NZ199110A - N-(heterocyclomethyl)haloacetamides herbicidal compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 99110 1 991 1 0 Priority Dotc("}: .. &°-ConnpScta SnccaffcaijonJFsllcd:^0. J1.

Publication Dsts: P.O. Jo'jrn;:J, r«c; No.: Date: NEW ZEALAND PATENTS ACT, \ 953 COMPLETE SPECIFICATION nHERBICIDAL 2-HALOACETAMIDES B b/ We, MONSANTO COMPANY, a Corporation of the State of Delaware, United States of America, of 800 North Lindbergh Boulevard, St. Louis, Missouri 63166, United States of America, hereby declare the invention for which T/ we pray that a patent may be granted to fne/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - - 1 - (followed by la) 1 991 -la- AQ-1293 HERBICIDAL 2-HALOACETAMIDES Background of the Invention Field of the Invention This invention pertains to the field of 5 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 10 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, 15 halogen, haloalkyl, aryl, aralkyl, N-, O- 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 20 radicals substituted on the acetamide nitrogen atom; however, such known compounds require that aromatic groups also be substituted on the nitrogen atom. Illustrative of ouoh N-agolylmothyl oubotitutod 2-haloacetanilido—oompoundc—arc thOGO diooloood—tft 0^25 Corman Patent Application Numbers—2,704,201,—2 ,G40,000 ■■and 2/744/396* Other relevant prior art discloses compounds having 1-cycloalken-l-yl groups on the nitrogen atom, but such compounds also require that other non-heterocyclyl radicals also be attached 30 thereto. See U. S. Patent No. 3,574,746 and 3,586,496. Still other relevant prior art includes 2-haloacetamides having 1-alken-l-yl radicals substituted on the nitrogen atom, but such compounds require that alkoxyethyl, alkoxypropyl, alkyl or alkenyl radicals be substituted on the nitrogen.

■ Couth African PaL&nL No.—753,918'. ,1991 -2- AG 1203 Perhaps the most relevant prior art known to the inventor herein are disclosures of 2-haloacetamides having simultaneous substitutions on the acetamide nitrogen atom of 1-cycloalken-l-yl or 5 acyclic-l-alken-l-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-l-yl and N-heterocyclyl radicals. The 2-haloacetamides containing 10 the acyclic 1-alken-l-yl. and N-heterocyclyl radicals require that when there is a heterocyclic radical attached to said nitrogen atom, the 1-alken-l-yl radical must have a substitution thereon other than hydrogen, alkyl or 15 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 C^_7 cycloalken-l-yl or 20 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 25 the present invention as described in more detail below.

Summary of the Invention The present invention relates to herbicidal-ly-active compounds, herbicidal compositions containing 30 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 1 991 AO 1293 O XCH-C CH„-A \ / N *>*> v20 R wherein X is chloro, bromo or iodo; R is an acyclic l-alken^i—l-yl radical having up to 12, preferably up to 8 carbon atoms, a 1-cycloalken-l-yl radical or one of said radicals substituted with one or more alkyl radicals and A is an unsubstituted or C^_4 alkyl-substi-tuted pyrazolyl, imidazolyl, triazolyl or tetrazolyl rad ical.

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-l-yl radical and wherein R is a 1-cyclohexen-l-yl radical, any of which radicals may be substituted with a alkyl radical. Individual preferred species of the invention are as follows: c c pRof>i£f-t-yu N-[2-methyl-l-(1-methylethyl)-l ] —N- (lH-pyrazol-l-ylmethyl)-2-chloroacetamide. 1 P&oP'zrt-i-y^ N- (1, 2-dimethyl-]>proponyiir)-N- (lH-pyrazol-1-ylmethyl)-2-chloroacetamide.

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

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

N-(2,6-dimethyl-l-cyclohexen-l-yl)-N-(lH-imid-azol-l-ylmethyl)-2-chloroacetamide.

