GB2092131A - Herbicidal 2-haloacetamides - Google Patents

Abstract

Compounds of general formula XCH2CONRCH2A wherein X is chloro, bromo or iodo; R is an acyclic 1-alken- 1-yl radical having up to 8 carbon atoms, a C5-7 1-cycloalken-1-yl radical or one of said radicals substituted with one or more C1-4 alkyl radicals and A is an unsubstituted or C1-4 alkyl-substituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical are useful as herbicides exhibiting both pre- and post-emergence activity.

Description

SPECIFICATION Herbicidal 2-haloacetamides Background of the Invention Field of the Invention This invention pertains to the field of 2-haloacetamides and their use in the agronomic arts, e.g., as herbicides.

Description of the Prior Art It is known in the prior art to use various 2-haloacetamides as herbicides, either individually or in combination with other herbicides.

Among the herbicidal compounds of the prior art are 2-haloacetamides having in varying arrangements and combinations of substituents on the nitrogen atom of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkoxy, halogen, haloalkyl, aryl, aralkyl, N-, 0- and/or S-containing heterocyclyl, etc.

groups, all of which may be further substituted with other radicals.

Illustrative of prior art compounds relevant to the present invention are those having azolylmethyl radicals substituted on the acetamide nitrogen atom; however, such known compounds require that aromatic groups also be substituted on the nitrogen atom. Illustrative of such N-azolylmethyl substituted 2-haloacetanilide compounds are those disclosed in German Patent Application Numbers 2,704,281,2,648,008 and 2,744,396. Other relevant prior art discloses compounds having 1 cycloalken-1-yl groups on the nitrogen atom, but such compounds also require that other nonheterocyclyl radicals also be attached thereto. See U.S. Patent No. 3,574,746 and 3,586,496.Still other relevant prior art includes 2-haloacetamides having 1 -alken-1 -yl radicals substituted on the nitrogen atom, but such compounds require that alkoxyethyl, alkoxypropyl, alkyl or alkenyl radicals be substituted on the nitrogen. See South African Patent No. 753,918.

Perhaps the most relevant prior art known to the inventor herein are disclosures of 2haloacetamides having simultaneous substitutions on the actamide nitrogen atom of 1 -cycloalken-1 -yl or acyclic-1 -alken-1 -yl radicals and a nitrogen-containing heterocyclyl radical. Thus, U.S. Patent No.

4,155,744 (assigned to the assignee herein) discloses said 2-haloacetamides containing the 1 cycloalken-1-yl and N-heterocyclyl radicals. The 2-haloacetamides containing the acyclic I -alken- 1 -yl and N-heterocyclyl radicals require that when there is a heterocyclic radical attached to said nitrogen atom, the 1 -alken-1 -yl radical must have a substitution thereon other than hydrogen, alkyl or alkenyl.

And in said '744 patent, whenever the 2-haloacetamide contains a nitrogen-containing heterocyclyl radical, said nitrogen atom must be substituted with a non-ring member selected from the group consisting of hydrogen, a C57 cycloalken-1 -yI or cycloalkadienyl radical or a saturated or unsaturated heterocyclic radical.

Therefore, it will be appreciated that the most relevant 2-haloacetamides of the prior art are devoid of disclosures of the novel 2-haloacetamides of the present invention as described in more detail below.

Summary of the Invention The present invention relates to herbicidally-active compounds, herbicidal compositions containing these compounds as active ingredients and herbicidal method of using said compositions to combat weeds in various crops.

The compounds of this invention include those within the formula

wherein X is chloro, bromo or iodo; R is an acyclic 1 -alkenyl-1 -yl radical having up to 12, preferably up to 8 carbon atoms, a C57 1 cycloalken-1 -yl radical or one of said radicals substituted with one or more C14 alkyl radicals and A is an unsubstituted or C14 alkyl-subsituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical.

Preferred species of this invention are compounds within the above formula wherein A is a pyrazolyl, triazolyl or imidazolyl radical bound to the methylene radical through a nitrogen atom, most preferably a pyrazol-1-yl radical and wherein R is a 1-cyclohexen-1-yl radical, any of which radicals may be substituted with a C14 alkyl radical. Individual preferred species of the invention are as follows: N-[2-methyl-1 -(1 -methylethyl)- 1 -propenyl]-N-(1 H-pyrazol-1 -ylmethyl)-2-chloroacetamide.

N-( 1 ,2-dimethyl- 1 -propenyl)-N-(1 H-pyrazol-1 -ylmethyl)-2-chloroacetamide.

N-(2,6-dimethyl-1 -cyclohexen-1 -yl)-N-( 1 H-pyrazol-1 -ylmethyl)-2-chloroacetamide.

N-(2,6-dimethyl-l -cyclohexen-l -yl)-N-(l H-1,2,4-triazol-l -ylmethyl)-2-chloroacetamide.

N-(2,6-dimethyl-1 -cyclohexen-1 -yl)-N-(1 H-imidazol-1 -ylmethyl)-2-chloroacetamide.

N-(2,5-dimethyl-1 -cyclopenten- 1 -yl)-N-(1 H-pyrazol-1 -ylmethyl)-2-chloroacetamide.

Other species of the invention will be described below.

The utility of the herbicidal compositions according to this invention is exemplified in Tables II and Ill below.

Detailed Description of the Invention The novel 2-haloacetamides of this invention suitably may be prepared by reacting the appropriate heterocyclic azole compound with the corresponding N-halomethyl-N-(1-alken-1-yl) or (1cycloalken-1 -yi)-2-chloroacetamide to effect replacement of the halogen on the halomethyl group with the appropriate azolyl radical. The starting N-halomethyl 2-haloacetamides may be prepared by a novel process involving the reaction of a concentrated hydrogen halide with the corresponding N (alkoxymethyl)-2-haloacetamide to effect replacement of the alkoxy moiety with the halogen atom.

