IE51697B1 - Herbicidal 2-haloacetanilides - Google Patents

Abstract

N-alkyl-2-haloacetanilide compounds, herbicidal compositions containing said compounds as the active ingredient and herbicidal method of use in various crops, particularly, soybeans, cotton, peanuts, rape, bush beans, etc. The herbicides herein are particularly effective against the hard-to-kill annual weeds Texas panicum, itchgrass, wild proso millet, alexandergrass, red rice, shattercane and seedling johnsongrass.

Description

Price 90p This invention pertains to the field of 2-haloacetanilides and their use in the agronomic arts, e.g., as herbicides.

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

As relevant to the invention compounds, which are characterised 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 postion, the closest prior art known to the inventor are U.S. Patent Numbers 3,268,584, 3,442,945, 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-alkyl15 substituted 2-haloacetanilide compound specifically disclosed by either of the '492 or '137 patents is propachlor, i.e., N-isopropyl-2chloroacetanilide, a well-known commercial herbicide; neither patent discloses any herbicidal data relative to propachlor. U.S. Patent Number 2,863,752 (Re 26,961) discloses compounds of a class encompassing propachlor (not specifically named) and homologs and analogs thereof. - 3 51697 Of the compounds within the scope of the '752 patent, propachlor was found to be the most herbicidally efficacious, hence, was developed as a commercial herbicide. Said '752 patent discloses that 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 lb/A (28 kg/ha). Additionally, N-ethyl-e-chloroacetanilide is a named species in said '752 patent; yet, U.S. Patent No. 4,137,070 discloses that compound (Example 406 in the '070 patent) is an antidote for the herbicide EPTC.

In contrast to the foregoing '752 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 '945 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 2'-methoxy-6'-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 well as the particular alkyl radical attached to the nitrogen atom. Said Example 13 in said '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 radicals, respectively, attached to the ortho positions of - 4 the anilide molecule.

U.S. Patent No. 4,146,387 discloses 2-haloacetanilide compounds which may be substitued with alkyl radicals on the nitrogen atom and in both ortho positions. The compounds of the '387 patent are described as known herbicides of the type disclosed, e.g., in the above-mentioned '945 and '752 patents, including propachlor.

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 and analogous 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 millet, alexandergrass, red rice, shattercane and seedling johnsongrass, while also controlling or suppressing a broad spectrum of other noxious perennial and annual weed, 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. Uith many prior art herbicides, weedcontrol is adequate only for 2 or 3 weeks, or, in some superior caes, perhaps up to 4-6 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 - 5 to soil longevity under normal weather conditions, is their susceptibility to leaching into the soil, hence, 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 effective in soils having small amounts of organic matter, they are ineffective in other soils high in organic matter or vice-versa. It 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 preplant soil 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 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 to provide a group of herbicial compounds which overcome the 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 and seedling johnsongrass, while also controlling or suppressing a broad spectrum of less-resistant perennial and annual weeds such as mentioned above, while maintaining crop safety in a plurality of crops including soybeans, cotton, peanuts, rape, bush 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 10 resist leaching and dilution due to high moisture conditions, e.g., as heavy rainfall.

Still 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 in the mode of application, i.e., by preemergence surface application and by preplant soil incorporation.

Finally, it is an advantage of the herbicides 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.

The present invention relates to herbicidally active compounds, herbicidal compositions containing these compounds as active ingredients and herbicidal method of use of said composition in various crops. - 7 It has now been found that a selective group of 2-haloacetanilides characterised 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 unexpectedly superior and outstanding herbicidal properties vis-a-vis prior art herbicides, including the mostclosely-related 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 a plurality of crops including, particularly, soybeans, cotton, peanuts, rape, bush beans (snap beans), alfalfa and others as well. 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 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 other less-resistant perennial and annual weeds.

The compounds of this invention are characterised by the formula 0 '2' •R •OR51697 wherein R is methyl or ethyl; R^ is a alkyl radical, preferably C35 alkyls; R2 is methyl, ethyl or t-butly, preferably methyl, and R3 is hydrogen or methyl in a meta position, preferably hydrogen; provided that: When R is ethyl, is n-butyl, R^ is methyl and R3 is hydrogen; When R3 is methyl, R and R^ are also methyl and R-j is isopropyl or n-butyl; When R3 is hydrogen and R and R^ are both methyl, R-j 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 When R2 i s ^t-butyl, R and R^ are both methyl.

Preferred compounds of this invention are as follows:N-methyl-2'-isopentyloxy-6'-methyl-2-chloroacetanilide.

N-methyl -21-n-propoxy-6'-methyl-2-chloroacetanilide.

N-roethyl-21-n-butoxy-61-methyl-2-chloroacetani1ide.

N-methyl-21-sec-butoxy-6' -methyl-2-chloroacetanilide.

N-ethyl-2'-n-butoxy-6'-methyl-2-chloroacetanilide.

N-methyl-2'-isopropoxy-61-methyl-2-chloroacetani!ide.

N-methyl-2'-i sobutoxy-6'-methyl-2-chloroacetanilide.

N-methyl-2' - i sopropoxy-61-ethyl-2-chloroacetanilide.

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.

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 - 9 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 British Patent Specification No. 2 094 783.

Example 1 This example describes the preparation of N-methyl-21-n-butoxy6'-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. 21-n-butoxy-6'-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 CH^Clj 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 MgSO4 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 reerystallised upon standing to a colorless soild, m.p. 41-42.5°C. Anal. Calc'a for C14H2f)ClN02 (%): 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-2'-n-butoxy-61-methyl-2cloroacetanil ide.

Example 2 To a chilled (15°C) mixture of 2'-n-butoxy-6'-methyl-2chloroacetanilide, 5.6g (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 5169? - 10 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 4.1 g (66% yield) of a clear liquid, b.p. 114°C at 0.05 mm Hg.

Anax. Calc'd tor Ci5H.;2CiNU2 (<): C t bJ.4b; H, 7 . ox; Cl, 12.49. Found: c, ϋJ.5u ; H, 7. bi; Cl, 12.48.

The product was identified as N-ethyl-2'-n-bUtoxy-6'methyl-2-cnloroacetaniiiue.

