NZ196549A - 2-haloacetanilides and herbicidal compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 96549 8) 196549 Pricd^y D&ieH): Af.'&M CompJeto Specification. Filed: It A : c PubHcation Date: .. ■PiO.'i n". ......

P.O. Journal, Wo: NEW ZEALAND No.: Date: PATENTS ACT, 1953 COMPLETE SPECIFICATION C £ \"JV-" "HERBICIDAL 2-HALOACETANILIDES" fe'We, MONSANTO COMFANY, a corporation of the State of Delaware, United States of America, now residing at 800 North Lindberg Boulevard, St. Louis, Missouri 63166, the United States of America, hereby declare the invention for which-t-/ we pray that a patent may be granted to JBe-/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (Followed by page la) 196549 -f3- —AO-12 5 2 HERBICIDAL 2-HALQACETAHIL1PES Background of the Invention Field of the Invention This invention pertains to the field of 2-5 haloacetanilides and their use in the agronomic arts, e.g., as herbicides, particularly for use in transplant rice.

Description uf the Prior Art The invention compounds are characterized as 10 2-chloroacetanilides having specific combination of an n-butoxy radical in one ortho position, an ethyl radical in the other position, and as a substituent on the anilide nitrogen ring a radical selected from the group consisting of allyl, ciiloroallyl, propargyl, 2-15 methoxyprop-2-yl or a radical of the formula -CI^OR^ wherein is a aikyl radical.

The prior art relevant to this invention includes numerous disclosures of 2-haloacetanilides which may be unsubstituted or substituted with a wide 20 variety ot substituents on the anilide nitrogen atom and/or on the anilide ring including alkyl, alkenyl, alkynyl, alkoxy, poiyalkoxy, alkoxyaikyi, heterocyclyl, halogen, etc., radicals. The most relevant compounds of the prior art in this area appear to be those 25 disclosed in the following references: U.S. Patent &S. Numbers 3,268,5b4, 3,442,945, 3,547,b20, 3,773,492, 4,152,137. and Belgian Patent No-.—ij-10 , 7-frSs. However, none of those prior art references disclose any data for compounds of the type disclosed herein as being 30 useful transplant rice herbicides, nor do they disclose or suggest the particular species of this invention.

The 2-haloacetanilides of the prior art which are known to have utility as transplant rice herbicides differ significantly in structure from those disclosed 35 herein. Specifically, said prior art herbicides all contain lower alkyl radicals in both ortho positions to \' « 19654 -2- A6-1232 the anilide nitrogen atom and an alkoxyalkyl radical on said nitrogen atom. Accordingly, those prior art rice herbiciues at't non-related and non-suggestive ot those disclosed herein. However, in order to provide a basis for comparison, the relative herbicidal efficacy ot compounds according to this invention is compared with . that of MACHETE© herbicide (registered traaeraark ot Monsanto Company), the active ingredient of which is 2' , 6 '-diethyl-N- (n-butoxymethyl)-2-chioroacetaniiide (common name "butachlor"). Butachlor and a homolog thereof ("ethyl butachlor" herein) are disclosed as rice herbicides in U.S. Patent Number 3,663,200. Of the known prioc art of 2-haloacetaniiiae herbicides, only MACHETE herbicide has achieved commercial status to date.

While prior art rice herbicides have been found useful, there is a continuing need for improved rice herbicides which control resistant weeds of economical significance at lower rates of application, maintain control or suppression of such weeds for longer periods of time, while maintaining safety to the rice crop ana improved toxicity with respect to fish and mammals.

The above prior art herbicides have been found to share one or more undesirable properties as transplant rice herbicides. Among certain disadvantages of prior art transplant rice herbicides are their generally weak performance in the control and/or suppression of the economically-significant resistant perennial weeds Cyperus serotinus, Eleocharis kuroguwai and Sagittaria trifolia together with diminishing efficacy in the control or suppression of the annual weeds Echinochloa crus-galli and, to a lesser extent, fbnochoria vaginalis, within a period from 2-b weeks. These performance weaknesses are particularly apparent at lower rates of application, i.e. down to 0.17 lb/A (0.19 kg/ha) and lower. In 1965 -3- AG 12521 fact, fieia tests have shown that in some treatments some of the prior art herbicides failed to selectively control Eleocharis kuroguwai at rates below 5.3b lb/A (6 kg/ha) or even 2.67 lb/A (3 kg/ha) for periods as 5 short as 2 or 3 weeks, similarly, in field tests, it was also found that some prior art rice herbicides failed to provide any meaningful suppression of Sagittaria trifolia after four or five weeks.

It is, therefore, an object of this invention 10 to provide a class of herbicides which is particularly useful in transplant rice.

A further object of this invention is tne provision of selected herbicides which: (1) are safe (i.e., produce no more than about 15* injury) on 15 transplant rice at rates up to at least 2.0 lb/A (2.24 kg/ha); (2) selectively control Echinochloa crus-gaili, Monochoria vaginalis, Cyperus serotinus and Eleocharis kuroguwai, and (3) proviae increased suppression of Sagittaria trifolia.

Finally, it is an advantage of the heroicides 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 25 below.

Summary of the Invention The present invention relates to herbicidally active compounds, herbicidal compositions containing these compounds as active ingredients and herbicidal 30 methou of use of saia compositions in various crops, particularly transplant rice.

It has now been found that a selective group of 2-haloacetanilides characterized by specific combinations of radicals on the anilide nitrogen atom, 35 a specific alkoxy radical in one ortho position ana an ethyl radical in tiie other ortho position possess unexpectedly superior and outstanding selective 1S6549 heruiciuai properties as transplant rice herbicides vis-a-vis prior art herbicides of related structure of the most relevant prior art, including a commercial rice herbicide.

A primary feature of the herbicidal compositions of this invention is their ability to control and/or suppress annual and perennial narrowleaf weeds in transplant rice, particularly the prevalent and euonomically-siynificant annuals such as 10 Echinochloa crus-galli, Monochoria vaginalis and resistant perennial species such as Cyperus serotinus, Eleocharis kuroguwai and Sagittaria trifolia and other noxious weeds.

The compounds ot this invention are 15 characterized by the formula MX PATENT QPflCS | 28 JUN1983 i fr- WECBVeP Wherein R is allyl, chloroallyl, propargyl, 1-methoxy- prop-2-yl or a radical of the formula -Ct^OR^, where R^ is methyl, isopropyl, N-butyl, isobutyl, sec-butyl, isoamyl or 2-methyl-butyl.

Preferred species of this invention are those where in the above formula R is propargyl, 1- methoxyprop-2-yl and species wherein R^ is n-propyl, sec-butyl, 2-methybutyl or isoamyl. Other species of this invention are those where R in the above formula is allyl, chloroallyl or -CH^OR^ groups wherein R^ is methyl, isopropyl n-butyl or isobutyl.