Said N-alkoxymethyl amides suitably may be prepared by the N-alkylation process described in U.S.

Patent 4,258,196 issued March 24,1981.

Example 1 This example describes the preparation of one novel species of this invention. Paragraph (a) describes the preparation of the N-(alkoxymethyl)-2-haloacetamide used to prepare the corresponding N-halomethyl 2-haloacetamide; paragraph (b) describes the reaction of the amide prepared in paragraph (a) with a hydrogen halide to produce said N-halomethyl compound and paragraph (c) describes the reaction of said N-halomethyl amide with the appropriate azole compound to obtain the invention compound.

(a) This paragraph describes the use of a multiphase system to generate the anion of the desired secondary 2-haloacetamide and alkylation of said anion, preferably in the presence of a phase transfer catalyst to produce the desired corresponding tertiary 2-haloacetamide.

A mixture of 400 g of the sec-amide, N-(2,6-dimethyl-1-cyclohexen-1-yl)-2-chloroacetamide, m.p. 114-1150C, in 760 ml methylene chloride and 300 ml chloromethyl methyl ether were mixed with 2 g benzyl triethyl ammonium bromide. The mixture was cooled to 1 OOC then added in a thin stream over 0.5 hour to a vigorously stirred mixture of 1100 ml of 50% sodium hydroxide, 300 ml methylene chloride and 9 g benzyl triethyl ammonium bromide contained in a 5-liter 4-necked round bottomed flask.Exterior cooling with an ice/acetone bath was necessary to maintain the temperature under250C. The mixture was stirred for an additional one hour. GLC showed 78% tertiary amide produced and 22% of corresponding O-alkylated by-product, O-(methoxymethyl)-N-(2,6-dimethyl-l- cyclohexn-1 -yl)-2-chloroacetimidate. The reaction mixture was separated, and the organic layer given a simple wash with 5% HCI solution to convert the imidate to starting secondary amide. To the washed mixture in methylene chloride was added an additional 120 ml of chloromethyl methyl ether and 5.0 g of the quaternary ammonium phase-transfer catalyst, followed by 350 ml of 50% NaOH with stirring.

After separation of layers and additional water washing, the product was filtered through clay; methylene chloride solvent was evaporated and the residue heated to 850C (0.55 mm Hg), then filtered through clay to purify the product. The product was recovered in about 99% yield and had a boiling point of 1270C (0.15 mm Hg).

Calc'd for C,2H20CINO2 (percent): C, 58.65; H, 8.20; N, 5.70; Found: C, 58.48; H, 8.22; N, 5.62.

The product was identified as N-(2,6-dimethyl-1 -cyclo-hexen-1-yl)-N-(methoxymethyl)-2- chloroacetamide.

The above process may be performed without imidate formation thus obviating acid-catalyzed reformation of sec-amide when lesser quantities, i.e., up to 50 g of the sec-amide are used, the catalyst concentration is increased up to 2050% of the amount of sec-amide used and the base, NaOH, is added all at once.

Structure proof of the products obtained in this and the following examples was afforded by mass spectroscopy, gas liquid chromatography, nuclear magnetic resonance and/or elemental analysis.

(b) One (1.0) g of the product produced in paragraph (a) above was placed in 10 ml of CCl4, stirred 2 hours with 10 ml of 37% HCI. After reaction had gone to completion as indicated by NMR, the formed layers were separated, 5 ml of fresh HCI added and the mixture stirred for 1 hour. After layer separation, the organic layer was vacuum stripped to 750C/0.2 mm Hg to give 0.8 g (93% yield) of oil.

Anal. calc'd for C1lH,8Cl2NO(%): Element Theory Found C 52.60 51.87 H 7.22 6.79 N 5.58 5.27 The product was identified as N-(2,6-dimethyl-1 -cyclohexen-1 -yl)-N-(chloromethyl)-2chloroacetamide.

(c) To 8.9 g (0.036 mol) of the amide produced in paragraph (b) dissolved in toluene was added 4.9 g (0.072 mol) of pyrazole; this mixture was heated to 900C with stirring for 7 hours. The following day, the toluene solution was decanted, washed twice with water, then vacuum distilled to remove the solvent and traces of moisture. The residue was 9.0 g of an oil which crystailized on standing. A sample of the product was recrystallized from a heptane/methylcyclohexane solvent to give a solid product, m.p. 83-840C, in 89% yield.

Anal. calc'd for C14H20CIN30(%): Element Theory Found C 59.67 59.64 H 7.15 7.17 N 14.91 14.96 The product was identified as N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1H-pyrazol--ylmethyl)-2- chloroacetamide.

Example 2 Two (2.0) grams of N-(methoxymethyl)-N-[2-methyl-1-(1-methylethyl)-1-propen-1-yl)-2chloroacetamide dissoived in 20 ml of CCl4 were contactd with 20 ml of 37% HCl and sheken in a separatory funnel. When NMR analysis of lower layer indicated complete reaction, the material was vacuum stripped at about 500C/0.05 mm Hg to give 1.6 g of product.

