preparation of the secondary anilide starting material used to prepare a species of the compound of this example, i.e. the compound of Example 13. 2-Trifluoromethyl-6-ethylaniline, 6.0 gm (0.03174 mol) was dissolved in 75 ml of toluene and 3.77 gm (0.033 mol) of chloroacetyl chloride added cautiously. The resulting slurry was raised to reflux temperature and held for 4 hours. Thereafter, the mixture was diluted with an equal volume of hexane and the mixture let stand. The product crystallized and the resulting solid was filtered and air dried to give 5.8 gm (69% yield); the filtrate was stripped to produce another 2.7 gm of white solid, m.p. 121-124°C (sealed tube).

Anal, for C^H^lFgNO (%) Element Theory Found 49.36 C 49.73 H 4.17 4.09 N 5.27 5.38 The product was identified as 2'-trifluoromethyl-6'-ethyl-2-cloroacetanilide.

Primary amines of the type used to prepare secondary anilides by haloacetylation as described above are known in the literature; see, e.g., the above-mentioned U.S. Patent 3,966,811 and Irish Patent Specification No. 48057.

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 also been shown. The preemergence tests referred to herein include both greenhouse and field tests. In the - 15 greenhouse tests, the herbicide is applied either as a surface application after planting the seeds or vegetative 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 the field tests, the herbicide may be applied pre-plant incorporation (P.P.I.) into the 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, or the herbicide may be applied to the surface (S.A., surface application) after the crop seed is planted.

The surface application (S.A) 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 6.99 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 a level 0.5 inch (1.27 cm) from the top of the pots. The pots are then seeded with plant species to be tested, covered with a 0.5 inch layer of the test soils. The herbicide is then applied to the surface of the soil, e.g., with a belt sprayer at 20 gal/A, 30psi (187 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 needed. As an alternative procedure, the overhead irrigation may be omitted. Observations of herbicidal effects are made about three weeks after treatment.

The herbicide treatment by soil incorporation (S.I.) used in the greenhouse tests are as follows: A good grade of top soil is 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 is placed a number of seeds or vegetative - 16 propagules of various plant species. The soil required to level fill the pans after seeding or adding vegetative propagules is weighed into a pan. The soil and a known amount of the active ingredient applied in a solvent or as a wettable powder suspension are thoroughly mixed, and used to cover the prepared pans. After treatment, the pans are given an initial overhead irrigation of water, equivalent to one-fourth inch (0.64 cm) rainfall, then watered by sub irrigation as need to give adequate moisture for germination and growth. As an alternative procedure, the overhead irrigation may be omitted. Observations are made about 2-3 weeks after seeding and treatment.

Tables II and III summarise results of tests conducted to determine the preemergence herbicidal activity of the compounds of this invention; in these tests, the herbicides were applied by soil incorporation and sub-irrigation watering only. 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 0 -49 1 50-74 2 75-100 3 Undetermined 5 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 1egend: A Canada Thistle B Cocklebur C Velvetleaf D Morningglory E Lambsquarters F Smartweed G Yellow Nutsedge H Quackgrass I Johnsongrass J Downy Brome K Barnyardgrass -17Tablo II Pre-Smcrgent Plant Gpecies Compound of Example Mo. kg/h Λ B r· 0 j? F G Ί I 1 1 11.2 5 9 9 3 3 3 3 9 9 9 3 5.6 5 9 9 1 3 9 7 9 9 3 9 9 11.2 9 1 1 3 2 2 3 9 9 3 3 5.5 9 2 1 3 2 3 3 2 2 9 J 9 7 11.2 3 1 9 3 3 3 9 9 2 9 9 5.5 9 3 9 9 9 2 3 3 1 3Ί A ’1.2 5 3 9 3 3 9 3 3 3 9 3 5. G 5 2 1 2. 3 3 3 3 3 9 ς 11.2 5 3 2 3 3 3 9 9 3 3 3 5.5 5 G n 3 3 9 3 1 3 3 S 11.2 5 2 1 3 3 3 3 9 3 3 3 5.5 5 9 0 1 J 3 3 7 9 3 3 7 1’ .2 3 1 2 2 9 0 2 g 1 3 9 5.5 I 0 1 1 3 0 1 9 1 9 3 3 11.2 3 9 o 2 9 9. .3 9 3 g 9 5.5 9 1 P 9 9 3 32 2 3 3 n 11.2 9 9 9 3 9 3 9 3 3 9 3 5.5 3 2 1. 2 ? 3 3 9 1 3 3 1 0 11.2 9 9 1 9 3 9 J 9 3 3 9 9 5.5 3 1 1 L 2 3 9 9 5 n 3 3 1 1 11.2 9 1 1 3 3 3 3 3 n 3 g 5.5 3 1 1 9 3 3 1 3 1 3 3 ] 2 11.9 g 9 0 9 3 3 3 9 e 3 3 5.5 3 1 0 2 1 2 3 3 9 3 3 13 11.2 3 2 2 3 3 3 3 9 3 3 3 5.5 3 2 9 3 3 9 3 3 2 3 3 The corapo unds were further test ed by utilizing the above proce? •lure on the following plant species : -18L Soybean M Sugarbeet N Wheat 9 Rice p Sorghum B Cocklebur Q Wild Buckwheat D Morningglory R Hemp Sesbania E Lambsquarters F Smartwead C Velvetleaf ,1 Downy brome S Panicum Spp.

K Barnyardgrass T Crabgrass The results are summarized in Table Table III Pre-Emergent III. Compound of Example No. kg/h LMN9PBQDREFCI '5 il 1 5.5 1233303333323 3 3 3 1.12 0 1 1 2 3 0 1 2 2 3 2 0 3 3 3 3 0.23 0102101033302 3 3 3 0.055 0000000011100 2 2 3 0.0112 9000000C01100 1 2 2 ? 5.5 1 3 233123^3303 3 3 5 1.12 0323201312203 3 3 5 0.28 0201100111003 3 3 5 n.055 010000C000001 13 5 0.0112 0000000000000 0 1 5 3 5.5 0333313333313 3 3 3 1.12 01133103130^3 3 3 3 0.28 00022n0903001 3 3 3 0.055 0001000002300 3 3 3 0.0112 ooooooooniooo 3 3 3 0.005-5 00000000 0 3 000 1 0 1 4 5.5 2333323333313 3 3 3 1.12 1323313233313 3 3 3 0.23 0122101013202 3 3 3 0.055 0111221021100 2 2 3 0.0112 0190000001000 3 3 3 5 5.5 1233313333313 3 3 3 1.12 0223302023303 3 3 3 0.28 0213322323303 3 3 3 0.055 0101212013102 3 31 0.0112 0100011003101 2 3 3 -19AG—1245 Tahle III (Cont'd) P re-Emerqent Compound of Exanple No. kg/h LMNOPBQDRSFCJSKT .5 1333323333313333 1.12 0103313313303333 0.23 0202222133303333 0.05-5 020121222310233? 0.0112 02010222231011 3 3 .5 0322302223003333 1.12 0100101002000233 0.23 0000001200000223 0.055 0101000003200023 .5 2333323333313333 1.12 1233302013303333 0.23 0121202021102333 0.055 0011100001101333 0.0112 1000010010001023 1C .5 2233323332313333 1.12 1233113122203333 C.2S 12232011211 0 3 3 33 0.055 0000000002102333 0.0112 0000000000000033 .5 3333323333303333 1.12 1233303322303333 0.23 0222201023203333 0.055 0101000010000333 0.C112 0000000000000123 .5 0333313333313335 1.12 0313111212203335 0.29 0 2 1 2 1 0 0 0 1 1 1 0 3 3 3 5 0.055 01000000500 01235 0.0112 0100000 000000135 .5 1223312202103333 1.12 1212302212203333 0.28 0101001001001232 0.055 0500005000000020 .5 2333323333323333 1.12 1223302232303333 0.22 22331 01031303333 n.055 0111001000002333 n.0112 300000 901 5500022 -20The herbicides of this invention have been found to possess unexpectedly superior properties as preemergence herbicides, most particularly in the selective control of the hard-to-kill perennial and annual weeds, including such perennials as quackgrass, yellow and purple nutsedges; annual broadleaf weeds such as prickly sida, hemp sesbania, smartweed, lambsquarters, pigweed and annual grasses such as shattercane, alexandergrass, johnsongrass, Texas panicum, wild proso millet, red rice, itchgrass (Raoulgrass; Rottboellia exaltata) foxtails, e.g., green, yellow and giant) barnyardgrass, and large crabgrass. Weed stand reduction has also been achieved on other resistant species such as ragweed, velvetleaf, morningglory, cocklebur, purslane, etc.