A further aspect of the invention consists in a method for the combatting of weeds in transplant rice by application to the locus thereof of a herbicidally effective amount of N- (allyloxymethyl) -21 -n-butoxy-6-ethyl-2-chloroacetanilide.

The utility of the compounds of this 0 II CiCH2C c2a- R IS ifcy invention as the active ingredient in nerbiciaai compositions formulated therewith and the method of use thereof will be described below.

Detailed Description of the Invention 5 The compounds of this invention may be made in a variety of ways. For example these compounds may be prepared by an N-alkylation of the anion of tne appropriate secondary 2-haloacetaniiide with an alkylating agent under basic conditions.

Example 1 below illustrates the use ot said N-alkylation to prepare one species of this invention. A modified N-alkyiution process is described in Example 2 for preparing another species of the invention. The 15 modified N-aikyiation process described in Example 2 herein involves the in-situ preparation of halomethyl alkyl or alkenyi ethers used as starting materials in the N-alkylation process.

Example 1 2,-n-butoxy-6'-ethyl-2-chioroacetanilide, .4 g (0.02 mol), propargyi bromide, 2.6 g (0.022 moi) and 2.0 g of benzyl triethyiammonium chloride were mixed in 150 ml of methylene chloride and chilled. To the mixture at 15°C was added 45 ml of 50% NaOH all at once and stirred for 5 minutes, then 150 mi of coiu water was added. The layers were separated, washed with water, then dried over MgibC^ and evaporated by Kugelrohr to obtain 4.45 g (73% yield) of yellow oil, b.p. llbuC ac 0.03 mm hg.

Anal. Caic1 d for C^ClNO^ (%): C, bb.j3; H, 7.20; CI, 11.52; -6- Mi- i Found: C, bb.35; H, 7.2l; Ci, 11.50 The product was iuentified as N-propargyi-2'-n-butoxy-b'-fcthyi-2-chloroacetaniiide. 5 Example 2 Following substantially the same procedure described in Example 1, but substituting ally! bromide as the alkylating agent, 4.9 g (79% yield) of yeixow oil boiling at 128°C (at 0.05 mm Hg Kugelrohr) was 10 obtained.

Anal: Calc'd for C^^^ClNl^ (%): C,65.90; H, 7.81; CI, 11.44; Found: C, 65.89; H, 7.81; Ci, 11.42 The product was identified as N-ailyl-2-n-butoxy-61 - v ethyl-2-chioroacetanilide.

Example 3 This example describes a modification of the N-alkylation process described in Example 1. In this process embodiment, the alkylating agent is formed in-situ, thus effecting a more efficient, economic and simple operation.

To a chilled mixture of b.9b g (0.12 mol) of ally! alcohol, i.b g (0.12 mol) of anhydrous paraformaldehyde and 150 ml of methylene chloride was added 4.71 g (0.0b mol) of acetyl chloride; the mixture was stirred for 90 minutes until all the paraformaldehyde was dissolved. To the mixture was tiien added 5.4 g (0.02 mol) of 2'-n-butoxy-b 1 -ethyl-2- chloroacetanilide, 2.0 g of benzyl triethylammonium I P &S. chloride arid 50 ml of methylene chloride. The mixture \0°t- was cooled to ^-00 aC and 50 ml of 50% NaOH added all at 49 §t.. once anu stirred for i5 minutes. The layers were separated, washed with water, dried over Mg£o4 and 35 evaporated by Kugelronr to obtain 6.0 g (92% yield) ot clear oil, b.p. 122°C at 0.04 mm Hg.

Anal. Calcu £ql C^^H.^^ClNU-^ (%): C, 6 j.ti; H, 7.71; 196s -7- —rtG-liliii Ci , 10.43; Found: C, 63.60; H, 7.74 CI, 10.42 The product was identified as N-fellyloxymethyl)-21-n-5 butoxy-6'-ethyi-2-chloroacetaniiide.

Example 4 Following substantially the same procedure described in Example 3, but substituting 2-butanol as the alkylating agent, 4.15 g (7b% yield) of clear oil 10 was obtained, b.p. 118°C at 0.02 mm Hg (Kugelrohr). Anal. Calc'd for Cj^H^qCINO^ (%): C, 64.12; H, B.50; CI, 9.96; Found: C, 64.05; H, 8.52; CI, 9.90 The product was identified as N-(sec-butoxymethyl)-21-n-butoxy-b 1-ethyi-2-chioroacetanilide.

The secondary anilide starting material used in the above examples is prepared according to known methods, e.g., by haloacetylation of 'the corresponding 20 primary amine with such haiaoacetylation agents as a haloacetyl haiide or anhydride. Typically, the appropriate quantity of the appropriate primary amine is dissolved in a solvent such as methylene chloride containing a base, e.g. , 1U% NaOH, and stirred 25 vigorously while mixing with a solution of the haloacetyl haiide, e.g., chloroacetyl chloride, under external cooling, e.g., at 15-25°C. The layers are separated and the organic solvent layer washed with water, dried and evaporated in vacuo. 30 The primary amines used to prepare the secondary anil ides also may be prepared by known means e.g. , by catalytic reduction of the corresponding appropriately-substituted nitrooenzene, e.g., 2-alkoxy b-aikyi nitrobenzene, in a solvent such as an alcohol, 35 e.g., ethanol, using platinum oxide catalyst.

Example 5 This example describes tne preparation of N— 1 -6- ■*&*rTZS2 (2-methoxyprop-2~yi)-21-n-butoxy-b1-e tnyl-2-chloroace tanilide.

To a chiiied solution ot N-(2-methoxyprop-2-yl)-2'-n-butoxy-61ethylaniline, 4.42 g (0.016 mol), in 5- 0.0176 mol of 10% NaOH and 100 mi CH2CI2 was aoaed 2 g (0.0176 mol) of chloroacetyl chloride dropwise? the solution was stirred for 10 minutes, the formed layers separated and the organic phase washed with water, dried over M^S04 and evaporated by Kugeirohr to obtain 10 3.5 g (65% yield) of a yellow oil, b.p. 132°C at 0.07 mm Hg.

Anal.: Calc'd for CiaH2uCiNG3 (%):C, 63.24; H, 8.26; CI, 10.37; Found: C, 63.16; H, 8.27 15 CI, 10.36 The product was identified as in the lead sentence ot tnis example.

The seconcary aniiiue starting material usea ^ Example 5 is obtained by known means,-(a.g. ,—as in / 20 Be-lgian■ Patent 810,763 mentioned above K. Thus, i9.3 g (0.1 mol) of 2'-n-butoxy-6'-ethylaniline was. heated at 50°C in 15 ml of ethanol and i5 mi glacial acetic acid, then 9.68 g (0.11 mol) of methoxyacetone and 0.1 g Pt02 adaed ana the mixture hyarogenated at 50°C for 4 25 hours; the mixture was filtered, evaporated by Kugeirohr at 100°C 0.07 mm Hg to obtain a yellow oil. Anal. Calc'd for £1^27^02 C' 72.41; H, 10.25; N, 5.28; Found: C, 72.36; H, 10.27; 30 N, 5.23 The product was identified as N-(l-methoxyprop-2-yl)-21-n-butoxy-6'-ethylaniline.