Anal. calc'd for C10H17Cl2NO(%): Element Theory Found C 50.43 51.17 H 7.19 7.39 N 5.88 6.07 The product, structure confirmed by NMR, was identified as N-(chloromethyl)-N-[2-methyl-1 -(1 methylethyl)-1-propen-1-yl]-2-chloroacetamide. NMR characteristics for this product are as follows: (CDCl3) & 0.95, 1.1 CH(CH3)2 (2 doubiets, 3H each, J=7Hz); & 2.7, 2.84 (2 singlets, 3H each)=C(CH3)2; a 3,95, (CH3)2CH- (heptet 1 H, J=7 Hz); a 4.02, CI CH2CO (S, 2H); 8= 5.38, N-CH2CI (AB quartet, 2H, J=8.5 Hz).

To 1.4 g (0.0059 mol) of the N-(chloromethyl)-2-chloroacetamide prepared above was added 0.8 g (0.012 mol) of pyrazole and the mixture heated in about 20 ml of toluene at 80-900C for about 67 hours. The material was decanted, washed with 10% caustic then with water, stripped and recrystallized from methyl-cyclohexane to give 1.0 (63%) yield of white solid, m.p. 101.0-101.5 C.

Anal. calc'd for C13H20C1 N30(%): Element Theory Found C 57.88 57.41 H 7.47 7.59 N 15.58 16.25 The product, structure confirmed by NMR, was identified as N-[(2-methyl-1-(1-methylethyl)-1- propenyl]-N-(1 H-pyrazol- 1 -ylmethyl)-2-ch loroacetamide.

Example 3 Following the general procedure described in Example 2,2.0 g of N-(methoxymethyl)-N-(1,2dimethyl-1-propenyl)-2-chloracetamide were dissolved in 20 ml of CCl4 and shaken ln a small separatory funnel with 25 ml of 37% HCI. The lower organic layer was drawn off and NMR indicated complete reaction; the solvent was stripped qn a water bath (600 C) at pump pressure to give 1.2 g (57% yield) of product.

Anal. calc'd for C2H13Cl2NO(%): Element Theory Found C 45.73 45.24 H 6.24 6.21 N 6.67 6.35 The produet was identified as N-(chloromethyl)-N-(1,2-dimethyl-1-propen-1-yl)-2-chloroscetamide.

NMR characteristies for this product are as follows: (CDCl3) & 1.65, 1.8, 1.95 (3=C-CH3, 9 protons, each broad singlet with partial multiplicity): =4.O, CICH2 CO (singlet, 2H); & = 5.35, CICH2N (AB quartet, 2H, J=9 Hz).

Pyrazol, 0.54 g (0.008 mol) and 0.8 g (0.0038 mol) of the N-chloromethyl-2-chloroacetamide prepared above were mixed in toluene and heated at 90 C. On work-up as described in Example 1,0.6 g (62% yield) of an amber oil was obtained, ND25 1.5607.

Anal. calc'd for C11H16CIN3O(%): Element Theory Found C 54.66 54.71 H 6.67 6.80 N 17.38 17.51 The product, confirmed by NMR, was identified as N-(1,2-dimethyl-1-propen-1-yl)-N-(1H-pyrazol-1- ylmethyl)-2-chloroacetamide.

The N-(methoxymethyl)-N-(acyclic-1 - alken-1 -yl)-2-chloroacetamides used to prepare the corresponding N-(chloromethyl)-2-chloroacetamides used as starting materials in Examples 2 and 3 were prepared similarly as the analogous N-(methoxymethyl)-N-(1-cycloalken-1-yl)-2chloroacetamides as exemplified in Example 1(a). Thus, the precursor N-(alkoxymethyl) amide used in Example 3 is prepared as follows: To 200 ml of CH2CI2 are added 16.0 g (0.1 mol of N(1,2-dimethyl-1-propen-1-yl)-2- chloroacetamide, 4.0 g of benzyl triethylammonium chloride and 16 ml of bromomethyl methyl ether.

The mixture is cooled to 1 OOC and 100 ml of 50% NaOH added all at once. After aqueous workup, 4.0 g (19.5% yield) of the corresponding N-(methoxymethyl)-2-chloroacetamide product, b.p. 110- 1 200C/O.05 (Kugelrohr), are obtained.

Anal. caic'd for CgH16CNO2(%): Element Theory Found C 52.56 50.65 H 7.84 7.56 N 6.81 6.38 The product was identified as N-(methoxymethyl)-N-( 1 ,2-dimethyl-1 -propen-1 -yl)-2-chloroacetamide.

Examples 4--10 Following substantially the same procedures described in Examples 1-3, but substituting the appropriate starting materials and reaction conditions, other 2-haloacetamide compounds according to the above generic formula are prepared. The same or equivalent solvents, catalysts, etc., together with appropriate reaction times and temperatures are readily used in equivalent process embodiments.

Typical other compounds prepared in accordance with the above procedures are shown in Table I together with certain physical properties.