N-(2,5-dimethyl-l-cyclopenten-l-yl)-N-(lH-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 III below. 1991 -4- AC-1393 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 5 N-halomethyl-N-(1-alken-l-yl) or (1-cycloalken-l-yl)-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 10 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-aikyiation 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)-2-20 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 25 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, 30 preferably in the presence of a phase transfer catalyst to produce the desired corresponding tertiary 2-haloacetamide. 1991 -5- AG 1293 A mixture of 400 g of the sec-amide, N-(2,6-dimethyl-l-cyclohexen-l-yl)-2-chloroacetamide, m.p. 114-115°C, in 760 ml methylene chloride and 300 ml chloromethyl methyl ether were mixed with 2 g benzyl 5 triethyl ammonium bromide. The mixture was cooled to °C 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 10 4-necked round bottomed flask. Exterior cooling with an ice/acetone bath was necessary to maintain the temperature under 25°C. The mixture was stirred for an additional one hour. GLC showed 78% tertiary amide produced and 22% of corresponding O-alkylated 15 by-product, 0-(methoxymethyl)-N-(2,6-dimethyl-l- cyclohexen-l-yl ) -2-chloroacet imidate . The reaction mixture was separated, and the organic layer given a simple wash with 5% HCl solution to convert the imidate to starting secondary amide. To the washed mixture in 20 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 25 through clay; methylene chloride solvent was evaporated and the residue heated to 85°C (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 127°C (0.15 mm Hg) .

Calc'd for C12H20ClNO2 (Percent) : cr 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-l-cyclo-35 hexen-l-yl)-N-(methoxymethyl)-2-chloroacetamide.

The above process may be performed without imidate formation thus obviating acid-catalyzed 1991 -6- AC -1293 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 20-50% of the amount of sec-amide used and the base, NaOH, is added all at 5 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. 10 (b) One (1.0) g of the product produced in paragraph (a) above was placed in 10 ml of CCl^, stirred 2 hours with 10 ml of 37% HCl. After reaction had gone to completion as indicated by NMRf the formed layers were separated, 5 ml of fresh HCl added and the 15 mixture stirred for 1 hour. After layer separation, the organic layer was vacuum stripped to 75°C/0.2 mm Hg to give 0.8 g (93% yield) of oil.

Anal, calc'd for C-^H^gCl 2NO (% ) : 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-l-cyclo-hexen-l-y1)-N-(chloromethyl)-2-chloroacetamide. (c) To 8.9 g (0.036 mol) of the amide 25 produced in paragraph (b) dissolved in toluene was added 4.9 g (0.072 mol) of pyrazole; this mixture was heated to 90°C with stirring for 7 hours. The following day, the toluene solution was decanted, washed twice with water, then vacuum distilled to 30 remove the solvent and traces of moisture. The residue was 9.0 g of an oil which crystallized on standing. A sample of the product was recrystallized from a heptane/methylcyclohexane solvent to give a solid product, m.p. 83-84°C, in 89% yield.

Anal, calc'd for C14h2Qcin3o(%): Element Theory Found C 59.67 59.64 H 7.15 7.17 N 14.91 14.96 1991 -7- AG-^9-3 The product was identified as N-(2,6-dimethyl-l-cyclo-hexen-l-yl)-N-(lH-pyrazol-l-ylmethyl)-2-chloroacetamide .

Example 2 Two (2.0) grams of N-(methoxymethyl)-N- [2-methy1-1-(1-methylethyl)-1-propen-l-yl]-2-chloro-acetamide dissolved in 20 ml of CCl^ were contacted with 20 ml of 37% HCl and shaken in a separatory funnel. When NMR analysis of lower layer indicated 10 complete reaction, the material was vacuum stripped at about 50°C/0.05 mm Hg to give 1.6 g of product.