Examples 6-13 Following substantially the same proceaure 35 and conditions described in Examples 1-4 using the same secondary aniiiue out substituting tne appropriate alkylating agent as starting material ana quantities 1965 -9- -AG-rr2^2—' thereof, the corresponding products in Examples 6-13 corresponding to the formula in Table 1 were prepared. Thus, Examples 6-12 were prepared according to the N-alkylation process described in Examples 3 and 4 ana the product of Example 13 was prepared by the N-alkylation process of Examples 1 and 2. 9h3 ■CH2CHCH2CH3 TABLE I 0 II ClCHoC . C!I2OR1 \ / N c2H5 I 0-n-C^H9 0 BP°C (mmHg) Element i-Cj-H 137 C D 11 (0.04) H CI 1-CaHQ 120 C (0.03) H CI ri-CoH-j 117 C J 1 (0.02) H CI 134 C (0.03) H CI Analysis Calculated Found 64.94 64.96 8.72 8.75 ? 9.58 9.58 64.12 64.06 8.50 8.53 9.96 10.06 63.24 63.31 8.26 8.27 .37 10.42 64.94 64.86 8.72 8.72 9.58 9.62 M • • TABLE I (continued) BP°C Ex. No. R-^ (mmHg) n"c4H9 128 (0.03) 11 CH3 130 (0.04) 12 i-C3H7 119 (0.02) l J. P. & S. 4-3 Gl m.

Element Analysis Calculated Found c 64.12 64.05 H 8.50 8.49 CI 9.96 9.91 C 61.24 61. 31 H 7.71 7.71 CI . 30 . 33 C 63.24 63.41 H 8.26 8.31 CI .37 .46 £ 5-9rTT 11 £i 20.60 20.52 9^A CO Oi Os -12- -MHi2i>2 As noted above, the compounds ot chisj^ invention have been found to be effective against major Asian weeds as transplant rice herbicides. However, pre-emergence and post-emergence herbicidal activity 5 against other weeds in other crops has also been shown. Tables II and III summarize results of tests conducted to determine the pre-emergent herbicidal activity of the compounds of this invention.

The pre-emeryent tests were conducted as follows: A good grade of top soil is placed in aluminum pans and compacted to a depth of three-eights to one-half inch from the top of the pan. On the top of the soil is placed a number of seeds or vegetative 15 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 20 thoroughly mixed, and used to cover the prepared pans. After treatment, the pans are moved into a greenhouse bench where they are watered by subirrigation as needed to give adequate moisture for germination and growth.

Approximately 2 weeks after seeding and 25 treating, the plants were observed ana the results recorded. Tables II and III below summarize such results. The herbicidal rating was obtained by means of a fixed scale based on the percent injury of each plant species. The ratings are defined as follows: 30 % Control Rating 0-24 0 -49 i 50-74 2 75-100 3 Undetermined 5 The plant species utilized in one set of 1965 &G-M.25Z"" tests, the oata for which are shown in Table II are identified by letter in accordance with the following legend: C Lambsquartecs I F Smartweed J G Yellow K Nutsedge K Uuackgrass Canada Thistle Cocklebur Velvetleaf Johnsongrass Downy Brome Barnyardgrass D Morningglory 196549 Table II Pre-Emergent -5- - Compound of Example No. kg/ha A B C Plant D E Species F G H I J K 1 11.2 3 2 1 2 3 3 3 3 3 3 3 .6 3 2 1 2 3 2 3 3 0 3 3 2 11.2 3 2 2 3 3 3 3 3 3 3 3 .6 2 1 1 1 1 1 3 2 0 3 3 3 11.2 0 1 1 2 2 3 3 3 3 3 .6 0 0 0 3 2 2 3 3 3 3 4 11.2 3 0 0 0 2 1 3 2 0 3 3 .6 3 0 0 0 1 2 2 3 0 3 3 11.2 0 1 0 3 2 3 3 3 3 .6 0 0 0 2 3 1 3 3 3 6 11.2 0 0 0 0 1 0 3 0 3 3 .6 0 0 0 0 0 3 0 0 3 3 7 11.2 2 0 3 2 3 3 3 3 1 3 3 .6 3 1 2 3 3 3 2 3 1 3 3 8 11.2 3 0 0 0 2 1 3 2 1 3 3 .6 3 1 0 0 2 1 3 2 0 3 3 9 11.2 0 0 0 0 1 1 2 0 3 3 .6 0 0 0 0 0 0 0 0 3 3 11.2 3 0 1 1 1 2 2 3 3 3 3 .6 1 0 0 0 3 1 1 1 1 3 3 11 11.2 3 1 2 3 3 2 3 3 2 3 3 .6 0 0 2 2 2 1 3 2 3 3 3 12 11.2 2 0 1 3 3 1 3 3 2 3 3 .6 1 0 1 1 1 1 3 2 1 3 3 13 11.2 0 0 1 0 2 0 3 2 0 3 3 .6 0 0 0 0 1 0 0 1 0 3 3 The compounds were further tested by utilizing the above procedure on the following plant species: L Soybean R Hemp sesbania M Sugarbeet E Lambsquarters N Wheat F Smartweed 0 Rice C Velvetleaf 196 < AG^1252 P Sorghum B Cocklebur Q Wild Buckwheat D Morningglory J Downy brome S Panicum Spp.

K Barnyardgrass T Crabgrass The results are summarized in Table III.

Table III Compound of Example No. 1 Pre-Emergent Plant Species kg/ha L M N 0 p B Q D R E F C J S K T .6 2 3 3 3 3 1 2 3 3 3 3 2 3 3 3 1.12 0 2 3 3 3 0 2 0 3 3 2 0 3 3 3 0.28 1 2 3 2 2 0 1 0 3 3 3 0 3 3 3 0.06 0 0 1 1 0 0 0 0 0 0 0 0 2 1 3 0.01 0 0 0 0 0 1 0 0 0 0 0 0 0 0 2 .6 0 3 3 3 3 0 2 1 2 3 3 0 3 3 3 1.12 0 3 2 3 3 0 1 0 1 3 2 0 3 3 3 0.28 0 2 2 3 1 0 0 0 0 1 0 0 3 2 3 0.06 0 1 0 1 0 0 0 0 0 0 0 1 0 2 0.01 0 1 0 0 0 0 0 0 0 0 0 0 0 0 2 .6 0 2 3 3 3 0 3 0 1- 3 3 1 3 3 3 1.12 1 2 2 1 0 1 1 0 2 1 0 3 3 3 0.08 0 1 1 2 1 0 0 0 0 1 0 0 3 3 3 0.56 0 0 0 0 0 0 0 0 0 0 1 0 0 0 3 .6 0 2 3 3 3 0 1 0 2 2 2 0 3 3 3 1.12 0 0 1 1 0 0 0 0 1 0 0 0 3 2 3 0.28 0 1 0 0 0 0 0 0 0 0 0 0 2 1 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 .6 0 2 3 3 3 0 1 1 2 3 3 1 3 3 3 1.12 0 0 2 2 3 0 1 0 0 1 1 0 3 3 3 0.28 0 0 0 1 0 0 0 0 0 0 0 0 2 3 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 1 0 2 0.01 0 0 0 0 0 0 0 0 0 0 0 0 1 0 1 i M cr> I 2^' £ n M Oc) Table III (Continued) Pre-Emergent Compound of Example No.