Table 1 Example Phydical No. Compound Property Element Calculated Found 4 N-(6-ethyl-2-methyl-1-cyclohexen-1-yl)-N- Colorless oil C 60.90 60.84 [(1H-pyrazol-1-yl)methyl]-2-chioroacetamide N25 1.5300 H 7.50 7.51 in admixture with its N-(2-ethyl-6-methyl- N 14.21 14.20 1-cyclohexen-1-yl)isomer 5 N-(2,6-dimethyl-1-cyclohexen-1-yl)-N- Orange oil C 62.02 62.60 [3,5-dimethyl-1H-pyrazol-1-yl)methyl]- N25 1.5312 H 7.81 7.86 2-chloroacetamide N 13.56 14.04 6 N-(2,6-dimethyl-1-cyclohexen-1-yl)-N- Yellow oil C 55.22 54.90 (1H-1,2,4-triazol-1-ylmethyl)-2-chloro- N25 1.5377 H 6.77 6.90 acetamide N 19.81 18.87 7 N-(2,6-dimethyl-1-cyclohexen-1-yl)-N- m.p. 81-83 C C 59.67 59.60 (1H-imldazo-1-ylmethyl)-2-chloro- H 7.15 7.19 acetamide N 14.91 14.85 8 N-(2,6-diethyl-1-cyclohexen-1-yl)-N- Yellow oil C 62.02 62.13 (1H-pyrazol-1-ylmethyl)-2-chloro- N25 1.5287 H 7.81 7.84 acetamide N 13.56 13.46 9 N-(2-methyl-1-cyclohexen-1-yl)-N- Yellow oil C 58.31 57.50 (1H-pyrazol-1-ylmethyl)-2-chloro- H 6.78 6.67 acetamide N 15.69 15.46 10 N-(2,6-dimethyl-1-cyclohexen-1-yl)-N- m.p. 106-108 C C 60.91 60.79 (1H-2-methylimidazol-1-ylmethyl)-2- H 7.50 7.74 chloroacetamide N 14.20 14.08 The compounds of this invention have exhibited both preemergence and postemergence herbicidal activity, hence may be used in both modes of application. However, the compounds herein are preferably used as preemergence herbicides, as will be described in more detail below.

The pre-emergent herbicidal activity of representative compounds of this invention is determined by the following procedure: A good grade of top soil is placed in aluminum pans and compacted to a depth of three-eighths to one-half inch (9.5 to 12.7 mm) from the top of the pan. On the top of the soil is placed a number of seeds or vegetative propagules of various plant species. The soil required to level fill the pans after seeding or adding vegetative propagules is weighed into a pan. The soil and a known amount of the active ingredient applied in a solvent or as a wettable powder suspension are thoroughly mixed, and used to cover the prepared pans. After treatment, the pans are moved to greenhouse benches, then watered by sub-irrigation is needed to give adequate moisture for germination and growth.

Observations are made about 2-3 weeks after seeding and treatment.

Tables II and Ill summarize results of test conducted to determine the pre-emergence herbicidal activity of the compounds of this invention. The herbicidal rating was obtained by means of a fixed scale based on the percent injury of each plant species. The ratings are defined as follows: % Control Rating 0--24 0 25-49 1 50-74 2 75-100 3 Undetermined 5 The plant species utilized in one set of tests, the data for which are shown in Table II, are identified by letter in accordance with the following legend:: A Canada Thistle* E Lambsquarters I Johnson grass* B Cocklebur F Smartweed J Downy Brome C Velvetleaf G Yellow nutsedge* K Barnyard D Morningglory H Quackgrass* grass *Grown from vegetative propagules Table II Pre-Emergent Compound of Plant Species Example. Kg/Ka A B C D E F G H I J K 1 11.2 3 2 2 3 3 2 3 3 1 3 3 5.6 3 2 2 2 3 2 3 3 0 3 3 2 11.2 2 1 3 3 3 3 3 3 2 3 3 5.6 2 2 2 3 3 3 0 3 0 3 3 3 11.2 3 2 2 3 3 3 3 3 0 3 3 5.6 2 2 2 3 3 3 3 3 0 3 3 4 11.2 3 2 2 2 3 3 3 3 3 3 3 5.6 2 2 2 2 3 3 2 3 2 3 3 5 11.2 2 1 3 3 3 3 3 3 3 3 3 5.6 1 1 2 2 3 3 3 3 3 3 3 6 11.2 1 1 2 1 3 2 1 0 0 3 3 5.6 0 0 1 1 3 1 0 3 0 3 3 7 11.2 0 0 0 0 2 2 0 2 0 0 2 5.6 0 5 0 0 1 1 0 0 0 0 1 8 11.2 2 2 3 3 3 3 3 3 3 3 3 5.6 2 2 2 3 3 3 3 3 3 3 3 9 11.2 3 2 2 3 2 3 3 3 3 3 3 5.6 2 1 1 3 3 2 3 3 2 3 3 The compounds were further tested by utilizing the above procedure on the following plant species: L Soybean R Hemp Sesbania M Sugar Beet E Lambsquarters N Wheat F Smartweed O Rice C Velvetleaf P Sorghum J Downy Brome B Cocklebur S Panicum Spp.

Q Wild Buckwheat K Barnyard Grass D Morningglory T Crabgrass The results are summarized in Table Ill.