Anal, calc'd for C-^qH-^C^NO (%) 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-l-(1-methylethyl)-1-propen-l-yl]-2-chloroacetamide. NMR characteristics for this product are as follows: (CDCl3)«ff 0.95, 1.1 CH(CH3)2 (2 doublets, 3H each, J = 7Hz);5 2.7, 2.84 (2 singlets, 3H each) = C(CH3)2; S 3,95, (CH3) 2CH-(heptet 1H, J = 7 Hz);<5~4.02, CI CH2CO (S, 2H); Anal. Calc'd for C]_3H2qC1n3o (% ) : Element Theory Found c 57. 88 57. 41 H 7. 47 7. 59 N . 58 16. 1991 -8- .AG 120 3 The product, structure confirmed by NMR, was identified as N-[(2-methyl-1-(1-methylethy1)-1-propenyl]-N-(1H-pyrazol-l-ylmethyl)-2-chloroacetamide.

Example 3 Following the general procedure described in Example 2, 2.0 g of N-(methoxymethyl)-N-(1,2-dimethyl-1-propenyl)-2-chloracetamide were dissolved in 20 ml of CCl^ and shaken in a small separatory funnel with 25 ml of 37% HCl. The lower organic layer was drawn off and 10 NMR indicated complete reaction; the solvent was stripped on a water bath (60°C) at pump pressure to give 1.2 g (57% yield) of product.

Anal.calc'd for Cg H-^ Cl2NO(%): Element Theory Found C 45.73 45.24 H 6.24 6.21 N 6.67 6.35 The product was identified as N-(chloromethyl)-N-(1,2-d imethyl-l-propen-l-y1)-2-chloroacetamide. NMR characteristics for this product are as follows: 20 (CDd^s^l. 65, 1.8, 1.95 (3 = C-CH^, 9 protons, each broad singlet with partial multiplicity): ^=4.0, CICH2 CO (singlet, 2H);<§" = 5.35, C1CH2N (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, NQ i.5607» Anal, calc'd for C^H-^ClN 0 (%) : Element Theory Found c 54.66 54 1—1 H 6.67 6 • 00 0 N 17.38 17 .51 The product, confirmed by NMR, was identified as N— (1,2-dimethyl-l-propen-l-yl)-N-(lH-pyrazol-l-ylmethyl)-35 2-chloroacetamide.

The N-(methoxymethyl)-N-(acyclic 1-alken-l-yl)—2—chloroacetamides used to prepare the 1991 -9- AG 1293 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-l-yl)-2-chloroacetamides as exemplified in 5 Example 1(a). Thus, the precursor N-(alkoxymethyl) amide used in Example 3 is prepared as follows: To 200 ml of CI^C^ are added 16.0 g (0.1 mol of N-(1,2-dimethyl-l-propen-l-yl)-2-chloroacetamide, 4.0 g of benzyl triethylammonium chloride and 16 ml of 10 bromomethyl methyl ether. The mixture is cooled to °C 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. 110-120°C/0.05 (Kugelrohr), are obtained. 15 Anal, calc'd for CgH-^gCNC>2 (%) : 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-(1,2-20 dimethy1-1-propen-l-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, 25 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 30 compounds prepared in accordance with the above procedures are shown in Table I together with certain physical properties.

TABLE I Example No.