Plant Species 11 kg/ha L M N 0 P B Q D R E F C J S K T .6 0 1 2 1 1 0 0 1 0 0 0 0 3 3 3 1.12 0 0 0 0 0 0 0 0 0 0 0 0 3 3 3 0.28 0 0 0 0 0 0 0 0 0 3 0 0 2 0 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 .6 1 3 2 3 3 2 2 3 3 3 3 1 3 3 3 3 1.12 0 2 1 2 3 0 1 1 3 3 1 0 3 3 3 3 0.28 0 1 0 1 3 0 1 0 2 0 0 0 3 3 3 3 0.06 0 1 0 0 1 0 1 0 1 0 0 0 1 2 3 3 0.01 0 0 0 0 0 0 1 0 1 0 0 0 0 1 2 1 .6 1 2 3 3 3 0 3 1 2 3 3 0 3 3 3 1.12 0 0 2 3 2 0 2 0 2 0 1 0 3 3 3 0.28 0 0 0 1 1 0 0 0 0 0 0 0 3 3 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 1 0 3 0.01 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 .6 0 1 1 1 1 0 1 0 1 1 0 0 3 3 3 1.12 0 1 0 0 0 0 0 0 2 3 1 1 3 1 3 0.28 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 .6 0 1 2 2 3 0 1 0 1 1 1 0 3 3 3 1.12 0 0 1 0 1 0 0 0 3 0 0 0 3 2 3 0.28 0 0 0 0 0 0 0 0 0 0 0 0 2 1 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 .6 0 3 3 3 3 0 1 3 3 3 3 1 3 3 3 1.12 0 3 2 3 3 0 1 1 1 2 2 0 3 3 3 0.28 0 2 0 2 2 0 1 .0 2 2 1 0 3 3 3 •^i i Table III (Continued) Pre-Emergent Compound of Example No. 12 13 Plant Species kg/ha L M N 0 P B Q D R E F C J S K T .6 0 3 3 3 3 0 2 1 2 2 2 0 3 3 3 1.12 0 2 2 3 1 0 1 0 1 2 1 0 3 3 3 0.28 0 1 0 2 0 0 0 0 0 0 0 0 3 1 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 .6 0 2 3 3 2 0 2 1 2 3 1 0 3 3 3 1.12 0 1 2 2 1 0 2 0 2 1 0 0 3 3 3 0.28 0 0 1 1 0 0 0 0 1 0 0 0 3 1 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 00 I i 1965 -19- —AG The herbicides of this invention have been found to possess unexpectedly superior properties as transplant rice herbicides, most particularly in the effective selective control of the economically 5 significant resistant annual weeds, Echinochloa crus-gaili and *Monochoria vaginalis and the perennials Cyperus serotinus (but for an exception or two) and Eleocharis kuroguwai, while in some instances suppressing the perennial weed Sagittaria trifolia to a 10 greater extent than the commercial herbicide MACHETE, and also controlling or suppressing many other less-resistant perennial and annual weeds.

In order to illustrate the unexpectedly superior properties of compounds according to this 15 invention both on an absolute basis and on a relative basis, comparative tests were conducted in the greenhouse. In these tests MACHETE herbicide (the only current commerciai 2-haioacetaniiide rice herbicide) was tested for comparative purposes. 20 In the discussion of test data below, occasional reference is made to herbicide application rates symbolized as "GR^" and "GR^"; these rates are given in kilograms per hectare (kg/ha) which are convertible into pounds per acre (lbs/A) by dividing 25 the kg/ha rate by 1.12. GRi5 defines the maximum rate of herbicide required to produce 15% or less crop injury, and GRg^ defines trie minimum rate required to achieve 85% inhibition of weeds. The CR^ and GR^ rates are used as a measure of potential commercial 3q performance, it being understood, of course, that suitable commerciai herbicides may exhibit greater or lesser plant injuries within reasonable limits.

A further guide to the effectiveness of a chemical as a selective herbicide is the "selectivity 35 factor" ("SF") for a herbicice in given crops and weeds. The selectivity factor is a measure of the relative degree of crop safety ano weed injury and is 1 -20- AH-1? ^ ?—* exprusseu in teuus of the GR^/GR^ ratio, i.e., the GR15 rate for the crop divided by the GRQ5 rate for the weea, both rates in kg/ha (lb/A.) Since crop tolerance and weed control are 5 inter-reiated, 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, be high, since higher concentrations ot herbicide are frequently desired for 10 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 15 control certain weeds and a larger rate 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 20 made of selectivity factors (defined above) to quantify the relationship between crop safety and weed control; the higher the numerical value, the greater selectivity of the herbicide for weed control in a given crop.

In one comparative test in the greenhouse, 25 herbicidal activity data were obtained and are presented in Table IV comparing the relative efficacy of the compounds oi Examples 1, 3-b, b and y, representative compounds of this invention, with butachlor, (active ingredient in MACHETE, a commercial 30 rice herbicide) as selective herbicides against economically-significant Asian weeds commonly associated with transplant rice.

The test procedure used in this greenhouse test is as follows: Ray silt loam top soil containing 35 about 0.05% by weight of krillium and sifted through a 0.5 in. (0.6 cm) screen and is fumigated about 5-10 days prior to use. Pots are then filled with Sdia Ray sixt loam soil 1 -21- ^AC 125-2 to a level to allow for a 1 in. (2.54 cm) flooding depth. Rice plants (Bluebelle) of 2 to 3 weeks age are transplanted to the pots and bulbs or seeds of the test weeds also planted in the pots. The pots are then 5 flooded and the test chemical applied to the surface of the flood water. The flood water is reduced to allow for germination of the Echinochloa crus-galli (barnyardgrass) seed and subsequently reflooded and maintained in that condition. Observations of percent 10 inhibition using a scale of 0-100% are made about 3 weeks after treatment (WAT).