Selective control and increased suppression of the above-mentioned weeds with the invention herbicides has been found in a variety of crops including, of particular interest, corn and soybeans, but others such as cotton, peanuts, rape, snapbeans (bush beans), wheat and sorghum; however, the latter two crops are usually less tolerant to the invention herbicides than are the other named crops; such reduced tolerance may be improved by the use of safeners, i.e., herbicide antidotes.

In the discussion and tables of data below, reference is made to herbicide application rates symbolized as GR^ and GR^g; 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 hy 1.12. defines the maximum rate of herbicide required to produce 15% or less crop injury, and GR^g defines the minimum rate required to achieve 15% inhibition of weeds. The GR^^ and GRO^ rates are used as a measure of potential commercial performance, it being understood, of course, that suitable commercial -21herbicides 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 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^/GR^g ratio, i.e., the GR^j rats for the crop divided by the GR^^ rate for the weed, both rates in kg/ha (lb/A). In the tables below, selectivity factors are shown in parenthesis following the GRn(- rate for each weed; the symbol NS indicates non-selective. Marginal or undetermined selectivity is indicated by a dash (-) .

Since crop tolerance and weed control are inter-related, a brief discussion of this relationship in terras of selectivity factors is meaningful. In general, it is desirable that crop safety factors, i.e., herbicide tolerance values, be high, since higher concentrations of herbicide are frequently desired for one reason or another. Conversely, it is desirable that weed control rates be small, i.e., the herbicide possesses high unit activity, for economical and possibly ecological reasons. However, small rates of application of a herbicide may not be adequate to control certain weeds and a larger race may be 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 made of selectivity factors (defined above) to quantify the relationship between crop safety and weed control. With reference to the selectivity factors listed in the tables, the higher the numerical value, the greater selectivity of the herbicide for weed control in a given crop. -22In 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 conducted in the greenhouse with compounds of the prior art most closely related in chemical structure to the invention compounds. Said prior art compounds are identified as follows (using the same nomenclature as for the invention compounds): A. N-(methoxyethyl)-2'-trifluoromethyl-2chloroacetanilide.

B. ,N-(ethoxyethyl)-2'-trifluoromethyl-2chloroacetanilide.

In Tables IV and V, preemergence herbicidal activity data are presented comparing tha relative efficacy of the invention compounds and said prior art compounds as selective herbicides against the resistant and troublesome perennial weeds quackgrass and yellow nutsedge in soybeans and corn, respectively. These weeds are commonly associated with such major crops as corn and soybeans. The test data in Tables IV and V were obtained under identical conditions and represent the average of two replicate runs (except for the compound of Example 13 which was present in one comparative test). The test procedure was the same as described for Tables II and ΠΙ, but modified by the application of an initial overhead irrigation equivalent to 1/4” (0.64 cm) rainfall; subsequent watering was accomplished by subirrigation. NS means non-selective within the test limits. -23Table IV Compound GR. . Rate (Kg/Ha) Soybeans GR__ Rate (Kg/Ha) Quackgrass Yellow Nutsedge A >2.24 >2.39 (NS) 1.13(1.93) 3 1.35 0.61 (3.21) 0.44 (4.45) Ex. 1 2.57 0.17(15.6) 0.17(15.6) Ex. 3 1.53 0.27(6.22) 0.19 (8.34) Ex. 4 1.12 0.13(3.52) 0.17 (5.59) Ex. 5 1.45 0.25 (5.52) 0.25 (5.62) Ex. 13 2.13 0.20(10.65) 0.17(12.53) Raferring to the data in Table IV, it will be noted that every invention compound exhibited exceedingly higher selectivity factors (values in parentheses) against both quackgrass and yellow nutsedge in soybeans 5 than the compounds of the prior art. In more particular, it is noted that the unit activities (relative phytotoxicity per unit of herbicide) of the invention compounds are markedly higher against quackgrass and yellow nutsedge than those of the prior 20 art compounds, while maintaining crop safety. Of special note are the outstandingly high selectivity factors of the compounds of Examples 1 and 13.

Further comparative data showing the relative efficacy of invention compounds vis-a-vis the above prior art compounds against quackgrass and yellow nutsedge in corn is presented in Table V. -24Table V GR,~ Rate Rate (5g/Ha) _(Eg/Ha) yellow Nutsedge Compound Corn Quackgrass A >2.24 >2.39(NS) 1.13(1.93) B 0.31 0.51 (1.33) 0.44 (3.94) Ex. 1 3.75 0.13(4.47) 0.17 (4.47) Ex. 3 1.94 0.27 (7.19) 0.19 (10.2) Ex. 4 9.75 0.13(5.35) 0.17(4.47) EX. 5 1.33 0.25 (7.04) 0.25 (7.04) Ex. 13 2.24 0.20(11.2) 0.17(13.13 Referring to the data in Table IV, it will be noted that every invention compound exhibited exceedingly higher selectivity factors against both quackgrass and yellow nutsedge in corn than the compounds of the prior art. Again, it is noted that unit activities of the invention compounds were markedly higher against quackgrass and yellow nutsedge than those of the invention compounds while maintaining crop safety. Particular note is taken of the large selectivity factors for the compounds of Examples 3, 5 and 13, especially in comparison to those of the prior art compounds.

From the comparative data shown in Tables IV and V, it will be apparent that the invention compounds exhibited outstandingly higher and unexpectedly superior herbicidal efficacy against the herbicidally resistant perennial weeds quackgrass and yellow nutsedge in two major crops, i.e., soybeans and corn, than Compounds A and 3, tha most closely related compounds in the prior art.

Additionally, preemergence herbicidal data from other tests have established that compounds according to this invention also selectively control quackgrass, -25yellow nutsedge and/or other weeds in one or more of the crops cotton, peanuts, bush beans, wheat, sorghum and/or rape. For example, in Table Vl are presented data showing the herbicidal selectivity of the compounds of Examples 1 and 3 against quackgrass in rape, snap beans, sorghum and wheat. Unless otherwise noted, greenhouse tests in Table VI and in other tables below involved herbicide treatments by soil incorporation and an initial overhead irrigation followed by subirrigation as described above.