Compound Physical Property N- (6-ethyl-2-methyl-l-cyclohexen-l-yl) -N- Colorless oil [ (IH-pyrazol-l-yl) methyl]-2-chloroacetamide in admixture with its N- (2-ethyl-6-methyl-1-cyclohexen-l-yl) isomer 5300 N-(2,6-dimethyl-l-cyclohexen-l-yl)-N-[3,5-dimethyl-lH-pyrazol-l-yl)methyl]-2-chloroacetamide N-(2,6-dimethyl-l-cyclohexen-l-yl)-N-(1H-1,2,4-triazol-l-ylmethyl)-2-chloro-acetamide N- (2,6-dimethyl-l-cyclohexen-l-yl) -N-(lH-imidazol-l-ylmethyl)-2-chloroacetamide N-(2,5-diethyl-l-cyclohexen-l-yl)-N-(lH-pyrazol-l-ylmethyl)-2-chloroacetamide N-(2-methyl-l-cyclohexen-l-yl)-N-(lH-pyrazol-l-ylmethyl)-2-chloroacetamide N- (2,6-dimethyl-l-cyclohexen-l-yl)-N-(1H-2 -inethy limidazol-l-ylmethyl) -2-chloroacetamide Orange oil N^5 1.5312 Yellow oil N^5 1.5377 m.p. 81-83°C Yellow oil ^25 1.5287 Yellcw oil m.p. 106-108°C Element Calculated Found C H N 60.90 7.50 14.21 60.84 7.51 14.20 C H N 62.02 7.81 13.56 62.60 7.86 14.04 C H N 55.22 6.77 19.81 54.90 6.90 18.87 C H N 59.67 7.15 14.91 59.60 7.19 14.85 0 1 C H N 62.02 7.81 13.56 62.13 7.84 13.46 C H N C H N 58.31 6.78 15.69 60.91 7.50 14.20 57.50 6.67 15.46 60.79 7.74 14.08 vO v D do i ) 1991 -11- AG 1293 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 5 preferably used as preemergence herbicides, as will be described in more detail below.

The pre-emergent herbicidal acticity of representative compounds of this invention is determined by the following procedure: 10 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 15 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 20 cover the prepared pans. After treatment, the pans are moved to greenhouse benches, then watered by sub-irrigation as needed to give adequate moisture for germination and growth. Observations are made about 2-3 weeks after seeding and treatment. 25 Tables II and III summarize results of tests 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 30 species. The ratings are defined as follows: 1991 AGn.1293 % Control 0-24 25-49 50-74 75-100 Undetermined Rating 0 1 2 3 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 B Cocklebur F Smartweed J C Velvetleaf G Yellow Nutsedge* K D Morningglory H Quackgrass* grass *Grown from vegetative propagules 199110 -13- AG 120 3 Table II Pre-Emergent Compound of Example No.

Kg/Ha 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 .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 .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 .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 .6 2 2 2 2 3 3 2 3 2 3 3 11.2 2 1 3 3 3 3 3 3 3 3 3 .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 .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 .6 0 0 0 1 1 0 0 0 0 1 8 11. 2 2 2 3 3 3 3 3 3 3 3 3 .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 .6 2 1 1 3 3 2 3 3 2 3 3 1991 -14- AG-1293 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 0 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 III. 1991 AC-1293 Table III Pre-Emergent Compound of Example No.