Examples 3-19 Following substantially the same procedures, quantities of reactants ano general conditions described in Examples 1 and 2, but substituting the appropriate sec-anilide to obtain the corresponding N-alkylated end product, other N-methyl-2-halpacetaniliues accoraing to the above formula were prepared; these compounds are identified in able 1. - 12 Example Empirical B.P. °C _Analysis_ No. _Compound_ Formula (mm Hg) Element Calculated Found ©O'? CO CM o © o © © σ» cn © cm cn cm σι CM in r-i M* ΓΠ rt Γ- m CO Φ 00 Η r* r-i in ι—( © © co η· m © cn M1 ri CM If) rd © p- © <*> Ρ» CM © r- cn cm r** m r-i r- cn cm ρ* cn cm r* m cm r» cn σι © n· © rd © r-i © H © rd © rd © rd © rd in rd CO ri © m σι © cn p* n* in σι © cn r* -φ cn ρ- n* cn p- m* cn p- r- CO ’Φ Q O CO cn -φ η o o 00 cn «φ h cn M· rd m *Φ rd © © © cn P- CM H r* m cm r- cn rd cn cm r* m cm > cn cm P- cn σι © «Φ © ri © r-i © H © «rt © rd © rd © ri in rd rd υ sc υ 1—i U S3 U rd QSU rd a® a rd OB □ rd UM U rd umu H UMU ©«— . o eo · o in © in p* cn ΙΠ rd in cn rd fit m CL CM o r-i cn h CM o © © rt * ri © rd · o' e p- g o o o © © σι m »—» CM CM CM CM CM CM CM CM o o o o o o O O z z z z z B z r-i rt rd rd o u o u ϋ U U o CM co o co O © O © CM CM ri CM CM CM H 33 33 as S3 33 S3 33 33 m cn Φ M* •Φ CM rd rd rd rd rd U U o CJ a U O U 1 f > 4J 1 ! P iii >+> 1 >i I ι i 1 +1 0) 1 P X 0) >i 0 X a) X OJ X -P >, 0) 0 01 η ό X □ 0 0 0 o 0 01 X 0 1 fi 0 4-1 (Q 0 CO P nJ α β Q. 0 0 nJ > 0 I β c o ά o β 0 0 0 0 nJ P 0 X rt >1 0 ni rt 0 rt £3 5-1 rt rt P 0 β id 0 0 X rt Qj O rt 0 1 0 a o CLP Λ 0 0 0 0 rd O r-i 0 —1 0 0 0 H P 43 £3 rd 03 JS 1 43 01 43 in 43 in η in 43 0) 0 P £3 •rt υ c o in o •«d 0 •ri 43 •rt 0 £ I QJ U , i 1 1 1 ( i ( 1 0 ) I I CM 1 1 - - CM - CM • CM - 1 - CM - 1 - CM CM J CM I CM 1 CM CM 1 CM rt CM J 1 H 1 H 1 r-i 1 rd i i 1 ri I >< 1 ri H >i rd >< ri rt rd >1 rd P rt in j? tr: >iXJ OJ >t43 Φ >,43 0) >i > 0) 5pj3 aj X3 0) >,43 OJ XJ jj Ό 43 Ρ T3 43 Ρ Ό jM Ρ Ό 43 j3 Ό χ; +J Ό Λ Λ Ό 43 -Ρ Ό 4J fil »rd 4J 0) Μ 5 fl) Ή 5 fl) -d Ρ P -rt 53 Φ dJ I ri P 01 «rt OJ grH OJ 6 H OJ EH S 1 -i-i 0) £ rd ε 1 Ή QJ Q) rt g I -ri SB e-i ε 1 Ή QJ 4J rd g 1 Ή QJ E rt g 1 rt ι · n 1 - β i - β 1 - β ι - a i - fi I - β 1 - β S © β ΖΌ Ιί 2 UJ nJ Ζ © β Ζ © β J5 Ό «J Z © β 2 it! cn M· in © Γ-» © σι o rd cn m m 10 rrt © σ» rrt in γιο co .-η rt* O CO in co rt* VO CN CN tn co in σι rrt vo in rrt σι co m in in co rt* N* rrt co co oo in m in CO CO P* CN irt » 1 r- CN IO co CO [— CN CO Γ- CN rt* 00 rrt CO Γ— CN vo rrt 10 rrt VO VO rrt VO rrt V0 irt VO frt VO rrt σ» *ί·σ» rj· r— CO (fl •rt >+-l rt Φ (4 rt CO CN © in rrt σι CO rt cn rt* oo rt* co r- O' CO co ,47 .14 CO rt* .81 .49 oo rt σν rt* co rt* CO CN O in rt σι oo rt σι rt* oo rt* CO CN LO ι— co rt* rrt rt* 00 rrt CO P* CN CN r- in CN r- co CO t- CN CO Γ— CN rt* co rt co r* cn rt- CO vO rt VO rt VO VO rt VO rt vo rt VO rt VO rt VO rrt CJ S3 O rrt ί cj USJZ UBU UBU UBU CJ 2 O UBU (Cont'd) E CQ' rrt Φ id rrt rt fi ρ P •rt W Ca O g e fi fi §1 B o CT VO 1 f— x-s z—· O CO in rt tn rt rt CD f- rt* · vo CO © VO CO CN O CN rt 1 © CN © © © 1 CU rt O CN O CN rt * rt o • rt « rt · vo · rt · rt * 1— O O CN o O © •n* e © © rt •w* CN CN CN fN fN CN CN CN o O O o O o o o 2 2 2 2 2 2 2 2 rH rt rt rt rt rt rt u Cj CJ CJ a CJ CJ CJ rt* CN © o fN fN rt* CN CN CN CN CN CN CN fN CN 32 2 K 2 2 2 w 2 vo in rt* rt* in in vo in rt rt 1—1 rt rt rt rt rt u o CJ CJ CJ CJ CJ CJ I rrt I >|CN £ I P rrt φ >1 φ S£3 I P rt rrt φ rrt ‘rt I i fi -- id CN Ό P I 1 0) rrt -r*. □ >i >t Id £ X 0 POP Φ Ρ O g firt Φ£ cuo ι i p >1 Φ x o o id P 0 fi P Φ 0 firrt I £ fi o P p £ Φ §» 0 * S o 0 o- P o ?£ fi ϋ Pi-P X φ &s SP o fi<£ Ου W ι rt C\J CO I O P P Φ =3 U X5 ro O C *P Φ u I o >,$+ X θ υ fi I £<γ I I rrt I >i1 Φ S£ 3 I P -rt fN φ rt *** ε ·»η • · fi l rrt trt I £ Ν P I Φ rt φ ε * I Λ ·Η 5 Ο Φ Ρ Ό 3 ·»JO ι— ι—· ·Γ“ >> c _c φ Ρ Ρ φ φ ε υ (0 CN N J - IN CN 1 cn£ cn υ c\ij; CN - id vo P - 1 CN - id P I rt 1 rt 1 P I ι1 J i Φ 1 VO Φ rt rt rt ω rt -Η g rt — ϋ rt 1 ϋ >t£ Φ >ι£ Φ >,f= >ιΛ >1 >1 Id >1 — id £ P 3 £ P 3 £t3 (1) £ >) φ Λ-a £ X 0 £ r*1 O P Φ rt Ρ Φ rt Ρ Γ-a P .e ·σ 4J 1 X) P 0 p P X M Φ g rt φ g rt Φ- ·γ- Φ P 0 Φ 0 0 f 1 rt - fi g I rt T- fi gm »— c Or· = ε·ΓI εζ β νθ r1 -Λ c r fi rt Φ £ e -p < fi rt £ 2 vo id 2 vo id Ζ·λ § 2 3 Φ 2m ro •s fi< 0 2 £ ϋ <Ν >>-5 -c Ρ Ρ Φ φ ε ε ι ι Ζ ν£> Φ Ν* irt in rrt vo rrrt Η co στ rrt *“ Tile secondary aninues used «a starting materials in the above N-alkyiation process are prepared by known methods, e.g., naloacetylation of the corresponding aniline. For example, the starting sec-aniiiae used in Example 1 was prepared as follows: 2-n-butoxy-6-methylaniline, 27.4 g (0.0153 mol), in 250 mi of methylene chloride was stirred vigorously with a 10% sodium hydroxide solution (0.25 moi)) while a solution of chiocoacetyl chloride, 17.¼ gm (0.0154 mol), in methylene chloride was added over 30 ainuces keeping the temperature between i5-25°C with external cooling. The reaction mixture was stirred for a further b0 minutes. After tne addition was complete, the layers separated ana the methylene chloride iayer washed obtain with water, dried and evaporated in Vacuo solid, m.p. 127-128°C. to 28.3 g of a white Ansi » CS-lC 1 u for C,,H1SC1NO, (%): C, 61.05; H, 7.09; Cl, 13.86. Found: C, 61.04; H, 7. U8; Cl, 13.86.