Table III Pre-Emergent Compound of Example No. Kg/Ha L M N O P B O D R E F C J S K T 15.6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1.12 3 3 2 2 3 1 2 3 3 3 3 3 3 3 3 3 0.28 0 2 1 1 2 0 1 0 1 3 3 1 2 3 3 3 0.06.- 0 0 0 0 0 1 1 0 1 3 1 0 2 1 3 3 0.01 0 0 1 1 1 0 3 0 0 1 1 0 0 0 2 3 2 5.6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1.12 3 3 3 3 3 2 3 3 3 3 3 2 3 3 3 3 0.28 3 3 3 3 3 0 2 3 3 3 3 2 3 3 3 3 0.06 2 2 1 1 1 0 1 3 3 3 3 2 2 3 3 2 0.01 2 1 1 0 0 0 0 3 1 2 1 2 1 1 2 3 3 5.6 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1.12 2 3 3 3 1 2 3 3 3 3 3 3 3 3 3 3 0.2 8 1 3 1 1 0 0 2 3 3 3 3 1 2 3 3 3 0.06 3 2 0 1 0 1 2 3 3 2 1 0 2 3 3 3 0.01 1 1 0 0 0 0 1 2 1 1 0 0 0 1 2 3 4 5.6 2 3 3 3 3 1 2 3 3 3 3 2 3 3 3 3 1.12 1 2 3 3 3 5 2 3 3 3 3 1 3 3 3 3 0.28 0 2 3 3 3 5 1 0 2 3 3 0 3 3 3 3 0.06 1 1 1 3 0 0 0 0 0 2 3 0 3 2 3 3 0.01 0 1 0 1 0 6 0 0 5 2 2 0 0 1 3 3 0.006 0 1 0 1 0 0 0 0 0 2 2 0 0 0 1 2 5 5.6 3 3 3 3 3 2 2 3 3 3 3 3 3 3 3 3 1.12 1 3 3 3 3 0 3 3 2 2 2 0 3 3 3 3 0.28 0 2 2 3 1 5 0 0 0 2 3 0 3 3 3 3 0.06 0 1 0 1 0 0 0 0 0 2 3 0 0 2 3 3 0.1 0 0 0 1 0 0 0 0 5 0 0 0 0 1 3 3 6 5.6 1 3 3 3 3 3 2 3 3 3 3 2 3 3 3 3 1.12 0 2 3 3 1 0 2 0 2 3 3 0 3 3 3 3 0.28 # 0 1 2 2 0 0 0 0 2 1 3 0 2 2 3 3 0.06 0 1 0 1 0 0 0 0 3 2 2 0 0 1 3 3 8 5.6 1 2 3 3 3 3 1 3 3 3 3 2 3 3 3 3 1.12 2 2 2 3 3 3 1 1 3 3 1 0 3 3 3 3 0.28 0 3 2 3 2 0 1 0 2 3 3 0 3 3 3 3 0.06 0 1 1 1 1 0 0 0 0 1 1 0 0 2 2 3 0.02 0 0 0 0 0 5 0 0 0 0 0 0 0 0 1 2 0.006 0 0 0 0 0 5 0 0 5 0 0 0 0 0 1 1 9 5.6 3 2 2 3 0 1 3 3 2 3 3 0 3 3 3 3 1.12 2 2 0 3 0 1 2 5 1 1 1 0 3 3 3 3 0.28 1 2 0 1 0 0 1 2 1 1 1 0 3 3 3 3 0.06 0 0 0 0 0 0 0 0 0 0 0 0 1 2 2 3 0.01 0 0 1 0 0 0 0 0 0 1 1 0 0 0 2 3 Other representative compounds according to this invention include those corresponding to the above generic formula wherein X is bromo or iodo and the C14 alkyl substituents on the R and A members include methyl, ethyl and the isomeric propyls and butyls.Other compounds contemplated as within the purview of this invention include those within the scope of the above generic structural formula wherein the A and R members can be substituted with one or more additional radicals such as halogen, nitro, cyano, amino, trifluoromethyl, other lower haloalkyl, lower alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, polyalkoxy, thioalkyl or alkylthioalkyl having up to 8 carbon atoms, C37 cycloalkyl or cycloalkenyl or aryi, aralkyl or alkaryl radicals having up to 10 carbon atoms and the like. Additional exemplary compounds are shown in Table IV.

Table IV

Example No. X R A 1I Cl H3CCH3 pyrazol -1- yt 12 Br H,C CHQ pyrazol- l-yl 13 Cl 83CZECH3 imida201-t-yl 14 Br H3C CH3 imidazof-1-yl 15 Ct H3C CH3 1,2,4 triazoI-i-yt 16 Br H3Ce CH3 I,2,4-tri'azo1-t-t 17 Cl H3CC2H5 pyrazot - i- yt 18 Cl H3CC2Ii5 imidazol-i-yl 19 Cl H5C2 C2H5 pyrazol-l -yl 20 CI H5C2t - C2\\5 imidazol- l-yl 21 Ct HC e C7 pgrazo!-l-t 22 C1 H7C C3117 imida'zot-i-t Table IV (contd.)

Example No. X R A 1 23 Cl H3Cn-C4H7 pyrazol-l-yl 24 Cl H3Ctn c4H7 inidazot-i- Y1 25 C1 H3Ct n-c3H7 pyrazol -l-yl H3C-0 n-C3H, 26 Ct 3 kJ 3 7 imidazol--9i 27 Ct H3C C4Hs pyrazol t yl 28 Cl H3Cn-C9 imidazol-l-yl 29 Br H3ctn-C3H7 1,2,4-triazol-1-yl 30 Br n~C3H7tn-C3H7 1,2,4-triazol-1-gl 31 Br H3C tn-c4H9 pyrazol-l-yl 32 Cl H3Ct c83 pyrazol-1 - yi 33 Cl H3ctCH3 pyrazol-l- yl 34 Br H3C t CH3 pyrazol-1-yl 35 Cl 3C t C2H5 imidazot-1-yt 36 Br H3C yFCH3 imidazol-L-yt 37 Cl H3CC2H5 1,2,4-triazol-l-yt Table IV (contd.)

Example No. X R A 38 Br H3C t CH3 1,2,4-triazol-l-yl 39 Cl H3Ctn~c3H7 pyrazol-l-yl 40 Cl H3Ctn c3H7 imidazol-l-y 41 Cl H3C pyrazol-1-Yt 42 Ct H3C CF3 pyrazol- i-yt 43 Cl H3C0 CF3 imidazol-i-yl 44 Cl H3C CF3 imidazol-l-yt 45 C1 H3CCF3 imidazol-l-yl 46 CZ H3C-6 prazol-t-t 47 C1 H3CeCF3 pyrazol-l-l 48 Cl H3C +CF3 imidazol-l-yt 49 C1 CH3CH2-C-C=Co C2Hs pyrat ot CHQ CH2 CH3 50 CI H3CCH2-C=C-C-1-CH3 pyrazol-l-yt CH3 51 Cl H1=CH2 pyrazol-í-yl 52 CI HC=CH2 imidazol-f-yl Table IV (contd.)