Kg/Ha L M N 0 p B Q D R E F c J s K T 1 . 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 .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 .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. 28 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 .6 2 3 3 3 3 1 2 3 3 3 3 2 3 3 3 3 1. 12 1 2 3 3 3 2 3 3 3 3 1 3 3 3 3 0.28 0 2 3 3 3 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 0 0 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 .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 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 0.01 0 0 0 1 0 0 0 0 0 0 0 0 1 3 3 6 .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 .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 0 0 0 0 0 0 0 0 1 2 0. 006 0 0 0 0 0 0 0 0 0 0 0 0 1 1 9 .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 2 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 1991 -16- AC 1203 Other representative compounds according to this invention include those corresponding to the above generic formula wherein X is bromo or iodo and the C^_4 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, cycloalkyl or cycloalkenyl or aryl, aralkyl or alkaryl radicals having up to 10 carbon atoms and the like. Additional exemplary compounds are shown in Table IV. 11 12 13 14 16 17 18 19 21 22 X O II XO^C \ / N f R 1991 -17- AG 129: Table IV CI H-C—j." ^—CH- pyrazol-l-yl I J Br H3C_^ '^V'!_CH3 pyrazol-l-yl CI CH-. imidazol-l-yl L_J Br H^C imidazol-l-yl C1 H_C 1 f 2,4-triazol-l-yl J i -3 Br H3C—1,2,4-triazol-l-yl CI r..Fr_ pyrazol-l-yl h3C-<- CI ^C-^^v-c^Hg imidazol-l-yl CI imidazol-l-yl H5c2-r^r ^5 CI H-.C —r h_ pyrazol-l-yl CI rj n tj imidazol-l-yl ^3 I ! C3H7 23 24 26 27 28 29 31 32 33 34 36 19 9110 -18- ag-1293 No. X R A CI H^C n-C^H^ pyrazol-l-yl CI H3C imidazol-l-yl h3c rV-s^ n n , CI < J pyrazol-l-yl H3C "f T n^3H7 CI k,) imidazol-l-yl H_C - n-C.H- CI 3 1 I 4 9 pyrazol-l-yl CI 3 f j 4 9 imidazol-l-yl Br Br H,C^'X,_ n-C.H.. Br 3 • m 4 9 pyrazol-l-yl H3C n-C3H7 1,2,4-triazol-l-yl n-C^Y^pn-C^ 1,2,4-triazol-l-yl CI H3C -y" CH3 pyrazol-l-yl c1 h3C CH3 pyrazol-l-yl Br h3C pyrazol-l-yl C1 h3C -r^-V c2H5 imidazol-l-yl Br i imidazol-l-yl h3c rv Example No. 37 38 39 40 41 42 X CI Br CI R h3c -f C2H5 H_C CH- CI H,C h3c ¥*3 CI H0C ci h-.c—f^-cf 3 I iJjii i o 1,2,4-triazol-l-yl 1,2,4-triazol-l-yl pyrazol-l-yl imidazol-l-yl pyrazol-l-yl pyrazol-l-yl 43 CI H3C—T ^3 imidazol-l-yl 44 CI h3c -cf. imidazol-l-yl 45 Cl H3CT' imidazol-l-yl 46 Cl ¥Y^3 pyrazol-l-yl 47 Cl H3c--r'^rCP3 pyrazol-l-yl 48 Cl h-jc-" , - cf_ 3 : 1 ^3 imidazol-l-yl 49 50 Cl ^3 /C2H5 f i / O^O^-ch-OC V ch.

Cl CH2 i I ^CO^-OC-C-C-CH^ CH-, pyrazol-l-yl pyrazol-l-yl 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 No.

X Cl r HC=CH„ 1991 1 0 AG-1293 pyrazol-l-yl Cl Br HOO^ Ois \ I HC-C=CH-CH_ / J ch3 ,HC-C=CH-CH- CH. ch_ i / 3 H_,C-OC CH- H-,C-C=C J -j \ CH_ imidazol-l-yl pyrazol-l-yl pyrazol-l-yl pyrazol-l-yl imidazol-l-yl imidazol-l-yl I ^CH3 a ^ ~cir 013 pyrazol-l-yl 1,2,3,4-tetrazol-l-yl Cl CH- 1,2,3,4-tetrazol-l-yl Cl H3C >^_CH3 2-methylpyrazol-l-yl Cl no2 pyrazol-l-yl Cl Cl H3C_r^5:>_Cl u Cl H-.C -a^ci pyrazol-l-yl pyrazol-l-yl pyrazol-l-yl Example No. X -21- -A 1991 1 0 iG-1293 66 Cl H3C y^_CH3 3,5-dibutyl-pyrazol-l-yl 67 Cl pti 2,5-diethyl-imidazol-l-yl 1991 AG -1203 The herbicidal compositions of this invention including concentrates which require dilution pri >r 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 peteroleum 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 1991 -23- AG 1203 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, 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 95 15 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 20 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 25 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 0.1-10% 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 stable 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 199110 -24- AG-1293 contain from about 0.1-60% preferably 5-50% by weight of active ingredient, the upper limit being determined by the solubility limit of active ingredient in the solvent.