Test data shown in Table IV below represent percent inhibition of the plants within the test rate limits of 0.2b kg/ha to 2.24 kg/ha (0.25-2.0 lb/A). 15 The data are expressed in terms of anc* GR85 rates' respectively, for rice and the weeds* as explained above; selectivity factors are shown in parentheses below each weed; "NS" means non-selective within the test rate limits. The degree of control of Sagittaria 20 trifolia, one of the niost important commerciai problem weeds and the most 2-haioacetamide-resistant perennial of the test we,'jus, is shown in the last column of TaDle IV; the percent control shown is at the maximum test rate of 2.24 kg/ha. The weed species are identified as 25 follows: Echinochloa crus-galli (EC), Monochoria vaginalis (MV), Cyperus serotinus (CS), Eleocharis kuroguwai (EK) and Sagittaria trifolia (ST).

GR^Rate (Kg/Ha) Ccmpound Rice EC MV Butachlor 2.24 <0.28 (>8.0) <0.25 (>8.0) Ex. 1 2.24 <0.28 (>8.0) <0.28 (>8.0) Ex. 3 >2.24 <0.28 (>8.0) <0.28 (>8.0) Ex. 4 >2.24 <0.28 (>8.0) <0.28 (>8.0) Ex. 5 >2.24 <0.28 (>8.0) <0.28 (>8.0) Ex. 6 >2.0 <0.28 (>8.0) <0.28 (>8.0) Ex. 8 1.96 <0.28 (>7) <0.28 (>7.0) Ex. 9 1.87 <0.28 (>6.7) <0.28 (>6.7) TABLE IV GRg5Rate ST Control (Kg/Ha) at 2.24 Kq/Ha CS EK ST (%) <0.25 0.4 >2.24 15 (>8.0) (5.0) (NS) <0.28 <0.28 >2.24 65 (>8.0) (>8.0) (NS) <0.28 <0.28 >2.24 30 (>8.0) (>8.0) (NS) <0.28 <0.28 >2.24 20 ^ (>8.0) (>8.0) (NS) to <0.28 -<=0.28 >2.24 10 ! (>8.0) (>8.0) (NS) <0.28 0.43 >2.24 10 (>8.0) (>4.7) (NS) <0.28 <0.28 >2.24 70 C>7.0) (>7.0) (NS) 0.31 0.86 >2.24 25 (5.4) (1.9) (NS) I 1965^ - Z 3 — - Af-— 'h ii ^ i1 Reference to the data in Table IV will show several important advantages of the invention compounds relative to butachlor as follows: (1) Examples 3-6 had higher rice safety factors; (2) Examples 1, 3-5 and 8 5 had higher selectivity factors against EK and (3) Examples 1, 3, 4, 8 and 9 all exhibited a higher percentage control of ST than butachlor. The overall superiority of compounds according to this invention, particularly those of Examples 1 and 3-6, vis-a-vis the ]_0 commercial herbicide, is clearly shown by the data in Table IV.

In another comparative test in the greenhouse, other compounds according to this invention were also compared with butachlor as a standard 15 transplant rice herbicide. The compounds of Examples 2, 7 and 10-13 and butachlor were tested according to the above-described procedure; the test data are shown in Table V.

Compound Butachlor Ex. 2 Ex. 7 Ex. 10 Ex. 11 Ex. 12 Ex. 13 TABLE V GR-^ijRate (Kg/Ha) Rice EC MV 1.63 0.99 1.3 (1.7) (1.3) 1.8 <0,28 *0.25 (>7.2) (>7.2) >2.24 <0.28 <0.43 (>8.0) (>5.3) >2.24 <0.28 <0.28 (>8.0) (>8.0) 1.12 <0.28 <0.28 (4.0) (>4.0) 0.75 <0.28 <0.28 (>2.7) (>2.7) 1.12 <0.28 <0.28 (>4.0) (>4.0) GRo^Rate ST Control cs EK ST (%) >2.24 .71 >2.24 (NS) (2.4) (NS) 0. 78 <0.28 >2.24 (2.6) (>7.2) (NS) <0.52 .47 >2.24 0 (4.3) (4.8) (NS) >2.24 <0.28 >2.24 0 (NS) (>8.0) (NS) 0.95 <0.28 >2.24 (1.2) (>4.0) (NS) 1.8 <0.28 >2.24 (NS) (>2.7) (NS) 1.0 <0.28 >2.24 (1.1) (>4.0) (NS) M •P. I CO 196549 Referrmg to the test data in Table V, it is again noted that each of the invention compounds exhibited one or more advantages over butachlor as follows: (1) Examples 2, 1 and 10 exhibited higher safety factors in rice and (2) every invention compound exhibited higher selectivity factors against EC, MV, CS (except Example 10) and EK than butachlor. Although butachlor exhibited higher safety factors than Examples 11-13 and higher percentage control of ST than the invention compounds, these advantages were offset by significantly lower selectivity factors in most of the weeds in the test. It should be mentioned that although greenhouse and field test will vary from test to test (more in the greenhouse than the field usually), the comparative data shown in the tables herein were under identical conditions with respect to all herbicides in the test.

In otiier comparative tests in the greenhouse, one at a maximum test rate of 1.12 kg/ha and another a maximum test rate of 2.24 kg/ha, the compound of Example 3 and butachlor were tested in Upland seeded rice. It was found that as an average of the two tests, the compound of Example 3 selectively controlled Echinochloa crus-galli (barnyardgrass) at 0.31 kg/ha (0.277 lb/A) while maintaining rice safety at a rate of >1.43 kg/ha (1.23 lb/A), resulting in a selectivity factor of at least 4.6. In contrast, butachlor (a commercial rice herbicide), required 0.7 kg/ha (0.625 lb/A) to selectively control the same weed with rice safety maintained at >l.bd kg/ha (>1.5 lb/A) resulting in a selectivity factor of at least 2.4 i.e., about one-half that of the compound of Example 3.

In further tests in the greenhouse, the compound ot Example 3 was tested tor its activity against annual weeds in sugarbeets at test rates within the range of 0.07 to 1.12 kg/ha (0.0b25 to 1.0 lb/A). The GRi5 and GR^ rates for sugarbeets and the various 1965 -2o- AG-1T2-3TT weeds are shown in Table VI; the selectivity factors for the herbicide against the weeds in sugarbeets are shown in parentheses below the weeas; "NS" means non-selective within the test limits. The following abbreviations are used in the table: barnyardgrass (BYG), wild oats (WO), downy brorae (DB), redroot pigweed (RRP), blaekgrass (BG), large crabgrass (LCG) and yellow foxtail (YFT).

Table VI . GRi5 Rate GR85 Rate -(Kg/ha ) (Kg/ha) — Sugarbeets BYG WO DB _ RRP BG LCG YFT >1.12 <0.07 0.2b 0.21 >1.12 0.14 0.14 0.14 (>lb) (>4) (>5.3) (NS) (>8) (>8) (>8) The data in Table VI show that the compound of Example 3 selectively controlled every weed in the test, except redroot pigweeu, at rates well below 1.12 kg/ha, thus proving the versatility of that compound as an effective hetbiciae in important crops.

The invention compounds may be safely used with the normal degree of care required for handling herbicidal compounds; no special precautions are required.