Table VI GR.r Ra te (Kg/Ha) GR._ _ Ra fcs (Kq/Ua) Compound Rape Snapbeans Sorghum i'.'heat Quackgrass Ex. 1 0.35 - - 0.12 (7.2) 0.90 - - 0.12 (7.5) - 0.24 - 0.12(2.0) - 0.21 0.12(1.3) Ex. 3 1.9 . - 0.23(5.3) 2.24 - - 9.23 (3.0) - 0.34 - 0.23 (3.0) - - 0.28 0.28(1.0) The compound of Example 1 was also tested in the field to determine its preemergence selectivity against foxtail (spp), barnyardgrass and white proso millet in a plurality of crops; the data (representing three replicate runs) are shown in Table VII for both surface application (S.A.) and soil incorporation (PPI, i.e., preplant incorporation) of the herbicide. The seeds were planted in a fine seedbed of silt loam of intermediate moisture. The seeds were planted at a depth of two inches (5.OS cm). First rainfall 0.2; 0.51 cm) occurred the day following treatment, the second rain (0.25”; 54 cm) two days after treatment; cumulative rainfall 22 days after treatment was 1.3” (4.57 cm). Observations were made 5 weeks after t teatnent. -26rl Ο gas ί *P ω I id fl I fl it j >ι trJ in O O' o 1—1 § -rd •P •H a g Λ c Φ r—1 H 4-4 1 β 8 il £ x: 3 ω fl _ □ 71 O CO G OJ CQ 04 | 04 m i Λ fl -ul φαί ο ο ω n ft β| CM % SJi -P ο o t·· r*> Ό s E £8 S•M r-4 ·!“} a. -p r £S: TJ y o co cn cn c cun o .-4 Tf ω o > rc 04 t—I ro Tf Ol CO Ol CO m in 0% Ch m oi r·* cm r-r m m co r- m in 03 r—1 r-4 r-Η Ol in r- ο o Ol Tf o m o· © OJ Tf ο o in oi cn <1 ώΙ © οι Tf co in η CM Tf © r-d Ol Tf w Ci ft -27The data in Table VII show that, in general, the compound of Example 1 performed better as a selective herbicide in the surface application mode than when incorporated in the soil. In more particular, in the surface application tests the herbicide selectively controlled the three weeds in the test at application rates above 0.53 kg/ha (0.5 lb/Α) while maintaining crop safety (i.e., up to about 15% maximum injury) in field corn and soybeans up to 4.48 kg/ha (4.0 lb/Α) and safety in sweet corn, peanuts, and rape at greater than 2.24 kg/ha (2.0 lb/Λ) and in cotton, sorghum and bush beans at just under 2.24 kg/ha. In the PPI tests, the compound of Example 1 selectively controlled the foxtail species and barnyardgrass at less than 1.12 kg/ha (1.0 lb/Α) while maintaining crop safety in field corn, peanuts and rape at races up to 2.24 kg/ha and slightly below 2.24 kg/ha for soybeans.

Other field test data for the compound of Example 1 showed premergence selective control of other weeds in soybeans, corn, cotton and/or peanuts such as purple nutsedge, giant foxtail, yellow foxtail, lambsquarters, morningglory, cocklebur, velvetleaf, Pennsylvania smartweed, prickly sida, purslane, crabgrass, goosegrass, Texas panicum, Florida pusiey and/or bristly starbur. It will be understood by those skilled in the art that not all of the named weeds are selectively controlled in all of the named crops under all conditions of climate, soil, moisture and/or herbicide application modes. Selectivity data for control of the foregoing weeds in the crops soybeans, corn, cotton and peanuts from a plurality of field tests in various locations under various conditions of soil, moisture, etc. is shown collectively in Ta.bles VIII-XI, respectively. In the tables WAT means Weeks After Treatment of the plants with the herbicide, applied either by surface application - 28 (S.A.) or by preplant incorporation (PPI) in tbe soil; application rate data for each crop/weed combination is shown in terms of GR^g and GRg5 rates (defined above) ; the GR15/GRg5 ratio resulting in the selectivity factor, S.F.; NS indicates non-selective and a dash (-) indicates marginal or inderterminate slectivity, e.g., because actual GR-|g and GRgg rates were higher or lower than maximum or minimum rates used in the indicated test). In Tables VIII-XI, a blank.indicates that the plant species was not in a particular test plot or that the data was not obtained or was less significant than other data presented, e.g., some 3 WAT observations are omitted in favor of 6 WAT data or WAT data omitted because the 3 WAT data was definitve Table VIII Com- pound Crop/Weed Combination Appln. Mode WAT —15^R85 G.F. Ex. 1 Soybeans/Giant S.A. 3 foxtail 5 4.48/ 1.12 ( 4.0) P.P.I. 3 5 >4.48/41.12 (>4.0) 8 >4.48//1.12 (>4.0) Soybeans/Yellow foxtail S.A. 6 2.52/2.8 (NS) P.P.I. 6 1.4/41.12 (>1.3) Soybeans/ Lambsquarters S.A. 6 2.52/2.52 (1-0) P.P.I. 6 1.4/2.8 (NS) Soybeans/Pennsylvania SmartWeed P.P.I 8 4.43/2.52 (1-8) -29The data in Table VIII show that the compound of Example 1 selectively controlled giant and yellow foxtails, lambsquarters and Pennsylvania smartweed in soybeans from 5-3 WAT by either the S.A. or P.P.I. modes of application.

Table IX Com- Crop/Weed Appln. pound Combination Mode WAT 3R1C/GR35 S.F. Ex. I Corn/Giant S.A. 5 4.48/41.12 (4.9) foxtai1 S.A. 5.5 >7.84/8.4 (NS) P.P.I. Ί 4.75/1.95 (2.5) P.P.I. 5.5 >5.72/4.43 (1.5) Corn/Morning- S.A. 3 >4.43/>4.43 ( - ) glory S.A. 5 >4.48/>4.43 ( - ) P.P.I. 5 4.75/>4.43 ( - ) P.P.I. 5 4.75/M.4S ( - ) Corn/Cocklebur S.A. 3 >4.48/>4.43 ( - ) S.A. 5 >4.43/>4.43 ( - ) P.P.I. 3 4.75/>4.48 ( - ) P.P.I. 5 4.75/>4.4C ( - ) The data in Table IX show that the compound ι Example 1 selectively controlled giant foxtail in corn from 5-5.5 WAT by either the S.A. or P.P.I. mode of application; selectivity of morningglory and cocklebur was undetermined at test rates, but suppression of these weeds was exhibited. -30- Table X Com- Crop/Weed Appln. pound Combination Mode WAT 2^15ZSSg5 S.F. Ex. 1 Cotton/Purple S.A. 5 3.54/1.53 (2.17) nutsedge S.A. 9 3.35/2.24 (1.5) P.P.I. 5 3.35/4.2 (NS) Cotton/Prickly S.A. S 3.54/3.03 (1.13) sida S.A. 9 3.35/4.75 (NS) P.P.I. 5 3.35/4.75 (NS) Cotton/Purs- lane S.A. 9 3.35/1.96 (1.7) Cotton/Crabgrass (smooth S.A. 7 1.4/<1.12 01.25) and hairy) P.P.I. 7 0.84/1.12 (43) Cotton/Goose- P.P.I. 7 0.34/41.12 ( - ) grass Tha data in Table X show that the compound of Example 1 selectively controlled purple nutsedge and purslane up to 9 WAT, prickly sida up to 5 WAT and crabgrass up to 7 WAT; control of goosegrass was marginal or indeterminate.