Example No. X R A 53 Br ;HC-C=CH-CH3 pyrazo1-1-yt CH3 54 I %H3 pyrazol-i-yl HC- C=CH- CH3 CH3 55 1 I /CH3 55 I HSC-C pyrazol 3 56 I H3C e CxCH imida202-1-yl 57 I f%flCH3 imidazol-l-yl 58 I (yCH3 pyrazol-l-yt 59 Cl H3ctcH3 CH3 1,2,3,4 tetrazol 60 Ct b- CH3 1, 2,3,4 -tetrazot-l-yl 61 Cl H3CeCH3 2-m ethylpyrazol-l-yl 62 Ci ton02 prazot-l-t 63 Cl H3C OCH3 pyrazot- 1- yl 64 Cl H3CtCt pgrazol-l-Y 65 Cl H3C t CH2CI pyrazol-l-yl Table IV (contd.)

Example No. x R A 66 Cl H3C t CH3 3,5 -dibutyl-pyrazol-í-yl 67 Cl H3C tCH3 H,C CH3 2,5- diethyl imidazol-l-yl The herbidical 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 surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into the compositions greatly enhances their efficacy. By the term "surface-active agent" it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein.

Anionic, cationic and non-ionic agents can be used with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters petroleum sulfonates, sulfonated vegetable oils, ditertiary 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 methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkyl, naphthalene sulfonates, sodium naphthalene sulfonate, and the polymethylene bisnaphthalene sulfonate.

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, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such extenders include kaolinites, attapulgite clay and synthetic magnesium silicate.The wettable powders compositions of this invention usually contain from about 0.5 to 95 parts (preferably from 5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent, from 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant and from 5 to about 95 parts (preferably 5-50 parts) of inert solid extender, all parts being by weight of the total composition. Where 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 concentrates 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 about 0.1-1 0% by weight.

Aqueous suspensions or emulsions may be prepared by stirring an aqueous mixture of a waterinsoluble 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 about 0.160% preferably 550% 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 encapsuiated 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 waterimmiscible 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 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/l of total composition, preferably 480 to 600 g/l. The microencapsulation process referred to here is described in more detail in United States Patent Number 4,280,833 issued July 28, 1981.

Concentrates are usually solutions of active ingredient in water-immiscible or partially waterimmiscible solvents together with a surface active agent. Suitable solvents for the active ingredient of this invention include dimethylformide, 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 compositions herein generally contain from about 0.1 to 95 parts (preferably 5-60 parts) of active ingredient, about 0.25 to 50 parts (preferably 1-25 parts) surface active agent and where required about 4 to 94 parts solvent, all parts being by weight based on the total weight of emulsifiable oil.

Granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert, finely-divided particulate extender. In order to aid leaching of the active ingredient from the particulate, a surface active agent such as those listed hereinbefore can be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of operable classes of particulate mineral extenders. The preferred extenders are the porous, absorptive, preformed particles such as preformed and screened particulate attapulgite or heat expanded, particulate vermiculite and the finely-divided clays such as kaolin clays, hydrated attapulgite or bentonitic clays. These extenders are sprayed or blended with the active ingredient to form the herbicidal granules.

The granular compositions of this invention may contain from about 0.1 to about 30 parts preferably from about 3 to 20 parts by weight of active ingredient per 100 parts by weight of clay and O to about 5 parts 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 like used as adjuvants or in combination with any of the above-described adjuvants. Chemicals useful in combination with the active ingredients of this invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acid, nitriles, biphenyl ethers and the like such as:: Heterocyclic Nitrogen/Sulfur Derivatives 2-Chloro-4-ethylamino-6-isopropylamino-s-triazine 2-Chloro-4,6-bis(isopropylamino)-s-traizine 2-Chloro-4,6-bis(ethylamino)-s-triazine 5-Amino-4-chloro-2-phenyl-3(2H)-pyridazinone 3-lsopropyl-l H-2, 1 ,3-benzothiadiazin-4-(3H)-one 2,2-dioxide 3-Methyl-4-amino-6-phenyl- ,2,4-triazine-5-one 3-Amino-1 ,2,4-triazole 6.7-Dihydrodipyrido( 1 ,2-a::2', 1 '-c)-pyrazidiinium salt 5-Bromo-3-isopropyl-6-methyluracil 1,1 '-Dimethyl-4,4'-bipyridinium salt 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-benzothiazolyl) urea 3-(p-Chlorophenyl)- l,l-dim ethylurea 1 -Butyl-3-(3,4-dichlorophenyl)-1 -methylurea Carbamates/Thiolcarbamates 2-Chloroallyl diethyldithiocarbamate S-(4-chlorobenzyl)N,N-diethylthiolcarbamate Isopropyl N-(3-chlorophenyl) carbamate S-2,3-dichloroallyl N,N-diisoprnpylthiolcarbamate Ethyl N,N-dipropylthiolcarbamate S-propyl dipropylthiolcarbamate Acetamides/Acetanilides/Anilines/Amides 2-Chloro-N,N-diallylacetamide N,N-dimethyl-2,2-diphenylacetamide N-(2,4-dimethyl-5-[[(trifluoromethyl)sulfonyl}aminojphenyl)acetamide N-isopropyl-2-chloroacetanilide 2',6'-Diethyl-N-methoxymethyl-2- chloroacetanilide 2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacetanilide a,,-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine N-( 1 , 1 -dimethylpropynyl)-3,5-dichlorobenzamide Acids/Esters/Alcohols 2,2-Dichloropropionic acid 2-Methyl-4-chlorophenoxyacetic acid 2,4-Dichlorophenoxyacetic acid Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate 3-Amino-2,5-dichlorobenzoic acid 2-Methoxy-3,6-dichlorobenzoic acid 2,3,6-Trichlorophenylacetic acid N-l -naphthylphthalamic acid.