Therefore, it will be appreciated from the foregoing detailed description that compounds according to this invention have demonstrated unexpected and outstandingly superior herbicidal properties both absolutely and relative to structurally-relevant compounds af the prior art, one of which (butachlor) is the active ingredient in a commercial herbiciae. More particularly, the compounds of this invention have proven to be outstanding selective heroiciues, particularly in the control of economically-significant Asian annual and perennial weeds in transplant rice. 19654 In more particular, compounds according to this invention exhibit outstanding control of the annual grasses Echmochioa crus-galli and Monochoria vaginalis and perennials such as Cyperus serotinus, 5 Eleocharis kuroguwai ano some members are particularly effective against Sagittaria trifolia, while controlling and/or suppressing other less-resistant annual grasses and perennials, including those mentioned in Tables II, III and VI above, and others.

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 5 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 10 active ingredient can be used with an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.

The compositions of this invention, 15 particularly liquids and wettable powders, preferably contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into 20 the compositions greatly enhances their efficacy. By the term "surface-active agent" it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Anionic, cationic and non-ionic agents can be used with equal 25 facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, 30 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 35 mono-higher fatty acid esters of hexitol anhydrides (e.g., sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl, naphthalene sulfonates, sodium naphthalene sulfonate, and the polyinethylene bisnaphthalene sulfonates.

Wettable powders are water-dispersible compositions containing one or more active ingredients, an inert solid extender and one or more wetting and dispersing agents. The inert solid extenders are usually of mineral origin such as the natural clays, 10 diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate. The wettable powders compositions of this invention usually contain from about 0.5 to GO j_5 parts (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent, from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 95 parts (preferably 5-50 parts) of inert 20 solid extender, all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts of the solid inert extender can be replaced by a corrosion inhibitor of anti-foaming agent or both.

Other formulations include dust 25 concentrates comprising from 0.1 to 50% by weight of the active ingredient on a suitable extender; these dusts may be diluted for application at concentrations within the range of from about 0.1-10% by weight.

Aqueous suspensions or emulsions may be 30 prepared by stirring an aqueous mixture of a water-insoluble active ingredient and an emulsification agent until uniform and then homogenized to give emulsion of very finely-divided particles. The resulting concentrated aqueous suspension is 35 characterized by its extremely small particle size, so that when diluted and sprayed, coverage is very uniform. Suitable concentrations of these formulations 1 -30- .AG*1252 - contain from about 0.1-50%, 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 suspension, a water-iminiscible 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 10 sulfonate emulsifier and a water-immiscible chemical and polymethylene polyphenylisocyanate, dispersing the water-immiscible 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 15 around particles of the water-immiscible chemical, thus forming microcapsules thereof. Generally, the concentration of the microencapsulated material will range from about 480 to 700 g/1 of total composition, preferably 480 to 500 g/1.

Concentrates are usually solutions of active ingredient in water-immiscible or partially water-immiscible solvents, together with a surface active agent. Suitable solvents for the active ingredient of this invention include dimethylformide, 25 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 30 concentration.

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

Granules are physically stable particulate 5 compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender. In order to aid leaching of the active ingredient from the particulate, a surface active agent such as those listed 10 hereinbefore can be present in the composition.

Natural clays, pyrophyllites, illite and vermiculite are examples of operable classes of particulate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles,such as preformed and 15 screened particulate attapulgite, or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the 20 herbicidal granules.

The granular compositions of this invention may contain from about 0.1 to about 30 parts, preferably from about 3 to 20 parts, by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts 25 by weight of surface active agent per 100 parts by weight of particulate clay.

The compositions of this invention can also contain other additaments, for example, fertilizers, other herbicides, other pesticides, safeners and the 30 like used as adjuvants or in combination with any of the above-described adjuvants. Other herbicidal compounds useful in combination with the active ingredients of this invention, particularly for use in transplant rice, include, for example, methyl-5 (2,4-35 dichlorophenoxy)-2-nitrobenzoate (common name "bifenox", active ingredient in MODQWN® herbicide), 1-3-dimethy1-4-(2,4-dichlorobenzoyl)-5-pyrazolyl J. i? Ot) -32- .AG-1253— paratoluene sulfonate (code designation "SW-751"), o*—(^-naphthoxy) propionanilide (coded MT-101"), 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether (coded "X-52"), 3,4-dichloropropionanilide (common name "propanil") , etc. For use in other non-rice crops, other herbicidal compounds may also be combined with compounds according to this invention. For example, such other compounds include triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like such as: Heterocyclic Mitrogen/Sulfur Derivatives 2-Chloro-4-ethylamino-6-i sopropylamino-£-triazine 2-Chloro-4,6-bis(isopropylamino)-s-triazine 2-Chloro-4,6-bis (e thylamino) -_s- tr ia zine 3-Isopropyl-lH-2,1,3-benzothiad iazin-4-(3II)-one 2,2 dioxide 3-Amino-1,2,4-triazole 6 ,7-Dihydrod ipyr ido(l,2-a:2' ,1'-c) -pyrazid i in iurn salt -Bromo-3-isopropyl-6-methyluracil 1,1,-Dimethyl-4,4,-bipyridinium -tert-butyl-3- (2,4-dLchloro-5-isopropoxyphfinyl) -1,3,4-cocadiazol-2-cne Ureas N•-(4-chlorophenoxy) phenyl-N,N-dimethylurea N,N-dimethyl-N(3-chloro-4-methylphenyl) urea 3-(3,4-dichlorophenyl)-1,1-dimethylurea 1 ,3-Dimethyl-3- (2.-benzo thiazolyl) urea 3-(p-Chlorophenyl)-1,1-d imethylurea l-Butyl-3-(3,4-dichlorophenyl)-1-methyl urea Carfaamates/Thiolcarbamates 2-Chloroallyl diethyIdithiocarbamate S- (4-chlorobenzyl)N,N-d iethylthiolcarbamate Isopropyl N-(3-chlorophenyl) carbamate £-2,3-dichloroallyl N,N-diisopropylthiolcarbamate Ethyl N,N-dipropylthiolcarbamate S-propyl dipropylthiolcarbamate Acetamides/Acetanilides/Anilines/Amides 2-Chloro-N,N-diallylacetamide N,N-dimethy1-2,2-diphenylacetamide N- (2,4-dimethy1-5-[[(trifluororaethyl)sulfonyl] amino]phenyl)acetamide N-Isopropyl-2-chloroacetanilide 2',5'-Diethyl-N-methoxymethyl-2-chloroacetanilide 2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2- chloroacetanilide c*, ot -Tr if luoro-2, 6-dinitro-N ,N-d i propyl-£-toluid ine N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide 20 Acids/Esters/Alcohols 2,2-Dichloropropionic acid 2-Methyl-4-chlorophenoxyacetic acid 2,4-Dichlorophenoxyacetic acid Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy] 25 propionate 3-Amino-2,5-dichlorobenzoic acid 2-Methoxy-3,5-dichlorobenzo ic ac id 2,3,6-Trichlorophenylacetic acid N-l-naphthylphthalamic acid Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2- ni trobenzoate 4,6-Dinitro-o-sec-butylphenol 196549 -M-1252— N-(phosphonornethyl) glycine and its C, r monoalkyl amine and alkaline metal salts and combinations thereof Ethers 2 /4-Dichiorophenyl-4-nitrophenyl ether 2-Chloro- oC, , oC-trifluoro-_g-tolyl-3-ethoxy-4-nitrodiphenyl ether Miscellaneous 2,^-Dichlorobenzonitrile Monosodium acid methanearsonate Disodium methanearsonate The herbicides of this invention may be used singly, as mixtures with other herbicides and may be used in sequential use with other herbicides. For example, treatments of a transplant rice crop with the herbicides of this invention may be followed with treatments of other herbicides or mixtures such as S-4-chlorobenzyl diethylthiocarbamate (common name "benthiocarb") plus 2-chloro-4,S-di(cthylamino)-1,3,5-triazine (common name "simazine") or 3-i sopropyl-(1H)-benzo-2,l,3-thiadiazine-4-one-2,2-dioxide (common name "bentazone") or 4-(4-chloro-2-methylphenoxy)butyric acid (common name "MCPB").