In Table XI is presented preemergencs activity data for the compound of Example 1 against three resistant annual weeds, i.e., Texas panicum, bristly starbur and Florida pusiey in peanuts for periods up to 12 WAT. The data in Table XT represent the average of three replicate runs in sandy loam soil having 1.3% organic matter, 79.2% sand and IC'i clay; herbicide surface applied.

CM -31to rt Φ μ rt ο ω rt fi U-. pu co X Φ ι—I £ CO H 4-> c Φ CJ μι Φ pu ta cO * Φ E-* CJ rt c co P4 CM o m co cd PS φ 4-) bi co X & CM CM £ CO CO CO Mf Ό B o o.

ET -32Reference to the data in Table XI shows that the compound of Example 1 selectively controlled Texas panicum in peanuts for up to 3 weeks and provided a large degree of control even at 12 WAT with about a.43 kg/ha (4.0 lb/A); selective control of bristly stsrbur was achieved at 3.34 kg/ha (3.0 lb/A) for 3 weeks and complete control maintained for 12 WAT at 4.43 kg/ha '4.0 lb/A) and selective control of Florida pusley was achieved with less than 2.24 kg/ha at 3 WAT and with 4.13 kg/ha 95% control was attained at 12 WAT.

In other greenhouse tests, compounds according to this invention have shown selective control of a variety of annual and perennial weeds in various crops. As further illustration, the compound of Example 1 selectively controlled purple nutsedge in both corn and soybeans, the respective crop/weed Ga^/GR^^ ratios (expressed in kg/ha) being 0.47/0.25 (S.F. = 2.7) ir. corn and 1.12/.25 (S.F. = 4.5) in soybeans. The compound of Example 11 has shown selective control of yellow nutsedge and quackgrass in corn and soybeans. The respective crop/yallow nutsedge Ga,./GRor ratios being >2.24/0.95 (S.F. = 2.4) in io 00 corn; 2.24/0.5 (SF = 4.5) in soybeans and the respective GR^/GR^^ ratios for both corn ar.d soybeans in quackgrass being >2.24/n.5 (S.F. = >4.5). In ·> test against yellow nutsedge in cotton, the 3.3^./0Π„ς ratio (average of two replicates) was 1.95/0.95 (S.F. = 2.1). Similarly, the compound of Example 13 exhibited selective control of yellow nutsedge in cotton and of quackgrass in wheat, the respective GR^,./GR03 ratios being 0.7/0.47 (S.F. = 1.7) in cotton and 0.53/0.47 (S.F. = 1.2) in wheat.

In one multi-crop test in the greenhouse, tha compounds of Examples 1, 13, 14 and 15 were tested against yellow nutsedge in cotton, soybeans, corn and rice; each compound was non-selective with respect to yellow nutsedge in rice. However, markedly high selectivities for yellow nutsedge in cotton, soybeans and corn were shown for each of the compounds in the test; the respective GRqg and GRgg rates for these compounds are shown in Table XTI; selectivity factors are shown in parenthesis after each crop.

Table XIIgr85 (Xg/Ha)GR15 (Xg/Ha) Com- pound Yellow Nutsedg e Cotton Soybeans Corn EX. 1 0.24 1.96 ( 3.2) 0.87 (3.5) 0.59( 2.9) EX. 13 0.21 2.52 (12.0) 1.95 (9.3) 2.52(12.0) EX. 14 0.33 2.3 ( 7.4) 2.24(5.9) 1.53( 4.4) EX. 15 0.44 2.8 ( 5.4) 1.95(4.5) 1.9-5( 4.5) further The tested conpounds of Examples 1 and 13-15 were against quackgrass in wheat, soybeans □ nd corn; each compound was found to be non-selectivs in wheat. The selectivity data for the above compound aga inst quackgrass in soybeans and corn is shown in Table XIII.

Table XIII gr55gri5 (Xg/Ha) (Xg/Ha) Compound Quackgrass Soybeans Corn Ex . 1 0.07 0.01 (11.5) 0.59 (9.9) Ex. 13 0.36 1.58 ( 4.7) 1.53 (4.7) Ex . 14 0.45 1.45( 3.2) 2.52(5.5) Ex. 15 0.75 1.95( 2.5) 2.24 (3.9) In yet other greenhouse tests of herbicidal e fficacy, the compounds of Examples 1 and 3 were tested against a number of annual grasses including resistant 15 weeds such as Texas panicum, seedling johnsongrass, shattercane, cilexancergrass, wild proso millet (panicum -34milicaeum) , rad rice and itchgrass. The results of these tests are shown in Table XIV; selectivity factors re noted in parentheses; a dash indicating marginal or jndetermined selectivity. -35I (Ω Α ΙΩ Ο (Π Ρ Ρ Η 0’ Φ ro υ ω -ρ rt oil CM · • in Ο Λ, • CO o ε Ο r-H ·Η r—f G fi fi b CU ι O r-H J Δ O rrt J *> φ Ρ d in cr ω έέ Ο Pl O Φ Ό Wrt r—f 0 rH •rt Ρ ·Η s cu ε rH Λ I I Ρ ω X Φ ΙΩ φ ro fi rrt G Ρ < fi tr} I P φ Φ P G P fi fi □ fi ω ro cm cn · * rH Ο A fi fi 0 P ro tr c • o (Λ (Ω o rH · • CO ο Λ o CM · • -M* Ο Λ ε W U fi ·<Η X G Φ fi cu P (Ω fi fi C 04 GJ fi Φ tn tr fi rrt * > 04 — 0 O ω ro I G ε fi o o u Qj -36Table χν Φ μ β X in οο X ο Ο Μ •Η φ β 4-> β -Ρ ΰΡ σ» β M2 ο Λ Ο ΓΜ CN cn >1 β ε β ο ι—I >1 μ >1 •μ 4J |Η φ ri CC μ β β •Η Λ φ Ό Ό ω >1 w £ •Η •Η CU β 5 μ μ >1 rt Λ ρ 0 0 β β β μ ι—) rt X ω 5 α fM Cm Χί ω -37The data in Table XIV indicate that the compound of Example 1 selectively controlled every annual weed in the test in soybeans. The compound of Example 3 exhibited positive selective control against all weeds, except Texas panicum, wild proso millet and itchgrass at the maximum test rate of 1.12 kg/ha; a higher rate would have been required to determine selectivity of the compound against the three weeds not exhibiting selective control at the test rate. j_q a distinct advantage of a herbicide is its ability to function in a wide variety of soil types. Accordingly, data is presented in Tabla χν showing the herbicidal effect of the compound of Example 1 on quackgrass in soybeans in a wide variety of soil types of varying organic matter and clay content. The herbicide treatments were by soil incorporation with seeds planted 0.375 in. (0.95 cm) deep, with 0.25 in (0.54 cn) overhead irrigation. Observations were made about three weeks after treatment. Selectivity factors ore shown in parentheses.