The product was identified as 2'-n-butoxy-b'-methyl-2chioroacetanilide.

The secondary anilides used as starting materials in Examples 3-19 were prepared in a similar manner.

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

As noted above, the compounds of this invention nave been found to be effective as herbicides, particularly as pre-emergence herbicides, although post-emergence activity has oiso been snown. The pre-emergence tests referred to nerein include ooth greenhouse ano field tests. In tne greennouse tests, the nerbicide is applied eitner as a surface applicac.on after planting tne seeas or vegetative - 15 propayuJ.es or by incorporation into c quantity or soil to be applied as a cover layer over the test seeds in pre-sceueu test containers, in tne fiexc tests, the herbicide is pre-plant incorporated (P.P.I.) into tne soil, i.e., the nerbicide is applied to the surface of the soil, then incorporated therein by mixing means followed by planting of the crop seeas.

The surface application test method used in the greennouse 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 b.9a cm) or plastic pots 3.75 x 3.75 x 3 (9.53 cin x 9.53 cm x 7.62 cm) having drain holes in the bottom, are level-fiiied with Ray silt loam soil then compacted to a level 0.5 inch (1.27 cm) from tne top of tne pots.

The pots are then seeded with piant species to be tested, then coverea with a 0.5 incn layer of tne test soil. The herbicide is then applied to the surface of the soil with a beit sprayer at 2C gal/A, 30 psi (ia7 1/ha, 2.11 kg/cm ). Each pot receives 0.25 inch (0.64 cm) water as overhead irrigation ana the pots are tnen 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 mace about tnree weeks after treatment.

The herbicide treatment by soil incorporation used in greenhouse tests are as follows: A gooa graae of top soil is placed in aluminum pans and compacted to a depth of three-eights to one-haif inch from the top of tne pan. On tne top of the soil is placed a predetermined numDer of seeds or vegetative propayules of various piant species, 'ine soil required to level fili the pans after seeding or aoding vegetative propagules is weighed into a pan.

The soil and a known amount of the active ingredient appiieu in a solvent or as a wcttame powaer suspension are thoroughly mixed, and used to cover the prepared - 16 10 pans. Alter treatment, the pans are given on initial overhead irrigation of water, equivalent to one-fourtn inch (0.64 cm) rainfall, then waterec Dy subirrigation as needed to give adequate moisture for germination and growtn. as an alternative procedure, the overneao irrigation may be omitted. Observations are made about 2-3 weens 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 ano sub-irrigation watering only; a dasn (-} means that the indicated plant was not tested. The herbicidal rating was obtained by means of a fixeo scale based on tne percent injury of eacn plant species. The ratings are defined as follows: % Control 0-24 25-49 50-74 75-iOU The plant species tests, the data for which are shown in Table II, art identified by letter in accoruance with the following legend : Rating utilized in one set of A Canada Thistxe E Lambsquarters I Johnsongrass B Cockleour C Velvetleaf D Morninggiory F Smartweed G Yellow Nutsedge H Quackgrass J Downy Brome K Barnyardgrass - 17 Table II Pre-Emergent Compound of Example No. 4. kg/h Plant Species ABCDEF6HI J K 11.2 .6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 1.12 11.2 .6 11.2 ,6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 11.2 .6 33333333333 32233333333 1 1 2 3 3 - 3 3 3 3 0 1 1 3 3 - 3 1 3 3 32333333333 3 1 3 2 3 3 3 3 2 3 3 32333333333 1 3 2 3 3 3 3 3 3 3 32333333333 32333333333 32233333333 32233333233 33333333333 1 2 3 3 3 3 3 3 3 3 32333333133 32223333333 30333333333 3 0 2 3 3 3 3 3 3 3 3 20233123133 22333333333 3 1 3 2 3 2 2 3 2 3 3 32233333333 22223233333 2 2 3 3 3 3 3 3 3 3 1 1 3 3 2 3 3 2 3 3 - 2223333-33 - 1 1 1 3 3 2 3 - 3 3 31333233333 002332331 33 1 2 3 3 3 3 3 3 3 3 0 1 2 2 1 3 2 0 3 3 1 1 2 3 3 3 3 3 3 3 20003233333 - 18 Tabie II (Cont'u) Pre-Emergent Plant Species Compound of Example Nc ). kg/ha A B C D E F G H I J K 17 11.2 3 1 1 0 2 3 3 3 3 3 3 5.t) 3 0 2 2 3 2 3 3 3 3 J 18 11.2 3 2 3 3 3 3 3 3 3 3 3 5.6 3 2 2 3 3 3 3 it 3 3 3 19 11.2 3 1 2 2 3 3 3 3 2 3 3 5.6 3 0 2 2 3 3 3 3 1 3 3 The compounds were further testea by utilizing the above procedure on the following plant species : L Soybean M Sugarbeet N Wheat 0 Rice P Sorghum B Cocklebur Q Wild Buckwheat D Morningglory R Hemp Sesbania E Lambsquarters F Smartweed C Velvetleaf J Downy Brome S Panicum Spp.

K Barnyardgrass T Crabgrass The results are summarized in Table III - 19 Compound of Example No.

Table III Pre-Emergent Piant Species kg/ha LMNOPBQDREFCJsKT .6 3333333333333333 1.12 2323ol22333x335o 0.28 0213312123303333 0.06 0111312012203333 0.01 0000001011100133 0.006 00000-0011000232 .6 1233311233313331.12 0233301033303330.28 0122200031103330.06 0002000030001130.01 0001000010000015.6 2333323333333333 1.12 1333322023323333 0.28 1223301003303333 0.06 0111000003100333 0.01 0000301000002333 0.006 0000000001100011 .6 2333335333323333 1.12 0223313233223333 0.28 02333-1333113333 0.06 01113-0010003333 0.01 0000000-00000x25 .6 3333323333333333 1.12 2335313333323j3j 0.28 0 2 2 2 3 l 1 l 3 3 3 2 3 3 3 3 0.06 01122000333i2o33 0.01 000000001110013ο 0.006 Ul0000002110u012 .6 3333323233333331.12 2 j 3 3 3 1 2 2 2 5 3 2 5 o 3 0.28 0213301123223OJ0.U6 OlUOOUOOlolOooO — 0.01 0001001011002035.6 i3333l0333oo33o3 1.12 033330333332333ο 0.2ο 023220222ο 2 io335 0.06 0211110322111333 0.01 il010O0ii0O01U2o 0.006 000000ol20001022 - 20 Table Hi (Cont'ci) Pre-Emergent Plant Species Compound of Example No. xg/ha L M N 0 P B Q D R E F c J 5 K in X 8 5.6 2 3 3 3 3 1 2 3 3 3 3 3 3 3 3 3 1.12 0 2 2 3 3 0 2 2 2 3 2 i 3 3 3 3 0.28 0 2 2 3 3 0 1 0 2 3 2 0 3 3 3 3 0. Ub 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 5.6 3 3 3 3 3 2 3 3 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 0.2o 0 1 2 2 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 10 5.6 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 i 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 5. b 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 0.2b 0 1 2 3 3 - 0 1 1 3 3 0 3 3 3 2 0.06 0 0 1 2 1 0 0 0 2 3 2 0 2 2 3 3 0. Ul 0 0 0 0 0 0 G u 0 0 0 0 0 0 1 3 12 5.6 2 2 3 3 3 1 3 1 3 3 3 1 3 3 3 3 1.12 0 2 3 3 3 1 J 2 3 3 J 1 3 3 3 3 0.28 0 2 3 3 3 0 0 0 1 3 2 0 3 3 3 3 0.0b 0 0 2 3 3 0 2 0 0 1 2 0 3 3 3 3 0.01 0 0 0 0 0 0 0 0 2 0 0 0 1 0 3 3 i J 5. b 1 2 3 2 3 2 3 3 3 3 3 2 3 3 3 1.12 0 2 2 3 3 1 2 2 3 3 3 1 3 3 3 - 0.28 0 2 2 3 0 0 1 1 2 3 2 0 2 3 3 - ϋ * 06 0 1 1 1 0 0 0 0 1 2 1 0 0 3 3 - 0.01 0 0 0 0 0 0 0 0 0 0 1 0 i 6 1 - 14 5.6 3 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 1.12 2 3 2 3 3 0 2 3 3 3 3 2 3 ·> 3 □ 0.28 2 2 2 2 3 0 2 3 2 2 2 1 3 3 3 3 0. Ob 0 2 i 2 1 0 1 2 1 2 2 0 2 2 □ 3 0.01 0 i 1 1 0 0 1 1 1 1 0 0 0 u 2 3 0.006 0 i 0 1 0 0 i i 1 1 0 0 υ u i -> 15 5.6 2 3 3 3 3 Ϊ 3 3 3 3 3 2 3 3 3 i.x2 u 2 3 3 3 1 2 1 1 3 2 0 3 j 3 3 U. 28 0 1 1 1 1 0 1 0 0 1 I 0 3 j 3 3 0. Ub u I u 0 0 0 0 0 u 1 0 0 0 2 3 3 0.01 0 0 0 0 u 0 0 0 0 1 1 0 0 υ 2 2 - 21Tabie 111 iCont'o) Pre-Emergent Compound of Example Ho.