The compounds of this invention have their primary utility in transplant rice. However, as indicated by the test data for the compound of Example 3 in Table V, at least some members of this class may also be used in direct-seeded rice. However, because of the high unit activity of compounds according to this invention, direct-seeded ricc may be less tolerant of some members of the invention compounds.

Accordingly, it is within the purview of this invention to combine these herbicides with safeners or antidotes to enhance the tolerance of both transplanted and diroct-seeded rice thereto. Exemplary safeners contemplated as useful with the herbicides of this invention include the phenylglyoxylonitrile-2-oxime cyanomethyl ether described in U.S.Patent No. 4 , 152, 137, 2,4-disubstituted -5-thiazolecarboxylic acids and derivatives thereof as descxibedin U.S. Patent No. 4,199,506 and other known safeners for 2-ha.ioanp-t-aniliin rice.

Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

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

I. Emulsifiable Concentrates A. Compound of Example 1 Weight Percent 50.0 Phosphate ester of ethoxylated alcohols (e .g. GAFAC® 'KE-610) 4.125 Ethoxylated tertiary amine derived from fatty oils such as palm oil (e.g. Ethomeen® C/12) 0.875 13.5 31 .5 Monochlorobenzene Cg aromatic Solvent (T-400) 100.00 B. Compound of Example 3 GAFAC RE—'ill Ethomeen® C/12 MCB 4 5.45 4.125 0.875 43 .55 100.00 196549 -36- ■' AG 12£'2 C. Compound of Example No. 4 5.0 Calcium dodocylbenzene sulfonate/ polyoxyethylene ethers blend (e.g., Atlox 34 3 7F) 1.0 Xylene 94.0 100.00 II. Liquid Concentrates Weight Percent A. Compound of Example No. 5 10.0 Xylene 90.0 100.00 B. Compound of Example No. 5 85.0 Dimethyl sulfoxide 15 .0 100.00 m C. Compound of Example No. 7 5 0.0 N-methylpyrrolidone 50 .0 100.00 D. Compound of Example No. 3 5.0 Ethoxylated castor oil 20.0 Rhodamine B .5 Dimethyl formamide 74.5 100.00 III. Sinul s ions Weight Percent A. Compound of Example No. 9 40.0 Polyoxyethylena/polyoxy-propylene block copolymer with butanol 196 (e.g., Tergitol^ XH) Water 4.0 56.0 100.00 B. Compound of Example No. 10 Polyoxyethylene/polyoxy-propylene block copolymer with butanol Water .0 3.5 91.5 100.00 IV. Wettable Powders Compound of Example No. 1 Sodium iignosulfonate Sodium N-methyl-N-oleyl-taurate Amorphous silica (synthetic) B. Compound of Example No. 3 Sodium dioctyl sulfosuccinate Calcium 1ignosulfonate Amorphous silica (synthetic) Weight Percent 25.0 3.0 1.0 71.0 100.00 80.0 1.25 2.75 16.00 Compound of Example No. 4 Sodium 1iynosulfonate Sodium N-methyl-N-oleyl-taurate Kaolinite clay 100.00 .0 3.0 1.0 86.0 100.00 V. Dusts Compound of Example No. 10 Attapuig ite Weight Percent 2.0 98.0 100.00 VI. Granules -AG 125 ^ B. Compound of Example No. 11 60.0 Montmorillonite 40.0 100.00 C. Compound of Example No. 12 30.0 Bentonite 70.0 100.00 D. Compound of Example No. 13 1.0 Diatomaceous earth 99.0 100.00 Weight Percent A. Compound of Example No. 1 15.0 Granular attapulgite (20/40 mesh) 85.0 100.00 B. Compound of Example No. 3 30.0 Diatomaceous earth (20/40) 70.0 100.00 J. P. & S. 3o' o m-61 C. Compound of Example No. 4 -6-rS" .....20 Bentonite (20/40) 70.0 100.00 D. Compound of Example No. 5 5.0 Pyrophyllite (20/40) 95.0 100.00 VII. Microcapsules A. Compound of Example No. 1 encapsulated in polyurea shell wall bodium lignosuifonate (e.g. 49.2 1965 4" -39- -AG" 123 a Redx Ub'-'B) 0.9 Water 49.9 100.GU B. Compound of Example No. 3 encapsulated in polyurea shell wail 10.0 Potassium lignosuifonate (e.g., Reax« C-21) .5 Water a9.5 100.00 C. Compound of Example No. 4 encapsulated in polyurea shell wall 80.0 Magnesium salt of lignosulfate (Treax® LTM) 2.0 Water 18.0 100.00 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 20 convenient fashion. The application of liquid and particulate solid compositions to the soil can be carried out by conventional methods, e.g., power dusters, booiu and hand sprayers and spray dusters. 'i'ne compositions can also be applied from airplanes as a 25 dust or a spray because of their effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired. 30 The application of an effective amount of tne compounds of tills invention to the iocus of undesireu weeds is essential and critical for the practice of th^ present invention. The exact amount of active ingredient to be employed is dependent upon various 1965 4 -40- -AG-4r255 factors, including use in aqueous or soil media, the plant species and stage of development thereof, the type and condition of soil, the amount of rainfall and the specific anilide employed. In selective preeinergence application to the plants or to the soil a dosage of from 0.02 to about 11.2 kg/ha, preferably from about U.U4 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 suffice or be required in some instance. For example, in some upland-seeded rice tests, compounds according to this invention have shown a measurable amount of injury to barnyardgrass at extremely low rates. Thus, the compound of Example 3 exhibited 5% control of barnyardgrass at 0.035 kg/ha (0.0313 lb/A) and the compound of Example 5 exhibited 10% control of barnyardgrass at 0.0175 kg/ha (0.01563 lb/A). One skilled in the art can readily determine from this specification, including the above example, the optimum' rate to be applied in any particular case.