The data in Table XV show that the compound of Example 1 appears to be quite insensitive to soil types of varying organic matter content, exhibiting selective control of quackgrass in soybeans in soils ranging from 1.0% to 50% organic matter and clay content from at least 1.3% to about 37% The data on soybeans in Wabash silty clay was indeterminate in this test. Also, the indicated selectivity factors in sarpy and Drummer silty clay and Florida muck are minimum values, since the maximun test rate was 2.24 kg/ha and the herbicide was safe on soybeans at the same rate above 2.24 kg/ha.

Laboratory tests were conducted to determine the resistance of herbicides according to this invention to leaching into the soil and resulting herbicidal efficacy. In these tests, the compounds of Examples 1 and 4-5 were formulated in acetone and then -38sprayed at different concentrations onto a weighed amount of Ray silt loam and Drummer silty clay 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 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 through the filter paper and drainage holes. The pots were then allows to sit for three days at ambient room temperature. The treated soil in the pots was then removed, crumbled and placed as a surface layer on top of other pots containing the above soils seeded with barnyardgrass seeds. The pots were then placed on greenhouse benches, sub-irrigated and allowed to grow for 2-3 weeks. Visual ratings of percent growth inhibition compared to control (untreated) pots and fresh weights for barnyardgrass were recorded; the data from the control represents six replications and that for the test compounds three replications,- test data are shown in Table XV.

Fresh weights of the weed were not measured for the tests in Drummer silty clay loam soil. 39ι—j υ £ σ· I I I I ιιιι © m ο ο cm το Ο CM rt rt Ο Ο Ν > rt CM ο r- Ί* το CM rt Γ* CM O © rt rt CM Ο Ο O CM o Η ί 0) Γ—ι £ ι0 Η oooo oooo rt rt rt rt oooo oooo o r*» in o o or cn CM ο o in in ο ο σ> co rt rt O rt > rt in to oo o σι o in cm fi -•η ε 10 f-> 00 O CM O rt γ·* oo το O CM O rt rt tn > CO TO O CM O rt rt in o rt r* co το CM O rt rt m o 100 100 1.27 100 100 .08 100 100 .16 95 100 <0 X rt o CM CM 40_Barnyardgrass_ Percent Inhibition_ _Fresh. Weight (Grams) •H ω φ -μ ι—I •H ω fl i—ι o -P J-4 Φ § ft P I—I •H ω c -* Ή £ fl U ft '—'I Ο Ο Μ* γCM CT) in cm ro in © cm in «-ι Ο Ο ι—I CO CO H CM Ο τρ H O TP Tp Ο H > CM Tp r- © OH ΟΟΗΠ ©H © © ra © cm cn o o o o ©ooo H Η ι—I H Ο O TP CM ο o ra in Η ι—1 r· ra © © CM Ο H H in O «-ι ra τρ tp co σ> ω in ra in ra tp © or © H ο ο ο o ooo© Η ι—I ι—I H © © CM r-i © © σ» rOOO© © o © ra Η Η H σ» © © rra o ra h r-. oo © r». co © r·* co © OCMOH OCMOH O CN O rl H in © h tn ο h tn o Η rl r-l TP H o o © in t*» r- ra CO Tp O CO CM ra ra ra H > 00 O CM O r-4 in © TP in H © © .61 ft -41I I I I 1111 I I I I till I I I I I I I I tn tn d rt σ' τ5 rt nJ >1 β rt (fl CQ -H g (fl U οϊ -Ί Γ- 00 kO © CM O rt rt in o kO ΓΌ CM CM ko γ- σ CM kO O CM H CM CM rt P* CD VD O CM O rt rt m o (fl B Φ \ σ (fl B I—I © Ό I β ε ο ο ο Ο QJ -42Referance to the data in Table χνΐindicate that the compounds of this invention were quite resistant to leaching into the soil under varying conditions of rainfall. In particular, at the 2.24 kg/ha (2.0 lb/A) rate of application, each of the invention compounds controlled barnyardgrass under the equivalent of 11.15 cm (4.0 inches) of rainfall in Ray silt loam and Drummer silt clay loam soil except the compounds of Examples 1 and 5 in Ray silt wherein control was maintained under the equivalent of 5.03 cm (2.0 inches) of rainfall. Even at the low application rate of 0.14 kg/ha (0.125 lb/A), the compounds of Examples 1, 4 and 5 controlled barnyardgrass in Drummer silty clay loam under the equivalent of 5.93 cm rainfall.

Toxicology studies on the compound of Example 1 have indicated the compound to be quite safe. It is slightly toxic (OLDg0 2300 mg/kg; MLD^g >5910 mg/kg) and has slight eye irritation ar.d no skin irritation. Ho special handling procedures beyond normal precautions are deemed necessary.

Therefore, it will be appreciated from the foregoing detailed description that compounds according to tiiic invention have demonstrated unexpected and outstandingly superior herbicidal properties both absolutely and relative to the most structurally-relevant compounds of the prior art. More particularly, the compounds of this invention have proven to be outstanding selective herbicides, particularly in the control of hard-to-kill perennial and annual grasses in soybeans and corn, but also in peanuts, cotton and other crops. In more particular, compounds according to this invention exhibit outstanding control of persnnial weeds such as quackgrass and nutsedges and resistant annual grasses such as Texas panicum, itchgrass, wild proso millet, alexar.dargr-ass, seedling johnsongrass, shattercane -43and/or red rice, while also controlling and/or suppressing other less-resistant annual grasses and perenn i als. -44The lic-tbiciual compositions ot tnis invention including concentrates which require dilution prior to application contain at least one active ingreulent and an adjuvant in liquid or solid form. The compositions are prepared by admixing tne active ingredient witn an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in tne form of finely-divided particulate solids, granules, pellets, solutions, dispersions or emuxsions. Thus tne active ingredient can be used with an adjuvant such as a fineiy-diviaeu solid, a .Liquid of organic origin, uater, a wetting agent, a dispersing agent, an emulsitying agent or any suitable combination of these.

The compositions of this invention, IS particularly liquids ana wettable powaers, preferably contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition reaoily 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 effiUxSifying agents ate included Liuu-in, anionic, cationic and non-ionic agents can be usea with equal facility.

Preferred wetting agones ate axkyi benzene and aikyi naphthalene sulfonates, sulfated fatty alcohols, amines or acid amices, long chain acid esters of sodium isotnionate, esters of soaium suifosuccinate, suifateo or suxfonated fatty acia esters, petroleum sulfonates, sulfonated vegetable oils, uitertiary acetyienie glycols, polyoxyethylene derivatives of alkylphenols (particularly isooctyipnenoi ana nonylpuenoi) a.id polyoxyethylene uerxVatives of the mono-higher fatty acid esters of hexitoi anhydrides (e.g., sorbitan). Preferred dispersants are metuyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, -45poiymcric alkyl, naphthalene sulfonates, sodium naphthalene sulfonate, and the polymethylene bisnapntnalene sulfonate.