Plant species kg/ha LhNOPbQDREFCJaKT .6 1333312233313331.12 0223302122303330.28 0213300013302330.06 0101000031003230.01 0000000000001115.6 0333301133313331.12 0223301022203330.28 0213200010103330.06 0001000011001130.01 00000-0000000015.6 3333333333323333 1.12 0333303333323333 0.28 0223302023213333 0.06 0200202002303333 0.01 0200000000-00033 - 22 The herbicides of this invention have been found to possess unexpectedly superior properties as pre-eiuergence herbicides, most particularly m the selective control of the hard-to-kill annual weeds, Texas panicum, seedling johnsongrass, snattercane, alexandergrass, wild proso millet, red rice and itchgrass, while also controlling or suppressing many other less-resistant perennial and annual weeds.

Selective control and inert.. _ t-d suppression 10 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 (oush beans). Selectivity has been shown in some tests at varying rates of application in sugarbeets ano garden peas; nowever, some crops, particularly grass crops, are usually less tolerant to the invention nerbicices than are the foregoing crops.

In order to illustrate the unexpectedly superior properties of the compounds of tnis invention both on an absolute basis and on a relative basis, comparative tests were conducted in the greennouse with compounds of the prior art most closeiy related in chemical stiucture to the invention compounds. The prior art compounds are identified as follows: A. N-tert-Dutyi-2-methoxy-2-chioroacetaniliae.

(Example 13, U.S. Patent No. 3,263,584) B. 2'-t-butyl-6'-methoxy-2-chloroacetanilide. (Example 67, U.S. Patent No. 3,442,945) C. N-isopropyi-2-chxoroacetaniiiue (common name propachlor). U.S. Patent No. 2,363,752 (Ke Patent No. 26,961); Propachior is referenced in the abovementioned U.S. Patent Nos. 3,773,4s2 and 4,i52,i37 and is the active ingreaient in tne commercial herbicide Kainroa*, a registered traaemark of Monsanto Company.

In tiie discussion of Guta teiow, reterence is - 23 mace co herbicide application rates symooiiaed as GRi5 ana GRa5“; tnese rates are given in kilograms per hectare (kg/ha) which are convertible into poutics per acre (lbs/Λ) by dividing the kg/ha rate by 1.12. GR^g defines che maximum rate of nerbicide required to produce 15¾ or less crop injury, and GR^ defines the minimum rate requireu to achieve 05« inhibition of weeds. The GR^^ ana GRgg rates are used as a measure of potential commercial performance, it being understood, of course, that suitable commercial herbicides may exhibit greater or lesser plant injuries witnin 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 weeu ingury ana is expressed in terms of the GRi5/GRg5 ratio, i.e., tne GR^j rate for the crop divided by the GRgg rate for the weed, both rates in kg/ha (lb/Α). In the tables below, selectivity factors are shown In parenthesis following the GRgj rate for each weed; the symbol NS indicates non-seiective. Marginal or questionable selectivity is indicated by a dash (-); a blank space means that the indicated piant was not in tne test or that thcpiant failed to germinate.

Since crop tolerance ana weed control are inter-related, a brief discussion of this relationship in terms of selectivity factors is meaningful. In general, it is desirable that crop safety factors, i.e., herbicide tolerance values, oe nigh, since Higher concentrations of herbicide are frequently desired for one reason or anotner. Conversely, it is cesiraoie that weed control rates De small, i.e., the nerbicide 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 οι51687 - 24 required. Hence tne best herbiciues are tnose whicn control the greatest number of weeas with the least amount of hc-rDicide and provide tne greatest dugrte 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.

In a first comparative test, greenhouse preemergence herbicidal activity aata are presented in Tabie IV comparing che relative efficacy of the compound of Example 1, representative compounds of this invention, with relevant compounds of the prior art, viz., Compounds A, B and C, as selective herbicides against particular weeas commonly associated with soybeans. The test data in Tabie IV for ail compounds was obtained under identical test conditions, i.e., soil incorporation with an initial overhead irrigation; tne aata represent the averages of two replicate runs for each compound; two different samples of the compound of Example i were usea and the data in tne table represent the average from both test samples.

Tne weeas usea in the tests herein have tne following abbreviations in the tables: Texas panicum (TP), seedling jonnsongrass (8JG), shattercane (bC), alexandergrass (AG), wild proso millet (WPM), fall panicum iFP), rea rice (RR) ana itchgrass (IG). - 25 TABUE IV J f! 9 7 - 26 Relevance to tne data in Taoie IV will snow that witn respect to weed control, none of the prior art compouncs 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 fall panicum, and even there, the selectivity factor was orie-foio less 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 tne compound of Example 1 controlled seedling johnsongrass, shattercane, alexandergrass, fall panicum ano itchgrass; at 0.07 kg/ha (the minimum rate useu) or less and also controlled the remaining weeds, i.e., Texas panicum, wild proso millet ano 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 herbicidai efficacy ot prior art compounas A-C witn the compounus of Examples 1, 3-5 and 8-17, representative of the invention compounds. The tests were conducted by soil incorporation of the herbicide at application rates witmn the range of from 0.07 to 1.12 kg/ha (0.0625-1.0 lb/A) ano an initial overhead irrigation followed by suosequent subirrigation watering as needed. Observations were made 19 days after treatment. The data from tne additional tests are snown in Tabie V; the names of tne weeds are abbreviated as in Table IV ana selectivity factors are shown in parentheses after the GR,JC rates for each weed. 51687 5169? - 29 10 Reterring to tne data in Taoie V, it wiix be noted that within the limits of the herbicide test rates, Compound A did not selectively controx any of test weeds in soybeans; Compound B only marginally selectively controlled fall panicum (not a particuiarly-resistant weed) and Compound C selectively controlled only faxi panicum and, marginally, Texas panicum, alexandergrass and red rice. But for the sole exceptions of Compound C against fail panicum (GR^ of 0.28 kg/ha) and Compound B against alexandergrass ana fall panicum (GR35 of 1·0θ kg/ha), none of tne 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, ail of tne 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 of Examples 8 and 17 against reu rice; Example 9 against wild proso miiiet and red rice; Example 14 against wild proso miiiet and Example i5 against shattercane. Moreover, in contrast with the prior art compounds and again with tne noteu exceptions, all of the invention compounds controixeo ail of the weeas at extremely low rates of application, ranging from no greater than 0.56 kg/ha (0.5 ib/A) downwardly to less tnan 0.07 kg/na (0.0b25 xb/nj, a remarkable performance in absolute terms in view or tne highly-resistant nature of the wteus tested (excepting fail panicum) and particularly relative to tne inaDility cf the most relevant compounds of tne prior art to control any of the test weeds, except as notec above.