Sodium 5-[2-ch loro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate 4,6-Dinitro-o-sec-butylphenol N-(phosphonomethyl) glycine and its C15 monoalkyl amine and alkaline metal salts and combinations thereof Ethers 2,4-Dichlorophenyl-4-nitrophenyl ether 2-Chloro-Kg,a,-trifluoro-p-tolyl-3-ethoxy-4-nitrodîphenyl ether Miscellaneous 2,6-Dichlorobenzonitrile Monosodium acid methanearsonate Disodium methanearsonate Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea, potash and superphosphate. Other useful 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 Weight Percent A. Compound of Example No. 1 50.0 Calcium dodecylbenzene sulfonate/ polyoxyethylene ethers blend (e.g., Atloxqs 3437F and Atlox 33438F) 5.0 Monochlorobenzene 45.0 100.00 B. Compound of Example No. 2 85.0 Calcium dodecyl suifonate/alkylaryl polyether alcohol blend 4.0 C9 aromatic hydrocarbons solvent 11.0 100.00 C. Compound of Example No. 3 5.0 Calcium dodecylbenzene sulfonate/ polyoxyethylene ethers blend (e.g., Atlox 3437F) 1.0 Xylene 94.0 100.00 II. Liquid Concentrates Weight Percent A. Compound of Example No. 4 10.0 Xylene 90.0 100.00 B. Compound of Example No. 5 85.0 Dimethyl sulfoxide 15.0 100.00 Weight Percent C. Compound of Example No. 6 50.0 N-methylpyrrolidone 50.0 100.00 D.Compound of Example No. 7 5.0 Ethoxylated castor oil 20.0 Rhodamine B .5 Dimethylformamide 74.5 100.00 III. Wettable Powders Weight Percent A. Compound of Example No. 8 25.0 Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyl-taurate 1.0 Amorphous silica (synthetic) 71.0 100.00 B. Compound of Example No. 10 80.0 Sodium dioctyl sulfosuccinate 1.25 Calcium lignosulfonate 2.75 Amorphous silica (synthetic) 16.00 100.00 C. Compound of Example No. 2 10.0 Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyl-taurate 1.0 Kaolinite clay 86.0 100.00 IV. Dusts Weight Percent A. Compound of Example No. 3 2.0 Attapulgite 98.0 100.00 B. Compound of Example No. 4 60.0 Montmorillonite 40.0 100.00 C. Compound of Example No. 5 30.0 Bentonite 70.0 100.00 D. Compound of Example No. 6 1.0 Diatomaceous earth 99.0 100.00 V. Granules Weight Percent A. Compound of Example No. 8 15.0 Granular attapulgite (20/40 mesh) 85.0 100.00 Weight Percent B. Compound of Example No. 1 30.0 Diatomaceous earth (20/40) 70.0 100.00 C. Compound of Example No. 2 0.5 Bentonite (20/40) 99.5 100.00 D. Compound of Example No. 3 5.0 Pyrophyllite (20/40) 95.0 100.00 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 convenient fashion. The application of liquid and particulate solid compositions to the soil can be carried out by conventionai methods, e.g., power dusters, boom and hand sprayers and spray dusters.

The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired.

The application of an effective amount of the compounds of this invention to the locus of undesired weeds is essential and critical for the practice of the present invention. The exact amount of active ingredient to be employed is dependent upon various factors, including the plant species and stage of development thereof, the type and condition of soil, the amount of rainfall and the specific acetanilide employed. In selective pre-emergence application to the plants or to the soil a dosage of from 0.02 to about 1 1.2 kg/ha, preferably from about 0.04 to about 5.60 kg/ha, or suitably from 1.1 2 to 5.6 kg/ha of acetanilide is usually employed. Lower or higher rates may be required in some instances. One skilled in the art can readily determine from this specification, including the above example, the optimum rate to be applied in any particular case.

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

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

Claims (42)

Claims

1. Compounds according to the formula

wherein X is chloro, bromo or iodo; R is an acyclic 1 -alkenyl-1 -yl radical having up to 8 carbon atoms, a C57 1 -cycloalken-1 -yl radical or one of said radicals substituted with one or more C14 alkyl radicals and A is an unsubstituted or C14 alkyl-substituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical.

2. Compounds according to Claim 1 wherein R is an unsubstituted or C14 alkyl-substituted acyclic 1-alken-1-yl radical.

3. Compounds according to Claim 2 wherein A is a pyrazolyl radical.

4. Compound according to Claim 3 which is N-(1,2-dimethyl-1-propen-1-yl)-N-(1H-pyrazol-1ylmethyl)-2-chloroacetamide.

5. Compound according to Claim 3 which is N-[2-methyl-1-(1-methylethyl)-1-propen-1-yl]-N- (1 H-pyrazol-1-ylmethyl)-2-chloroacetamide.

6. Compounds according to Claim 1 wherein R is an unsubstituted or C14 alkyl-substituted C57 cycloalken-1-yl radical.

7. Compounds according to Claim 6 wherein A is a pyrazolyl radical.

8. Compound according to Claim 7 which is N-(2,6-dimethyl-1-cyclohexen-1-yl)-N-(1 H-pyrazol1 -ylmethyl)-2-chloroacetamide.