Wettable powders are water-oispersible 5 compositions containing one or more active ingredients, an inert solio 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 ana the nke. Examples ot suca extenuers include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powders compositions of this invention usually contain from about 0.5 to 00 parts (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parrs) of wetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 05 parts (preferably 5-50 parts) of inert solid extender, all parts being by weight of the total 2o composition. Where required, from about 0.1 to 2.0 parts ot the solid inert extender can be replaced by a corrosion lnmbitor of anti-foaming agent ot both.

Other formulations include dust concentrates comprising from 0.1 to GOs by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range ot from aoout 0.1-10% by weight.

Aqueous suspensions or emulsions may be prepared by stirring an aqueous mixture of a water-insoluble active ingredient ano an emulsification agent until uniform and then homogenized to give stable emulsion of very finely-divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so tnat when diluted and sprayed, coverage is very uniform, suitable concentrations or tnc-se formulations contain from about 0.1-60% preferably 5-50% by weight -46of active ingtecient, trie upper iimit ueiny Determined by the solubility limit of active ingredient in the solvent. in another form of aqueous suspensions, a water-immiscible herbicide is encapsulated to form microencapsulated phase dispersed in an aqueous phase. In one embodiment, minute capsules are formed by bringing together an aqueous phase containing a lignin sulfonate emulsifier and a water-immiscible chemical and polymetliyiene poiypnenylisocyanate, dispersing the water-immiscible phase in the aqueous phase followed by audition of a polyfunctiotial amine. The isocyanate ana amine compounds react to form a solid urea shell wall around pat'ticies of the water-immiscible cttemicai, tnus forming microcapsules thereof. Generally, tne concentration of the microencapsulated material will range from about 480 to 700 g/1 of total composition preferably 460 to 600 g/1. ιΜμηΗΜΜΙΜΜΜΜΜΜΜΜΙ* Concentrates are usualry solutions of active ingredient in water-immiscible or partially waterlmmisciore so,vents together with a surface active agent, suitable solvents for the active ingredient ot this invention include dimethyiformiue, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons ana water-immiscible ethers, esters or ketones.

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

The concentrate compositions herein generally contain from aoout 0.1 to 95 parts (preferably 5-o6 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, ail parts being -47by weigi.t bascu on tne total weight of emulsifiable oil.

Granules are physically stable particulate compositions comprising active ingreoient auhering to or distributee tnrough a basic matrix or an inert, finely-divided particulate extender. In order to aid leaching oi the active ingredient from the particulate a surface active agent such as those listed nereinherore c„n be present in tne composition. 3q Natural clays, pyrophyllites, illite and vermiculite arc examples oi operable classes ot particulate minera extenders. The preferred extenders are the porous, absorptive, preformed particles such as prerormeu ahd screened particulate attapulgite or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin ciays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the hetbicioui granules. 2o The granular compositions or tins invention may contain from about 0.1 to about 30 parts preferabi rrom about j to 20 parts by weight ot active mgrc-dien per 100 parts by weight of clay and 0 to about 5 parts by weight ot scitacc active agent per too paLts uy weight of particulate clay.

The compositions of tnis invention can jj.su contain other aoditaments, for example, fertilizers, other herbicides, other pesticides, safeners ana tne like used as adjuvants or in combination witn any of the above-descLlbeu adjuvants. Chemicals usetui in combination with the active ingredients of this invention include, for example, tnazmes, ureas, carbamates, acetamides, acetanilides, uraciis, aceti acid or pnenoi derivatives, thioicaibamates, tria2Oi benzoic acios, nitriles, biphenyl ethers and the like such as; -48Heterocyclic Nitrogen/ijuiiur Derivatives 2-Chloro-4-ethylamino-b-isopropyiamxno-s-triazine 2-Chioro-4,6-bis( isopropylamino)-s-tridzine 2- Chloro-4,6-bis(ethylamino)-s-triazine 3- Isopropyi-lH-2,1,3-benzothiaoiaain-4-(3H)-one 2,2 dioxide 3-Amino-i, 2,4-tnazoie 6,7-Dihydroaipyrloo (1,2-a:2', 1 '-cj-pyrazioiiniuin salt -Bromo--i-isopiOpyl-b-methyiuraCii i,1'-Dimethyl-4,4 '-bipyridimum Ureas N'-(4-chiorophenoxy) pheny1-N,N-dimethylurea H, N-uimethyl-N '-(3-chioro-4-ine thylphenyl) urea 3-(3,4-uichiorophenyl)-1,1-dimethylurea I, 3-Dimethy1-3-(2-benzothiazolyi) urea 3-(g-Chioropneny1)-1,1-dimethylurea 1- Butyl-j-(3,4-dichiorophenylj-i-metnyiurea Carbamates/Thiolcarbamates 2- Chioroaiiyi diethyldithiocaroamate S-(4-chlorobenzyl)N,N-uiethylthiolcarbamate isopropyl N-(3-chloropnenyi) carbamate -2,3-dichioroallyl N,N-oiisopropylthiolcarbamate Ethyl N,N-o ipropy1thιοίcarbama te S-propyi dipropylthiolcarbamate rtcetamiues/Acetaniligts/Aniiines/Amiues 2-Chloro-N,N-aialiylacetamide N,N-uimethyl-2,2-diphenyiacetaHiioe -49_ Ν-(2,4-aimec.ny.L-5- I 1 (trifluoroinetnyl)suxfonyxj amino)phenyl) acetamide N-lsopropyx-2-chxoroacetanxlxde 2',b'-Dxethyl-N-methoxymethyx-2-chloroacetanilxae 21-Methyx-61-ethyl-N-(2-methoxyprop-2-yl)-2cnloroacetanilide οί,αέ , oC -Trifiuoro-2,0-oxnxtro-N,Nd ipropyX-£-toxuid ine N-(x,i-αxmethyIpropyny1),5-d ichxorobenzaraxae IQ Acids/Esters/Alcohols 2,2-DichiOropropionic acid 2- Methyl-4-chlorophenoxyacetie acid 2.4- Dienxorophenoxyaeetic acid Methyl-2- l4-(2,4-dichiorophenoxy)phenoxyJ 25 propionate 3- Amxno-2,5-dxcn±orobenzoic acid 2-Methoxy-3,b-dichiorobenzoic acid 2,3, u-'i’r ichxoropheny lace tic acid N-l-naphthylphthalamic acxa aoaxum □-l2-cnioro-4-(trxtiuoromethyiJphcnoxyj-2nxtrobcnzoate 4,b-Oinx tro-o-scc-butylpnenox ' N-(phospnonomethyl) glycine and its Cj_b nionouikyi amine and alkaline metux saxts and eomoinations tnereof Ethers 2.4- Dichlorophenyl-4-nitrophenyl ether 2-Chioro- oi, aC , -trxfiuoro-g-toxyl-3-ecnoxy4- nitrodiphenyl ether 51688 -50Miscellaneous 2,b-Dichiorobenzonitriie Monosodiuin acid metiianearsonate Disodium methanearsonate Fertilizers useful in combination with tne active ingredients include, for example, ammonium nitrate, urea, potash ana superphosphate. Other useful additaments include materials in which plant organisms take root ana grow such as compose, manure, numus, sano and the like.

Herbicidal formulations ot the types described above are exemplified in several illustrative embodiments beiow.