Preferred compounds of this invention were further tested in the field to determine their selective preemergence heroicicai activity anc sul, .longevity against the annual weeds Texas panicum, bristiy siaiour ano Florida pusiey in peanuts - 30 (Florunner). Observations were made at 4, 8 and 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. - 31 I in oo oo ι o in m ο I in o Ο) Ο) ο» ο ο σι ρ* cr\ o H <-< © © 0) Λ ϋ) O Cl O CO Ο) O) 0) I in I I I I I I 0) in m in co o © tn © I I in in 000)0)0) CO w) ff)O 0)0) © o r- © ©m ο o in co in p* C0©©0 00 0)0)0 COCOO)© r-i H Percent Inhibition K Ail I in ί I fill O) CM CO p* © CM P1· CM © CO O 00 O m co oo ο © oo cn ο τρ r> co o H © co t** in co co in © © p* cn p* w ©co©© in oo © o r* oo © © c i _______ _______ .a 000)0)© β © Ο) Ο) Ρ* Ο) Ο) © r-4 ©©©r-i © © © © © © © cn o in ns © cn © in o © cn p* nJ Η Η Η K CM CM <· © © CM xl* © CO CM *3· © CO H CM CO ^p H CM CO ’M* r-i CM CO ^P ΗΝΠ'ί HN Πτρ rd CM M - 32 ΊΊι·.· due- in Ταϋΐ- Vi show tiiut die compound at Example 2 selectively controlled ail three weeas in peanuts at rates within the range of 2.24 to 4.4b kg/na for up to 12 WAT. Selective control of one or more of the g test weeds Was also exhibited by the compounds of Examples 1 and 3 at lesser rates for up to 12 WAT, indicating that of tne thLce test compounds, the compound of Example 2 naa the highest safety factor in peanuts under conditions of this test. 2_q Yet other tests were conducted in the field to determine the relative efficacy of the compounds of Examples 1, 3 and 4 against wile proso millet in soybeans for a period up to 12 weeks after treatment when applied either as surface applications (SA) or pre-plant 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 Tabie VII.

CO o o o rt If) so r© rt rt CN CN Ν' © © © Ρ» CN co rt ν* ν* in m r* in oo CN > © > in cn in rt cn r* co co rt oo cn tn © in oo oo Soybean w.'Ptoao Millet rt co o co *3· xp © r*> r- rt © © in tn r* r* m o co in © in r* © co © in Ν’ Γ* © © CN © © CN TO I-* © TO tn cn in oo co TO TO TO © © co oo © © © © rt in > to r* r>oo oo in in © o © co © σ» in cn »n cn © TO TO TO in in in tn to © Ch © ooort otn©© © © © © cui rt CN rt Oil <1 ooo© ©oor- ooo© ©I Hl CN rt CN O © in P* P* O TO © rt At I CN rt rt rt CN CN *3» rt rt rt rt Gt I rfJl οορπο ο o r* rt tn r* o in ©I rt CN rt rt rt h cn rt cn o r- r* o © tn cn tn co PL I rt rt rt in CN rt rf © rt CN fN Ν' pd <| m in in rt o in cn o ro in cn cn ©| rtrtrtrt rt CN rt rt CN CN to Φ w •M \ rt CT 0$ tt CNN'©© CN Ν'© TO CN N· © TO rt CN rt Ν' rt CN rt T|< rt (N rt Ν’ rt CN rt Ν' rt CN rt Ν' ι—I CN rt Ν' (0 +J tt +i Φ rt ϋ •ri rt Ot Φ It Φ x: 4J rt Φ Ot rt li :> tt - 34 The date in Table VII show that a 3.3b kg/ha rate of each compound selectively controlled wild proso millet in soybeans for 3, d and 12 WAT in tne surface applications. Thus, certain treatments of the crop with the invention compounds provided season long controx of wild proso millet, since germination and emergence of this 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 Ιθ 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.

In yet another field test, the compounds of 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 fierd test was conducted in a clay soil (58% clay and 3.1% organic matter). Observations were made at 4 and 3 weeks after treatment; the results are shown in Table VIII. - 35 51637 TABLE VIII ca co β rt Ci 00 β 0 Ώ C 43 0 »-> w β SSI β Φ 33 O OO 00 rrt 00 CO I**· cn o co co CM vO r*- vO ΟΟ CO 00 m ps co co ι in ν en oo oo σ* O © m O r- oo σ» co m r- co co co oo co fO S ιΓ ifl CM VO CO 00 in η- cm co cm vo oo rs cn co cm m CM VO 00 CO CQ trt 4J a> u co υ ♦rt rrt Cu Ms O CO rrt Mt Γr-> o cn in vo r-· rs m o rt 0) > < cn © r* cm ιη >· ιη cn © cm cn in rrt rrt CM i—1 CM irt rrt rrt cm co cm co cn cn cm cm co co o co fH cm cm cn trt r-ι cm cn cm cm cn cm m oo cn cn oo cm o co cm Is* ι—1 rrt «rt ι—I trt CM trt r—I r-1 m cn cn © o cm co cm © cn cn c*j rrtCMCn r-4 CM CM cn ι—I t—1 CM CM CM Mt Ό CO trt CM cn CM Mt VO CO rrt CM m Mt CM Mt Ό CO rrt CM cn Mt »rt cm cn r-ι cm cn Ed * Ed - 36 The compound of Example 4 selectively controlled seedling johnsongrass in soybeans at the 2.24 kg/na for as long as 8 weeks after treatment unuer PPI conditions and at the 3.36 and 4.48 kg/ha rates unaer 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 tne above tables, 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 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 different concentrations onto a weighed amount of Ray silt loam contained in pots having filter paper covering drainage holes in the pot bottoms. Tne pots containing the treated soil were suojected 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 tne amount of time on the turntable. Water was delivered to the soil in tne pots and allowed to percolate through tne filter paper and drainage holes. The pots were then allowed to sit for three aays at ambient room temperature. The treated soil in the pots was then removed, crumoiea and placed as a surface layer on top of other pots containing Ray silt loam soil seeded with barnyardgrass seeds. Tne pots were then placed on greenhouse Denches, sub-irrigated ano allowed to grow for 2-j weexs. Visuax ratings of percent growth inhibition compared to control (untreated) pots ano - 37 fresh weights for barnyardgrass were made io days alter treatment and recorded; the data from three replications of tnese tests are snown in Table IX.