In another form of aqueous suspensions, a water-immiscible herbicide is encapsulated to form microencapsulated phase dispersed in an aqueous phase. In one embodiment, minute capsules are formed by bringing together an aqueous phase containing a lignin sulfonate emulsifier and a water-immiscible chemical and polymethylene 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/1 of total composition, preferably 480 to 600 g/1. 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 water-immiscible 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 1991 -25- .AG-129-3 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 paticulate 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. Chemicals useful in combination witl^ the active ingredients of this invention include, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic 35 acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and the like such as: 199110 -26- AG -1293 Heterocyclic Nitrogen/Sulfur Derivatives 2-Chloro-4-ethylamino-6-isopropylamino-s-triazine 2-Chloro-4,6-bis(isopropylamino)-S-triazine 2-Chloro-4,6-bis(ethylamino)-s-triazine 5-Amino-4-chloro-2-phenyl-3(2H)-pyridazinone 3-Isopropyl-lH-2,1,3-benzothiadiazin-4-(3H)-one 2.2-diox ide 3-Methyl-4-amino-6-phenyl-l,2,4-triazine-5-one 3-Amino-l,2,4-triazole 6,7-Dihydrodipyrido(1,2-a:2', 11-c)-pyrazidiinium salt -Bromo-3-isopropyl-6-methyluracil 1,1'-Dimethy1-4,4'-bipyridinium salt Ureas N1-(4-chlorophenoxy) phenyl-N,N-dimethylurea N,N-dimethyl-N1-(3-chloro-4-methylphenyl) urea 3-(3,4-Dichlorophenyl)-l,1-dimethylurea 1.3-Dimethyl-3-(2-benzothiazolyl) urea 3-(£-Chlorophenyl)-l,1-dimethylurea l-Butyl-3-(3,4-dichlorophenyl)-1-methylurea Carbamates/Thiolcarbamates 2-Chloroallyl diethyldithiocarbamate S-(4-chlorobenzyl)N,N-diethylthiolcarbamate Isopropyl N-(3-chlorophenyl) carbamate 25 S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate Ethyl N,N-dipropylthiolcarbamate ^-propyl dipropylthiolcarbamate 199110 -27- .AG-I'm Acetamides/Acetanil ides/Anilines/Amides 2-Chloro-N,N-dially Lacetamide N,N-dimethyl-2,2-d iphenylacetamide N-(2,4-d imethyl-5-[[(trifluoromethyl)sulfonyl] amino]phenyl)acetamide N-isopropyl-2-chloroacetanilide 21,61-Diethy1-N-methoxymethy1-2-chloroacetanilide 2'-Methyl-61-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacetanilide t I -Trif luoro-2 , 6-dinitro-N ,N-dipropyl-£-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-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate 4,6-Dinitro-o-sec-butylphenol N-(phosphonomethyl) glycine and its monoalkyl amine and alkaline metal salts and combinations thereof Ethers 2,4-Dichlorophenyl-4-nitrophenyl ether 2-Chloro- rx, --*>trifluoro-jo-tolyl-3-ethoxy-4-nitrodiphenyl ether 1991 -28- AG 1293 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, said and the like.