9. Compounds according to Claim 6 wherein A is a triazolyl radical.

10. Compound according to Claim 9 which is N-(2,6-dimethyl-1 -cyclohexen-1 -yl)-N-(1 H-1,2,4triazol-1 -ylmethyl)-2-chloroacetamide.

11. Compounds according to Claim 6 wherein A is an imidazolyl radical.

12. Compound according to Claim 11 which is N-(2,6-dimethyl-1 -cyclohexen-1 -yl)-N-(1 Himidazol-1-ylmethyl)-2-jchloroacetamide.

13. Compounds according to Claim 6 wherein A is a tetrazolyl radical.

14. Herbicidal compositions comprising an adjuvant and a herbicidally effective amount of a compound of the formula

wherein X is chloro, bromo or iodo; R is an acyclic 1 -alkenyl-1 -yl radical having up to 8 carbon atoms, a C5~7 1 -cycloalken-1 -yl radical or one of said radicals substituted with one or more C14 alkyl radicals and A is an unsubstituted or C14 alkyl-subsituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical.

15. Compositions according to Claim 14 wherein in said compound R is an unsubstituted or C14 alkyl-substituted acyclic 1-alken-1-yl radical.

16. Compositions according to Claim 15 wherein said compound A is a pyrazolyl radical.

17. Composition according to Claim 16 wherein said compound is N-(1,2-dimethyl-1-propen-1- yl)-N-(1 H-pyrazol-1 -ylmethyl)-2-chloroacetamide.

18. Composition according to Claim 18 wherein said compound is N-[2-methyl-1 -(1 methylethyl)- 1 -propen- 1 -yl]-N-(1 H-pyrazol- 1 -ylmethyl)-2-chloroaceta mide.

19. Compositions according to Claim 14 wherein in said compound R is an unsubstituted or C14 alkyl-substituted C5-7 cycloalken-1-yl radical.

20. Compositions according to Claim 19 wherein in said compound A is a pyrazolyl radical.

21; Composition according to Claim 20 wherein said compound is-N-(2,6-dimethyl-1- cyclohexen-1-yl)-N-(1H-pyrazol-1-ylmethyl)-2-chloroacetamide.

22. Compositions according to Claim 19 wherein in said compound A is a triazolyl radical.

23. Composition according to Claim 22 wherein said compound is N-(2,6-dimethyl-1 cyclohexen- 1 -yl]-N-(1 H- 2,4-triazol- 1 -ylmethyl)- 2-chloroacetamide.

24. Compositions according to Claim 19 wherein in said compound A is an imidazolyl radical.

25. Compositions according to Claim 24 wherein said compound is N-(2,6-dimethyl-1 - cyclohexen- 1 -yl)-N-(1 H-imidazol-1 -ylmethyl)-2-chloroacetamide.

26. Compositions according to Claim 19 wherein in said compound A is a tetrazolyl radical.

27. Method for combatting undesirabie plants in crops which comprises applying to the locus thereof a herbloldally effective amount of a compound having the formula

wherein X is chloro, bromo or iodo; R is an acyclic 1-aikenyl-1-yl radical having up to 8 carbon atoms, a C57 1 -cycloalken-1 -yl radical or one of said radicals substituted with one or more C14 alkyl radicals and A is an unsubstituted or C14 alkyl-substituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical.

28. Method according to Claim 27 wherein in said compound R is an unsubstituted or C14 alkylsubstituted acyclic 1-alken-1-yl radical.

29. Method according to Claim 28 wherein in said compound A is a pyrazolyl radical.

30. Method according to Claim 29 wherein said compound is N-(1,2-dimethyl-1-propen-1-yl)-N- (1H-pyrazol-l -ylmethyl)-2-chioroacetamide.

31. Method according to Claim 29 wherein said compound is N-[2-methyl-1-(1-methylethyl)-1- propen-1-yl]-N-(1H-pyrazol-1-ylmathyl)-2-chloroacetamide.

32. Method according to Claim 27 wherein in said compound R is an unsubstituted or C14 alkylsubstituted C57 cycloalken-1-yl radical.

33. Method according to Claim 32 wherein in said compound A is a pyrazolyl radical.

34. Method according to Claim 32 wherein said compound is N-(2,6-dimethyl-1 -cyclohexen-1 - yl)-N-(1 H-pyrazol-1 -ylmethyl)-2-chloroacetamide.

35. Method according to Claim 32 wherein in said compound A is a triazolyl radical.

36. Method according to Claim 35 wherein said compound is N-(2.6-dimethyl-1 -cyclohexen-1 yl)-N-( 1 H- 1,2,4-triazol-1 -ylmethyl)-2-chloroacetamide.

37. Method according to Claim 32 wherein in said compound A is an imidazolyl radical.

38. Method according to Claim 37 wherein said compound is N-(2,6-dimethyl-1 -cyclohexen-1 - yl)-N-(1 H-imidazol- 1 -ylmethyl)-2-chlornacetamide.

39. Method according to Claim 32 wherein in said compound A is a tetrazolyl radical.

40. Compound according to Claim 7 which is N-(2,5-dimethyl-1 -cyclopenten-1 -yl)-2- chloroacetamide.

41. Composition according to Claim 20 wherein said compound is N-(2,5-dimethyl-1- cyclopenten- 1 -yl)-2-chloroacetamide.

42. Method according to Claim 33 wherein said compound is N~92,5-dimethyl-1-cyclopenten-1- yl)-2-chloroacetamide.