Table IX Barnyardgrass Compound Rate of Ex. 1 (Kg/Ha Rain ) (Cm) Percent Fresh Inhibition Weight (Avg. of 3 replications) Percent of Controls 2.24 0 100 0 0 0.64 100 0 0 1.27 100 0 0 2.54 100 0 0 5.08 100 0 0 10.16 95 0 U 0.56 0 100 0 0 0.64 100 0 0 1.27 100 0 0 2.54 100 0 u 5.08 95 0 0 10. 16 95 0 0 0.14 0 100 0 u 0.64 iuO 0 1.27 100 0 0 2.54 y5 υ ύ 5.08 95 0.20 3.3 10.16 90 0.83 14.1 The data in Table IX indicate that the compound of Example i, , representative of the invention compounds, was quite resistant to leaching into the soil under conditions of neavy rainfall anc exnibiteu no less than 90% control of barnyardgrass at application rates as iow as 0.14 Kg/na (O.iza ru/aj under 10.i6 cm of rainfall.

A distinct advantage of a herbicide is its ability to function in a wide variety of son types. Accordingly, data is presented in Tabie X snowing tne herbicioai effect of the compounds of Examples 1 ana J on alexandergrass (AG) ana barnyardgrass (BYG; in soybeans in a wide variety of soil types and organic matter content. The herbicide treatments were applied by surface application with overhead irrigation as - 38 described above; selectivity factors for the weeas are shown in parentheses after the GRgg rates for the weeas. 51637 - 39 tf ϋ Λ© Mm © · · · . ¢0 cm © ©A A A *3· *3* r—i H © CM © Tp CO o « » © co A A Tp © CM CM o • OT r-l Z CM Tp «-4 CM © • OT Η Z TP CM CM © O © (Kg/Ha) _(Kg/Ha) fi «ι Φ to > OT © © ί-l CM TP TP π4 ι—I . . ¢) ο Ο Ό fl έ o © © © ZS A TP TP CM CM H W i-4 r4 fl © Γ-4 dP · U I O) § β β 0) β ft3 ea H 0 .η υ o OT Z-S z—> —· z-x Ή O Γ* © © © © © © © © P « · • · • · • · fl © © © © © CM iP © © > A <-4 ι—1 ι—1 A A 34 A AA ««-* *—1· s—» *-*» Φ * W © r-l tP tP Tp © CM *3* TP Λ CM CM Η H H CM H CM r4 r-i O © © © O © © r-4 CM s° . V V V 01 TP CM CM d τ8· TP CM CM τρ TP CM CM CM CM r-l K CM CM ι—1 r4 CM CM r-4 r4 CM CM r4 j—| © co Γ*· i-4 cn © © CM >1 to r-4 •r4 w g P H cn fl r-4 ι-M CO r4 0 P ό a •H · * • Φ r-i • · Ό 03 X X >κ κ g > < κ •rl tf tf fttf tf g 4 tf P >1 P 3 fl 0 fl fl )4 i—l r4 tf w Q Q ft ε r fl Ό Μ I O r—I ft >1 nJ r4 ϋ fl OT >♦ -S C « nj ω •H rd •H 0 N >-t i ifl 3 ' Id Ifl ( CQ & r ; tf &5 «Η 4-) Π3 Ή «Η ft Φ >4 4J (0 4-» φ β © a) β έ M 4-) Φ fl > Φ fl Ρ •Ρ P Φ Φ 03 +J Φ 44 P fl ft φ 01 P >1 fl fl T3 P fl CO Q H fl - 40 The data in Table X snow that tne invention compounds were largely insensitive to soil type. ln more particular, the compound of Example 1 exhibited positive selective control of alexandergrass and barnyardgrass in soyoeans in ail soils in the test containing organic matter ranging from 1.0% O.M. concent m Ray siic loam to 22.1% O.M. in Florida muck soil. Similarly, the compound of Example 3 exhibited positive selective control of the weeds in test in soybeans in all soil types,except against barnyardgrass in Florida sand (b.8% O.M.) and Florida muck. Since the compound of Example 3 did selectively control both alexandergrass and barnyardgrass in Drummer silty clay loam soil having approximately the same organic matter concent as Florida sand, but a mucn 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-seiective control of 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 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 iD/a, in cotcon, rape, carrot and red beet up to 0.5 lb/a or more and in alfalfa, flax anu cabbage on the oruer of 0.25-0.5 io/a.

Toxicology studies on the compounds of Examples 1, 3 and 4 nave indicated the fonowing properties : - 41 Compound of Toxicology Example No. 1 3 4 OLD50, Mg/Kg 3370 2300 2400 DLD, Mg/Kg. >2000 >1000<12o0 >31U0<50iU Eye irritation slight severe moderate Skin irritation none corrosive 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 tnat compounds according to this invention have demonstrated unexpected and outstandingly superior herbiciaai properties botn absolutely and relative to the most structuraliyreievant compounds of the prior art, one of wmch (Compound C) is a commercial herbicide. More particularly, the compounds of tnis invention have proven to be outstanding selective herbicides, particularly in tne control of naru-to-kni annual grasses in soybeans, peanuts and other crops. In more particular, compounds according to tnis invention exhibit outstanding control of the annual grasses Texas panicum, itchgrass, wiia proso millet, alexandergrass, seedling johnsongrass, shattercane and red rice, wniie controlling αηα/or suppressing other iess-resistant annual grasses and perennials, including those mentioneu in Tables Ii and III above and ounces, sucn as bristly starbur, Florida pusiey, etc. - 42 The herbicidal compositions of this invention including concentrates which require dilution prior to application contain at least one active ingredient and an adjuvant in liquid or solid form. The compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.

The compositions of this invention, particularly liquids and wettable powders, preferably contain as a conditioning agent one or more surfaceactive agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into the compositions greatly enhances their efficacy. By the term surface-active agent it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Anionic, - 43 cationic ana non-ionic agents Can be useu witu eyua* facility.

Preferred wettiny ayents arc aakyi benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or aciu amities, long chain acid esters of sodium isothionate, esters of sodium sulfosuccmate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ditertiary acetylenic 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 metnyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl, naphthalene sulfonates, sodium naphthalene sulfonate, and the polymethylene bisnaphthalene sulfonate.

Wettable powders are water-dispersiDie compositions containing one or more active ingredients, an inert solid extender and one or more wetting ano dispersing agents. The inert solid extenders are usually of mineral origin such as tne natural clays, diatomaceous earth and synthetic minerals derived from silica ana the like. Examples of sucn extenders include kaoiinites, attapulgite ciay and synthetic magnesium silicate. The wettable powders compositions of this invention usually contain from 0.5 to 60 parts (preferably from 5-20 parts) of active ingredient, from 0.25 to 25 parts (preferably 1-15 parts) of wetting agent, from 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to 95 parts ''preferably 5-50 parts) of inert solid extender, all parts being Dy weight of the total composition. Where required, from 0.1 to 2.0 parts of the solid inert extender can be replaced oy a corrosion inhibitor of anti-foaming agent ot Dotn.

Other formulations inciuue oust concentrates - 44 comprising from 0.1 to 60% by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range of from 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 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 that when diluted and sprayed, coverage is very uniform. Suitable concentrations of these formulations contain from 0.1-60% preferably 5-50% by weight of active ingredient, the upper limit being 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 polymethylene polypheny!isocyanate, dispersing the waterimmiscible phase in the aqueous phase followed by addition of a polyfunctional amine. The isocyanate and amine compounds react to form a solid urea shell wall around particles of the water-immiscible chemical, thus forming microcapsules thereof. Generally, the concentration of the microencapsulated material will range from 480 to 700 g/1 of total composition, preferably 480 to 600 g/1.