I. Emuisifiabie Concentrates Weight Percent A. Compound of Example No. 1 50.0 Calcium doaecyibenzene sulfonate/polyoxyethyiene ethers biend ie.g., Atiox-' a437F) 4.35 Calcium aodecylbenzene sulfonate (FioMo uUH) U.i5 Cy aromatic solvent 45.00 IUO. UU B. Compound of Example No. 4 35.0 Calcium aoueeyi sulfonate/arkylaryl poiyetner alcohol blend 4.0 Cy aromatic hydrocarbons solvent il.U 100.00 -51C. Compound ot Example No. b 5.0 Calcium dodecylbenzene sulfonate/ poiyoxyecnylcne ethers biena (e.g., Atlox 3437F) i.O Xylene 94.0 100.00 Il. Liquid Concentrates A. Compound of Example No. 4 Xylene Weiqht Percent 10.0 90.0 100.00 B. Contpound of Example No. 5 85.0 Dimetnyi sulfoxiue 15.0 100.00 15 C. Compound of Example No. b 50.0 N-metnylpyrroiiaone 50.0 100.00 D. Compound of Example No. 7 5.0 Eti.cxyxated Cabtor on 2u. 0 20 Khoduinine B .5 Dimecnyi formamide 74.5 100.00 III. Emulsions A. Compound of Example Ho. 12 40.0 25 Poiyoxyethyiene/polyoxypropyiene brock uith Dutanoi ie.g. Tergitoio XH) 4.0 Water 56.0 luO.Uu -52B. Compound of Example No. 5.0 Poiyoxyethylene/poiyoxypropyiene Ciock copolymer with butanol j.5 Water 91.5 100.00 XV Wettable Powders Weight Percent A. Compound of Example No. 1 25.0 Souium lignosulfonate 3-0 sodium N-methyi-N-oieyl-taurate 1.0 Amorpuous sinca (synthetic) 7i.u 100.00 B. Compound of Example No. 12 dU.O sodium aioctyl sulf’osueeinatu i.za Calcium lignosulfonate 2.75 Amorphous silica (syntuetic) ib.QO 100.UO C. Compound of Example No. 13 10.J souium lignosulfonate 1.0 Sodium N-methyi-N-oieyl-taurate 1.0 Kaolinite may ab.O iOO.OO V. Dusts Weight Percent A. Compound of Example No. 7 2.0 Attapulgite 0b.0 ίου.oo B. Compound of Example No. b bO.O Montmorillonite 40.0 100.00 -53C. Compouno of Example No. 9 Bentonite . 0 70.0 100.00 D. Compound of Example No. 10 Diatomaceous earth 1.0 99.0 100.00 VI. Granules Weiqnc Percent Compound of Example No. 1 15.0 Granular attapulgite (20/40 mesh) 35.0 Compound of Example No. 6 Diatomaceous earth (20/40) C. Compound of Example No. 12 Bentonice (20/40) D. Compound of Example No. 13 Pyrophyllite (20/40) VII. Microcapsules 100.00 .0 70.0 100.00 0.5 99.5 100.0U .0 95.0 100.00 Weight Percent A. Compound of Example No. 1 encapsulated in poiyurea shall wall 49.2 Sodium lignosulfonate (e.g.

Reax db<-B) 0.9 Water 49.9 10U.Ou -54li. Compound ot Example No. 12 encapsulated in poiyurea shell wall 10.u Potassium iiyriosuiionate (e.g., ReaX^C—21) .5 Water a9.5 100.00 C. Compound of Example No. 13 encapsulated m poiyurea shell waix bu.O Magnesium salt of iignosulfcte (Treax, L'l'M») 2.0 Water 18.0 IdO.OO When operating in accordance with the present invention, effective amounts ot the acetanilides of this invention are applied to the soil containing tne pxants, or are incorporated into aquatic media in any convenient fashion. The application of liquid ana particulate solid compositions to the soil can be Carried out by conventional methods, e.g., power ousters, boom and hand sprayers ana spray dusters. The compositions can also be applied from airplanes as a dust or a spray because oi their effectiveness at iow dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding tne compositions to the aquatic media in the area where control of tne aquatic plants is uesireu.

The application of an effective amount of the compounds of this invention to the locus of unaesireu 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 ana stage of development thereof, the type and condition of soil, the amount of rainfall ana the specific acetanilide employed. In selective preemergence application to the -55piants or to tne son a dosage of from 0.02 to about ii.2 kg/na, preferably from about 0.04 to about 5.bd Kg/na, or suitaoiy from l.i2 to 5.b kg/ha of acetanij. ide 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 aoove examples, the optimum rate to be applied in any particular case.

The terra soil is employee in its broadest sense Ιθ to be inclusive of all conventional soils as defined in Webster's New International Dictionary, second Edition, Unabridged (i96i>. Thus the term refers to any substance or media in whicn vegetation may take root ana grow, and includes not only earth but also compost, manure, muck, numus, sand and the like, adaptea to support plant growth.

Claims (64)

1. Compounds having the formula 0 wherein R is C-|_ 5 alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and R.| is hydrogen, methyl or ethyl; provided that: 5 When R-| is hydrogen, R is isopropyl and When R 1 is ethyl, R is ethyl, n-propyl or isopropyl.

2. Compounds according to Claim 1 wherein R is C 2 _ 4 alkyl.

3. Compounds according to Claim 2 wherein R 1 is methyl.

4. Compounds according to Claim 3 which is N-(ethoxymethyl)-2' 10 trif1uoromethyl-6 1 -methyl-2-chloroacetani Tide.

5. Compound according to Claim 3 which is N-(n-propoxymethyl)-2'trifluoromethyl-6'-methyl-2-chloroacetanilide.

6. Compound according to Claim 3 which is N-(isopropoxymethyl)-2‘tri f1uoromethyl-6'-methyl-2-chl oroacetani1i de. 15

7. Compound according to Claim 3 which is N-(isobutoxymethyl)-2'trifluoromethyl-6'-methyl-2-chloroacetanilide. - 57

8. Compound according to Claim 2 wherein R^ is ethyl.

9. Compound according to Claim 3 which is N-( ethoxyinethyl)-2'trifluoromethyl-6'-ethyl-2-chloroacetanilide.

10. Compound according to Claim 8 which is N-(n~propoxymethyl)5 2'-tri f1uoromethyl-6‘-ethyl-2-chloroacetani1ide.

11. Compound according to Claim 8 which is N-(isopropoxymethyl)-2 1 -tri f1uoromethyl-6 1 -ethyl-2-chloroacetanilide.

12. Compound according to Claim 2 wherein R-| is hydrogen.

13. Compound according to Claim 12 which is N-(isopropoxymethyl)10 2 1 -tri f1uoromethyl-2-chloroacetanilide.

14. Compound according to Claim 1 wherein R is a Cg_g alkenyl radical.

15. Compound according to Claim 14 which is N-(allyloxymethyl)-2'tri f1uoromethyl-6‘-methyl-2-chloroacetanilide.

16. Compound according to Claim 1 wherein R is a Cg_g alkynyl radical. 15

17. Compound according to Claim 16 which is N-(propargyloxymethyl)2'-tri f1uoromethyl-6'-methyl-2-chloroacetanilide.

18. Compound according to Claim 1 wherein R is an alkoxyalkyl radical having up to 5 carbon atoms.

19. Compound according to Claim 18 which is N-(2-methoxyethoxymethyl)20 2'-trifi uoromethyl-6 1 -methyl-2-chloroacetani!ide. - 58

20. Herbicidal composition comprising an adjuvant and a herbicidally effective amount of a compound of the formula 0 wherein R is alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and 5 R-| is hydrogen, methyl or ethyl; provided that When R^ is hydrogen, R is isopropyl and When R-j is ethyl, R is ethyl, n-propyl or isopropyl.