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

I. Emulsifiable Concentrates Weight Percent 15 A. Compound of Example No. 1 50.0 Calcium dodecylbenzene sul-fonate/polyoxyethylene ethers blend (e.g., Atlox® 3437F and Atlox 33438F) 5.0 Monochlorobenzene 45.0 100.00 B. Compound of Example No. 2 85.0 Calcium dodecyl sulfonate/al-kylaryl polyether alcohol blend 4.0 Cg aromatic hydrocarbons 25 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 > 1991 -29- AG-129-3 II. Liquid Concentrates Weight Percent A. Compound of Example No. 4 Xylene .0 90.0 100.00 B. Compound of Example No. 5 Dimethyl sulfoxide 85.0 15.0 100.0 Compound of Example No. 6 N-methylpyrrolidone 50.0 50.0 100.00 D. Compound of Example No. 7 Ethoxylated castor oil Rhodamine B Dimethyl formamide III. Wettable Powders Compound of Example No. 8 Sodium lignosulfonate Sodium N-methyl-N-oleyl-taurate Amorphous silica (synthetic) . 0 20.0 . 5 74.5 100.00 Weight Percent 25.0 3.0 1.0 71.0 100.00 B. Compound of Example No. 10 Sodium dioctyl sulfosuccinate Calcium lignosulfonate Amorphous silica (synthetic) 80.0 1.25 2. 75 16.00 100.00 C. Compound of Example No. 2 10.0 Sodium lignosulfonate 3.0 Sodium N-methyl-N-oleyl- taurate 1.0 V Kaolinite clay 1991 AG-1293 86.0 100.00 IV. Dusts A. Compound of Example No. 3 Attapulg ite Weight Percent 2.0 98.0 100.00 B. Compound of Example No. 4 Montmorilionite 60.0 40.0 100.00 C. Compound of Example No. 5 Bentonite .0 70.0 100.00 D. Compound of Example No. 6 Diatomaceous earth 1.0 99 .0 100.00 V. Granules A. Compound of Example No. 8 Granular attapulgite (20/40 mesh) Weight Percent 15.0 85.0 100. 0 B. Compound of Example No. 1 Diatomaceous earth (20/40) .0 70.0 100.00 Compound of Example No. 2 Bentonite (20/40) 0.5 99.5 100.00 199110 -31- AC 1203 D. Compound of Example No. 3 5.0 Pyrophyllite (20/40) 95.0 100.00 When operating in accordance with the present 5 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 10 carried out by conventional 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 15 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 20 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, 25 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 11.2 kg/ha, preferably from about 0.04 to about 5.60 kg/ha, or suitably from 1.12 to 5.6 kg/ha of 30 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

Claims (45)

1991 -32- AG 1203 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 5 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 10 are not to be construed as limitations except to the extent indicated in the following claims. »> f 1 991 whay^w:: -/ aim is: CLAIMS: -33- AG 1296-

1. Compounds according to the formula 0 II XCH-C CH--A \ / N 10 Vt a wherein X is chloro, bromo or iodo; R is an acyclic 1-alken^fc-l-yl radical having up to 8 carbon atoms, a C^_^ 1-cycloalken-l-yl radical or one of said radicals substituted with one or more C-^_4 alkyl radicals and A is an unsubstituted or C^_4 alkyl-substi-tuted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical.

2. Compounds according to Claim 1 wherein R is an unsubstituted or C^_4 alkyl-substituted acyclic 1-alken-l-yl radical.

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

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

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

6. P Compound^ according to Claim 1 wherein R is an unsubstituted or C1_4 alkyl-substituted C5_? J-cycloalken-l-yl radical.

7. Compounds according to Claim 6 wherein A is a pyrazolyl radical. 199110 -34-

8. A compound according to Claim 7 which is N-(2,6-dimethyl-l-cyclohexen-l-yl)-N-(lH-pyrazol-1-ylmethyl)-2-chloroacetamide.

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

10. A compound according to Claim 9 which is N-(2,6-d imethyl-l-cyclohexen-l-y1)-N—(1H-1,2,4-triazol-1-ylmethyl)-2-chloroacetamide.

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

12. A compound according to Claim 11 which is N-(2,6-d imethyl-l-cyclohexen-l-y1)-N-(1H-imidazol-1-ylmethyl)-2-chloroacetamide.

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 0 II XCH-C CH--A \ / N i R 5 wherein X is chloro, bromo or iodo; R is an acyclic 1-alken-1-yl radical having up to 8 carbon atoms, a C1-cycloalken-l-yl radical or one of said radicals substituted with one or more C-^_4 alkyl radicals and 10 A is an unsubstituted or C-j^ alkyl-substi- tuted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical. * .. -J 1991 -35- ■/»;> O^1 S*

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

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

17. /? Composition according to Claim 16 wherein said compound is n-(1,2-dimethyl-l-propen-l-yl)-n-(lH-pyrazol-l-ylmethyl)-2-chloroacetamide.

18. ft Composition according to Claim 16 wherein said compound is N-[2-methyl-l-(1-methylethyl)-1-propen-l-yl]-N-(lH-pyrazol-l-ylmethyl)-2-chloroacet-amide.