Concentrates are usually solutions of active ingredient in water-immiscible or partially water51697 - 45 immiscible solvents together with a surface active agent. Suitable solvents for the active ingredient of tnis invention include aimetnylformide, dimethylsulfoxide, 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 compositicr- harem contain from θ-l to 95 parts (preferably 5-60 parts) active ingredient, 0-25 to 50 parts (preferably 1-25 parts) surface active agent and where required 4 to 94 parts solvent, ail parts being by weight based on the total weight of emulsifiable oil.

Granules are physically staoie particulate compositions comprising active ingredient adhering to or distributed through a basic matrix oi an inert, finely-divided particulate extender. In order to aia leaching of the active ingredient from the particulate, a surface active agent such as those listed hereinbefore can be present m the composition.

Natural clays, pyrophyllites, illite and vermiculite are examples of operable classes of particuiate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles such as preformed anc screened particulate attapulgite or heat expanded, particulate vermiculite ana tne f meiy-aiviccd clays such as kaolin clays, hydrated attapulgite or bentonitic days. These extenders are sprayed or blended with the active ingredient to rorm the nerDicidai granules.

Tne granular compositions of tnis invention may contain from 0.1 to 30 parts preferably from 3 to 20 parts by weight of active ingredient per 100 parts by weight of clay and 0 to 5 parts - 46 30 Dy weight. of surtace active agent per iuu pares by weignt of particulate ciay.

The compositions of this invention can also contain other additaments, for example, fertilizers, other herbicides, other pesticides, safeners and the like used as adjuvants or in combination with any of tne above-described adjuvants. Chemicals useful in combination with the active ingredients of tnis invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like sucn as: Heterocyclic Nitrogen/faulfur Derivatives 2-Chloro-4-ethylamino-6-isopropyiamino-s-triazine 2-Chloro-4,6-bis(isopropylamino)-s-tnazine 2- Chloro-4,6-bis(ethylamino)-s-triazine 3- Isopropyi-iH-2,1,3-benzothiaoiazin-4-(3H)-one 2,2 dioxide 3-,vmino-i,2,4-tnazoie 6,7-Dihydrooipyrioo(i,2-a:21,1'-c)-pyrazidiiniuis salt -3romo-3-isopropyl-6-methyluracii 1,1'-Dimethy1-4,4'-bipyridinium 25 Ureas N'- (4-chlorophenoxy) phenyl-N,N-aimethylurea N, N-c imetnyl-N ' - (J-chloro-4-me tiiyiphenyi) urea 3-(3,4-dichiorophenyl)-1,1-dimethylurea 1,3-Dimethyi-3-(2-benzocniazoiyi) urea 3-(£-Chlorophenyl)-1,i-dimethylurea 1-Buty1-3-(3,4-dichloropnenyi)-1-metnylurea - 47 Carbamates/Thioicarbamates 2-Chloroaliyi diethyldithiocarbamate S-(4-cnloroDenzyi)N,N-diethyltnioicarbaniate Isopropyl N-(3-chlorophenyi) carbamate S-2,3-dichloroallyi N,N-aiisopropylthiolearbamate Ethyl N,N-dipropylthiolcarbamate S-propyl dipropylthiolearbamate Acetamides/Acetanilides/Anilines/Amices 2-Chloro-N,N-dialiylaeetamide N,N-dimethy1-2,2-diphenyiacetamide N-(2,4-dimethyi-5-11 (trifluoromethyl)sulfonylJ amino)phenyl) acetamide N-Isopropyi-2-chioroacetanilide 2',6’-Diethyl-N-methoxymethyl-2-chloroacetanilide 21-Me thyl-b1-e thyi-N-(2-me thoxyprop-2-yl)-2chloroacetanilide o<, o£.,^jz -Trifiuoro-2,6-Cinitro-N,Ndipropyl-£-toluidine N-(i,1-dimethylpropynyi)-3,5-d ichiorooenzamice Acids/Esters/Alcohols 2,2-Dichloropropionic acid 2- Metnyl-4-cnlorophenoxyacetic acic 2,4-Dicnlorophenoxyacetic acia Methyl-2-[4-(2,4-cichiorophenoxy)phenoxyj propionate 3- Amino-2,S-Gichiorobenzoic acic 2-Methoxy-3,6-aichlorobenzoic acia 2,3, b-Tr icnioropnenyiacetic acic Soaium 5-12-cnioro—*-itrifluoromethyl)pnenoxyj-2ni trobenzoate - 48 4,6-Umi tro-o-sec-butyipnenol N-(phosphonomethyl) glycine and its C, monoalkyi amine and aikaline metal salts and combinations thereof Ethers 2,4-Dichiorophenyl-4-nitrophenyi ether 2-Chioro- a,a,a-trifluoro-£-tolyl-3-ethoxy4-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 ana superphosphate. Otner useful aaditaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

Herbicidal formulations of tne types describee above are exemplified in several illustrative embodiments below.

I. Emulsifiable Concentrates (EC's) A. Compound of Example No. 1 25 Calcium doaecylbenzene sulfonate/ polyoxyethylene ethers blend (e.g., Atiox-rf 34j7F) Monochlorobenzene rfeigtit Percent .6 .0 29.7 29.7 100.00 Β. Compound ot Example ho. j Calcium uodecyl suifonate/ai- 65. u kyiaryl polyetner aiconol blenu Cg aromatic hydrocarbons solvent 4 . i) 11.ϋ 100.on C. Compound of Example No. 4 5.0 Calcium aodecylbenzene sulfonate/ polyoxyethylene ethers blend (e.g. , Atiox 34J7F) 1.0 Xylene 94.0 100.00 XI. Liquid Concentrates Weight Percent A. Compound of Example No. 5 Xylene 10.0 90.0 100.00 B. Compound of Example No. 6 Dimethyl sulfoxide 85.0 15.0 100.00 C. Compound of Example No. 10 N-methyipyrroiidone 50.0 50.0 100.0 D. Compound of Example No. 19 Ethoxyiatea castor oil Rhoaamine B Dimethyl formamide 5.0 20.0 .5 74.5 100.OC - 50 lil. Emuxsions Weignt Percent A. Compound of Example No. 7 Poiyoxyetnylene/polyoxy- 40.0 5 propylene Diock copolymer with butanox (e.g., Tergitol^ Xll) 4.0 Water 56.0 loo.oo B. Compound of Example No. 8 5.0 10 Polyoxyethylene/poxyoxy- propylene block copolymer with butanol 3.5 Water 91.5 100.00 IV. Wettable Powders 15 Weight Percent A. Compound of Example No. 9 25.0 socium lignosulfonate 3.0 Sodium N-methyl-N-oleyl-taurate 1.0 Amorphous silica (synthetic) 71.0 20 100.00 ES Compound of Example No. 10 80.u Soaiuin dioctyl sulfosuccinate 1.25 Calcium lignosulfonate 2.75 Amorpnous sixica (synthetic) 10 . Ob 25 100.00 C. Compound of Example No. 11 10.0 Sooium lignosulfonate 3.0 Sodium N-methyl-N-oleyl-taurate 1.0 Kaoxinite clay 86.0 100.0b - 51 V. uusts weight PfeLatrit A. Compound of Example No. 12 2.0 Attapulgite 9a. u 100.00 B. Compound of Example No. i3 60.0 Montmorillonite 4G.ϋ 100.00 C. Compound of Example No. 14 30.0 Bentonite 70.0 100.00 D. Compound of Example No. 15 1.0 Diatomaceous earth 99.0 100.00 VI. Granules Weignt Percent A. Compound of Example No, 16 15.0 Granular attapulgite (20/40 mesh, 05. o 100.00 B. Compound of Example No. 17 30.0 Diatomaceous eartn (20/40) 70.0 100.00 C. Compound of Example No. la 0.5 Bentonite (20/40) 99.5 100.0u D. Compound of Example No. 19 5.u Pyiophyiiite (20/40) 95.u 100.o - 52 Vi χ. Miciocapsu^cs A. Compound of Example No. 1 encapsulated in polyurea snexl wall 45.2 Sodium lignosulfonate (e.g.