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

Although the invention is described witn respect to specific modifications, the details thereof are not to be construed as limitations except to the extent indicated in the following claims.

Claims (1)

1. WHAT WE CLAIM IS: 1. Compounds having the formula C1CH2C , „R • S C2H5 °-n-C4H9 wherein R is allyl, chloroallyl, propargyl, 1-methoxyprop-2-yl or a hydrocarbyloxymethyl radical of the formula -CI^OR^, wherein R^ is methyl, isopropyl, N-butyl, isobutyl, sec-butyl, isoamyl orf 2-methyl-butyl./ 2. Compound accoraing to Claim 1 which is N-propargyl-2'-n-butoxy-b'-ethyl-2-chloroacetanilide. 3. Compound accoraing to Claim 1 which is N-(l-methoxyprop-2-yl)-2'-n-butoxy-b'-ethyl-2-chloroacetanilide. 4. Compounds accoraing to Claim 1 wherein R-^ is a C3..5 alkyl raaical. 5. Compound accoraing to Claim 4 which is N-(sec-butoxymethy1)-2'-n-butoxy-61-ethy1-2-ciiloroacetanil ice. 6. Compound according to Claim 4 which is N-(2-methylbuty1)-2'-n-butoxy-6'-ethyi-2-chloroacet-anii ide. 7.| Compouna accoraing to Claim 4 which is N-(isoamyloxymethyl)-2'-n-butoxy-61-ethyl-2-chloroace tan nice. 8.1 Compouna accoraing to Claim 4 which is N-(isobutoxymethyl)-2'-n-butoxy-b'-ethyl-2-chloroacetanilide , N.Z. PATENT OFFICE 2 9SEP1983 1 f-' ' ^ / 9 i ✓ w -i y -42- 9. Compound accoraing to Claim 4 whicu is N-(n-butoxymethyi)-2'-n-butoxy-6'-ethyl-2-chloroacet-anilide. 10. Hecbiciaal compositions comprising an adjuvant and a herbicidally effective amount of a compound of the formula 0 C1CH„C R Z ^ N ^ 5 wherein R is allyl, chloroallyl, propargyl, 1- inetnoxyprop-2-yl or a hydrocarbyloxymethyl radical of the formula -CH..OR, , wherein R-. methyl, isopropyl, N-butyl, isobutyl, sec-butyl, isoamul or 2-methyl-butyl. 11.' Composition accoraing to Claim 10 wherein said compound is N-propargyl-21-n-butoxy-61-ethyi-2-chlorou<_fetaniiide. 12. i Composition according to Claim 10 wherein saia compound is N-(1-methoxyprop-2-yl) - 21-n-butoxy-0 '-ethyi-2-chioroacetanilide. 13. Composition accoraing to Claim 10 wherein in said compound ^ is a C3 5 alkyl radical. 14. Composition accoraing to Claim 13 wherein saia compound is N-(sec-butoxvmetnyl)-2'-n-butoxy-61-ethyi-2-chloroacetanilide. 15, Composition according to Claim 13 wherein said compound is N-(2-methylbutyl)-21-n-butoxy- 2 9SEP.1983 Y b 1 -etnyi-2-chj.oroact: tanil iae. 16. Composition accoruing to Claim 13 wherein said compound is N-(isoamyloxymethyl)-21-n-butoxy-61-etuyi-2-chloroacetanii iae. 17. Composition according to Claim 13 wherein said coiupouna is N-( isobutoxymethyl)-.2'-n-butoxy-b'-ethyl-2-chloroacetanilide. 18. Composition accoraing to Claim 13 wherein said compound is N-(n-butoxymethyl)-2*-n-•butoxy-b1-ethyl-2-cnloroacetaniliae. 19. Method for combatting undesirable plants in crops which comprises applying to the locus of said plants a herbicidally effective amount of a compound of the formula 0 C1CH2C 0-n-C4riy wherein R is allyl, chloroallyl, propargyl, 1-•methoxyprop-2-y i or a hydrocarbyloxymethyl radical of the formula -C^OR^, wherein R^ is methyl, isopropyl, N-butyl, isobutyl, sec-butyl, isoamyl or 2-methyl-butyl. 20. Methoa according to Claim 19 wherein said~crop is'transplanted rice. 21. Methoa according to Claim 20 wherein said compound is N-propargyl-2'-n-butoxy-6'-ethyl-2-chloroaeetaniliae. 22. Method accoraing to Claim 20 wherein said compound is N-(l-methoxyprop-2-yl)-2'-n-butoxy-6 ethyl-2-chloroacct^nilide. N-z- PATENT OFFirc 2 9S£PJ983 -44- 23. Me thou according to Claim 20 ;herein in said compouna is a alkyl radical. 24. Method accoruing to Claim 23 wherein said compound is N-(sec-butoxymethyl)-2'-n-butoxy-b'-e thyl-2-chloroacetanilide. 25. Method according to Claim 23 wherein said compound is N-(2-methylbutyl)-2'-n-butoxy-6'-ethyl-2-chioroacetanilide. 2$J Method _according to Claim 23 wherein i _ • said compound is N-(isoamyloxymethyl)-2'-n-butoxy-6'-ethy1-2-chloroacetanilide. 27.! Method according to Claim 23iwherein said compound is N-(isobutoxymethyl}-2'-n-butoxy-61-ethy1-2-chloroacetanilide. 28. Method accoruing to Claim 23 wherein said compound 'is N-(n-butoxymethyl)-21-n-butoxy-61-ethy1-2-chloroacetanilide. 29. Method for combatting weeds in transplant rice which comprises applying to the locus tnereof a herbiciaaxly effective amount of N- (allyloxymethyl)-21-n-butoxy-61-ethyl-2-chioroacetanilide. 30. Method for combatting weeds in transplant rice which comprises applying to the locus thereof a herbicidally effective amount of N-propargyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide. 31. Method for combatting weeds in transplant rice which comprises applying to the locus thereof a herbicidally effective amount of N-(l-methoxyprop-2-yl) 2'-n-butoxy-6'-ethyl-2-chloroacetanilide. - 45 - 32. A compound as claimed in any one of claims 1 to 9 substantially as hereinbefore described with reference to any example thereof. 33. A composition as claimed in any one of claims 10 to 18 substantially as hereinbefore described with reference to any example thereof. 34. A method as claimed in any one of claims 19 performed! to 31 when proformod substantially as hereinbefore described with reference to any example thereof. 35. A method as claimed in any one of claims 19, 23,26 to 31 and 34 when said compound is present as a composition as claimed in any one of claims 10 to 18 and 33. DATED THIS AY OF 19 ^3 A. J. PARK & SON AGENTS FOR THE APPLICANTS