19. Compositions according to Claim 14 wherein in said compound R is an unsubstituted or C, . alkyl-substituted C,-_7^cycloalken-l-yl radical.

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

21. A Composition according to Claim 20 wherein said compound is N-(2,6-dimethyl-l-cyclohexen-l-yl )-N-(lH-pyrazol-l-ylmethyl)-2-chloro-acetamide.

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

23. ft Composition according to Claim 22 wherein said compound is N-(2,6-dimethyl-l-cyclohexen-l-y 1)-N-(1H-1,2, 4-triazol-l-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-l-cyclohexen-l-y 1 ) -N- ( lH-imidazol-l-ylmethyl)-2-chloroacetamide.

26. Compositions according to Claim 19 wherein in said compound A is a tetrazolyl radical. * • - 199110 -36- AC-1293

27. ft Method for combatting undesirable plants in crops which comprises applying to the locus thereof a herbicidally effective amount of a compound having the formula 0 XCH9C CH--A \ / N' I yi- 10 >>1 wherein X is chloro, bromo or iodo; R is an acyclic 1-alken^-l-y 1 radical having up to 8 carbon atoms, a C^_^ 1-cycloalken-l-yl radical or one of said radicals substituted with one or more C-j^^ alkyl radicals and A is an unsubstituted or C^_4 alkyl-substituted pyrazolyl, imidazolyl, triazolyl or tetrazolyl radical.

28. ft Method according to Claim 27 wherein in said compound R is an unsubstituted or C-^_4 alkyl-suostitutea acyclic 1-alken-l-yl radical.

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

30. ft Method according to Claim 29 wherein said compound is N-(1,2-dimethyl-l-propen-l-y1)-N-(1H-pyrazol-l-ylmethyl)-2-chloroacetamide.

31. ft Method according to Claim 29 wherein said compound is N-[2-methyl-l-(1-methylethyl)-1-propen-l-y1]-N-(lH-pyrazol-l-ylmethyl)-2-chloroacetamide .

32. ft Method according to Claim 27 wherein in said compound R is an unsubstituted or C1-4 alkyl-substituted C^ ^cycloalken-l-yl radical. 199110 -37-

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

34. A method according to Claim 32 wherein said compound is N-(2,6-dimethyl-l-cyclohexen-l-yl)-N~ (lH-pyrazol-l-ylmethyl)-2-chloroacetamide.

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

36. A method according to Claim 35 wherein said compound is N-(2,6-dimethyl-l-cyclohexen-l-yl)-N-(1H-1,2,4-triazol-l-ylmethy1)-2-chloroacetamide.

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

38. A method according to Claim 37 wherein said compound is N-(2,6-dimethyl-l-cyclohexen-l-yl)-N-(lH-imidazol-l-ylmethyl)-2-chloroacetamide.

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

40. A compound according to Claim 7 which is N- (2 ,5-dimethyl-l-cyclopenten-l-yl^-N-UH-pyrazol -1-ylmethyl )-2-chloroacetami'de.

41. A composition according to Claim 20 wherein said compound is N-(2,5-dimethyl~l-cyclopenten-l-yl)-N-(lH-pyrazol-1-ylmethyl )-2~chloroacetamid

42. A method according to Claim 33 wherein said compound is N-(2,5-dimethyl-l-cyclopenten-l-yl)-N-(lH-pyrazol -1-ylmethyl)-2-ch1oroacetamid

43. A compound as claimed in any one of claims 1 to 13 substantially as hereinbefore described with reference to any examples thereof.

44. A composition as claimed in any one of claims 14 to 26 substantially as hereinbefore described with reference to any examples thereof. ^

45. A method as claimed in any one of claims 27 to 39 and 42 substantially as hereinbefore described with reference to any examples thereof. . ,v DATED THIS OF^ 18^ A. J. PARK & SON ilu Y PEB ■ ,£4 agehts for the applicants ^ ^ 1