Reax 8 oil® ) Q.9 Water 49.9 Ιϋϋ.00 B. Compound of Example No. 3 encapsulated in polyurea sheli wail 10.0 Potassium lignosulfonate (e.g., Rexas C-21® ) .5 Water 89.5 100.0u C. Compound of Example No. 4 en15 capsulatea in polyurea shell waii tSO.O Magnesium salt of lignosulfate (Treax LTil®) 2.0 Water 18.0 100.Ou When operating in accordance with the present invention, effective amounts of the acetanilides 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, ooom and nand sprayers and spray dusters. The compositions can also be applied from airplanes as a oust or a spray because of their effectiveness at row dosages. The appxication of herbicidal compositions to aquatic plants is usually carriec out by aaciing tne compositions to the aquatic media in the area where control of tne aquatic pxancs is deairec. - 53 The application or an effective amount of tiie compounds of this invention to tne locus of unoesirea weeas is essential and critical for tiie practice of tut 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 about 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 reaaiiy 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 tne 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 ana the like, adapted to support plant growth.

Claims (33)

1. Compounds having the formula C1CH 2 C ,R \ / N wherein R is methyl or ethyl; R]_ is a alkyl radical; 5 R 2 is methyl, ethyl or t-butyl and R g is hydrogen or methyl in a meta position; provided that; when R is ethyl, R^ is n-butyl, R 2 is methyl and R 2 is hydrogen; 10 when r 3 is methyl, R and R 2 are also methyl and R^ is isopropyl or n-butyl; when R g is hydrogen and R and R^ are both methyl, R^ is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 15 2-methylpentyl or 1,3-dimethylbutyl; when R 2 is ethyl, R is methyl and R^ is isopropyl and when R 2 is t-butyl, R and R^ are both methyl.

2. Compounds according to Claim 1 wherein R, is 20 a Cj_g alkyl radical and R and R 2 are methyl radicals.

3. Compound according to Claim 2 which is N-methyl-2'-isopentyloxy-6'-methyl-2-chloroacetanilide.

4. Compound according to Claim 2 which is N-methyl-2'-n-propoxy-6 1 -methyl-2-chloroacetanilide.

5. Compound according to Claim 2 which is N-methyl-2'-n-butoxy-

6. '-methyl-2-chloroacetanilide. 31697 - 55 6. Compound according to Claim 2 which is N-methyl-2'-sec-butoxy-6'-methyl-2-chloroacetanilide.

7. Compound according to Claim 2 which is N-methyl-2'-isopropoxy-6'-methyl-2-chloroacetanilide.

8. Compound according to Claim 2 which is N-methyl-2’-isobutoxy-6 1 -methyl-2-ohloroacetanilide.

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

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

11. Herbicidal composition comprising an adjuvant and a herbicidally effective amount of a compound having the formula It C1CH-C R 2 \ Z wherein R is methyl or ethyl; R^ is a C^_g alkyl radical ,r 2 is methyl, ethyl or t-butyl and R 3 is hydrogen or methyl in a meta position; provided that: when R is ethyl, is n-butyl, R 2 is methyl and Rj is hydrgen; when Rj is methyl, R and Rj are also methyl and is isopropyl or n-butyl; when Rj is hydrogen and R and Rj are both methyl, is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl; when Rj is ethyl, R is methyl and R^ is isopropyl and - 56 when R 2 is t-butyl, R and R^ are both methyl.

12. Composition according to Claim 11 wherein in said compound R^ is a C 2 _j alkyl radical and R and R 2 are methyl radicals. 5

13. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2'-isopentyloxy-6'methyl-2-chloroacetanilide.

14. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2 1 -n-propoxy-6 1 -methyl10 2-chloroacetanilide.

15. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2'-n-butoxy-6'methyl-2-chloroacetanilide.

16. Herbicidal composition according to Claim 12 15 wherein said compound is N-methyl-2'-sec-butoxy-6'-methyl2-chloroacetanilide,

17. Herbicidal composition according to Claim 12 wherein said compound is N-methyl-2 1 -isopropoxy-6 1 -methyl2-chloroacetanilide. 20

18. Herbicidal composition according to Claim 11 wherein said compound is N-methyl-2 1 -isobutoxy-6'-methyl2-chloroacetanilide.

19. Herbicidal composition according to Claim 11 wherein said compound is N-ethyl-2 1 -n-butoxy-6'-methyl-225 chloroacetanilide.

20. Herbicidal composition according to Claim 11 wherein said compound is N-methyl-2'-isopropoxy-6'-ethyl2-chloroacetanilide. - 57

21. Method for controlling undesirable plants in crop plants which comprises applying to the locus thereof a herbioidally effective amount of a compound having the fonnula rt C1CH-C R 2 \ / N wherein R is methyl or ethyl? Rj is a Cj_ g alkyl radical; Rj is methyl, ethyl or t-butyl and Rj is hydrogen or methyl in a meta position? 10 provided that: when R is ethyl, Rj is n-butyl, Rj is methyl and Rj is hydrogen? when Rj is methyl, R and Rj are also methyl and Rj is isopropyl or n-butyl; 15 when Rj is hydrogen and R and Rj are both methyl, Rj is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl; when Rj is ethyl, R is methyl and Rj is isopropyl 20 and when Rj is t-butyl, R and Rj are both methyl.

22. Method according to Claim 21 wherein in said compound Rj is a Cj_ g alkyl radical and R and Rj are methyl radicals.

23. Method according to Claim 22 wherein said compound is N-methyl-2'-isopentyloxy-6'methyl-2-chloroacetanilide. - 58

24. Method according to Claim 22 wherein said compound is N-methyl-2'-n-propoxy-6'-methyl2-chloroacetanilide.

25. Method according to Claim 22 wherein said compound is N-methyl-2'-n-butoxy-6'-methyl2-chloroacetanilide.

26. Method according to Claim 22 wherein said compound is N-methyl-2'-sec-butoxy-6'-methyl2-chloroacetanilide.

27. Method according to Claim 22 wherein said compound is N-methyl-2'-isopropoxy-6'-methyl2-chloroacetanilide. 22. Method according to Claim 22 wherein said compound is N-methyl-2'-isobutyl-6'-methyl2-chloroacetanilide. 2g Method according to Claim 21 wherein said compound is N-ethyl-z - -n-butoxy-6'-methyl2-chloroacetanilide.

28. 30. Method according to Claim 21 wherein said compound is N-methyl-2'-isopropoxy-6'-ethyl2-chloroacetanilide.

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

30. 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-6'-methyl-2-chloroacetanilide.

31. 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-2'n-propoxy-6'-methyl-2-chloroacetanilide. - 59 51697

32. 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.

33. 35. Method for controlling undesirable plants in soybeans, peanuts, rape, cotton, snap beans, and vegetable crops which comprises applying to the locus thereof a herbicidally effective amount of N-methyl-2'io isobutoxy-6'-methyl-2-chloroacetanilide.