21. Composition according to Claim 20 wherein said compound R is C 2 4 alkyl. 10

22. Composition according to Claim 21 wherein in said compound R 1 is methyl.

23. Composition according to Claim 22 wherein said compound is N-(ethoxymethyl)-2 1 -tri f1uoromethyl-6‘-methyl-2-chloroacetani1i de .

24. Composition according to Claim 22 wherein said compound is N15 (n-propoxymethyl)-2 1 -tri f1uoromethyl-6'-methyl -2-chloroacetani1ide.

25. Composition according to Claim 22 wherein said compound is N-(i sopropoxymethyl)-2'-tri f1uoromethyl-6 1 -methyl-2-chloroacetani Tide.

26. Composition according to Claim 22 wherein said compound is N-(i sobutoxymethyl)-2 1 -tri f1uoromethyl-6’-methyl-2-chloroacetani1ide. - 59

27. Composition according to Claim 21 wherein in said compound R-| is ethyl.

28. Composition according to Claim 27 wherein said compound is N-(ethoxymethyl)-2'-tri f1uoromethyl-6'-ethyl-2-chloroacetani1i de. 5

29. Composition according to Claim 27 wherein said compound is N-(n-propoxymethyl)-2'-trif1uoromethyl-6'-ethyl-2-chloroacetani1ide.

30. Composition according to Claim 27 wherein said compound is N-(i sopropoxymethyl)-2'-tri f1uoromethyl-6 1 -ethyl-2-chloroacetani Tide.

31. Composition according to Claim 21 wherein in said compound 10 R-| is hydrogen.

32. Composition according to Claim 31 wherein said compound is N-(i sopropoxymethyl)-2'-tri f1uoromethyl-2-chloroacetani1i de.

33. Composition according to Claim 20 wherein in said compound R is an alkenyl radical having up to 5 carbon atoms. 15

34. Composition according to Claim 33 wherein said compound is N-(al1yloxymethyl)-2 1 -tri fluoromethyl-6 1 -methyl-2-chloroacetanil i de.

35. Composition according to Claim 20 wherein in said compound R is an alkynyl radical having up to 5 carbon atoms.

36. Composition according to Claim 35 wherein said compound is

20. N-(propargyloxymethyl)-2 1 -tri f1uoro-methyl-6'-methyl-2-chloroacetani1i de.

37. Composition according to Claim 20 wherein in said compound R is an alkoxyalkyl radical having up to 5 carbon atoms. - 60

38. Composition according to Claim 37 wherein said compound is N-(methoxyethoxymethyl )-2 1 -trifluoromethyl-6 1 -methyl-2chloroacetani lide.

39. Method for combatting undesirable plants in crops which 5 comprises applying to the locus thereof a herbicidally effective amount of a compound having the formula. wherein R is C^_g alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms and R-j is hydrogen, methyl or ethyl; provided that: When R-j is hydrogen, R is isopropyl and 10 When R 1 is ethyl, R is ethyl, n-propyl or isopropyl.

40. Method according to Claim 39 wherein in said compound R is c 2-4 alkyl

41. Method according to Claim 40 wherein in said compound R^ is methyl. 15

42. Method according to Claim 41 wherein said compound is N-(ethoxymethyl)-2'-tri f1uoromethyl-6'-methyl-2-chloroacetanilide.

43. Method according to Claim 41 wherein said compound is N-(n-propoxymethyl)-2‘-tri f1uoromethyl-6'-methyl-2-chloroacetani1ide.

44. Method according to Claim 41 wherein said compound is 516 9 8 - 61 Ν- (i sopropoxymethyl)-2'-tri f1uoromethyl-6 1 -methyl-2-chloroacetani1i de

45. Method according to Claim 41 wherein said compound is N-(i sobutoxymethyl)-2'-tri fIuoromethyl-6'-methyl-2-chloroacetanili de.

46. Method according to Claim 40 wherein in said compound is 5 ethyl.

47. Method according to Claim 46 wherein said compound is N-(ethoxymethyl)-2'-tri f1uoromethyl-6'-ethyl-2-chloroacetani1i de.

48. Method according to Claim 46 wherein said compound is N-(n-propoxymethyl)-2 1 -tri f1uoromethyl-6 1 -ethyl-2-chloroacetani Tide. 10

49. Method according to Claim 46 wherein said compound is N(i sopropoxymethyl)-2'-tri f1uoromethyl-6'-ethyl-2-chloroacetani1i de.

50. Method according to Claim 40 wherein in said compound R^ is hydrogen.

51. Method according to Claim 50 wherein said compound is 15 N-(isopropoxymethyl)-2'-tri f1uoromethyl-2-chloroacetani1ide.

52. Method according to Claim 39 wherein in said compound R is an alkenyl radical having up to 5 carbon atoms.

53. Method according to Claim 52 wherein said compound is N-(a Πyloxymethyl)-2 1 -tri f1uoromethyl-6'-methyl-2-chloroacetani1ide. 20

54. Method according to Claim 39 wherein in said compound R is an alkynyl radical having up to 5 carbon atoms. 51G98 - 62

55. Method according to Claim 54 wherein said compound is N-(propargyloxymethyl)-2'-tri f1uoromethyl-6'-methyl-2-chloroacetani1i de.

56. Method according to Claim 39 wherein in said compound R is an alkoxyalkyl radical having up to 5 carbon toms. 5

57. Method according to Claim 56 wherein said compound is N-(methoxyethoxymethyl )-2’-trifluoromethyl-6 1 -methyl-2-chloroacetanilide.

58. Method according to Claim 39 wherein said crops are corn, sorghum, soybeans, cotton, peanuts, bush beans, wheat and rape.

59. Method according to Claim 58 wherein said compound is N10 (ethoxymethyl)-2’-trif1uoromethyl-6'-methyl-2-chloroacetani1i de.

60. Method for combatting undesirable plants in corn which comprises applying to the locus thereof a herbicidally effective amount of N-(ethoxymethyl)-2 1 -trif1uoromethyl-6 1 -methyl-2-chloroacetani Tide.

61. Method for combatting undesirable plants in soybeans which 15 comprises applying to the locus thereof a herbicidally effective amount of N-(ethoxymethyl)-2'-trif1uoromethyl-6 1 -methyl-2-chlorocetaniTide.

62. Method for combatting undesirable plants in cotton which comprises applying to the locus thereof a herbicidally effective amount of N-(ethoxymethyl)-2 1 -trif1uoromethyl-6'-methyl-2-chloroacetani1ide. 20

63, Method for combatting undesirable plants in rape which comprises applying to the locus thereof a herbicidally effective amount of N(ethoxymethyl)-2'-tri f1uoromethyl-6 1 -methyl-2-chloroacetani1i de. - 63

64. Method for combatting undesirable plants in snapbeans which comprises applying to the locus thereof a herbicidally effective amount of N-(ethoxymethyl )-2'-trifluoromethyl-6'-methyl-2chloroacetanilide.