CERTAIN 2-(2'SUBSTITUTED BENZOYL)-1,3-CYCLOHEXANEDIONES

Abstract: Compounds of the formula wherein n is the integer 0, 1 or 2; R is C₁-C₄ alkyl; R¹ is hydrogen or C₁-C₄ alkyl; R² is hydrogen, C₁-C₄ alkyl or R a -O-- wherein R a is C₁-C₄ alkyl; R¹ and R² together are alkylene having 3 to 6 carbon atoms; R³ is hydrogen or C₁-C₄ alkyl; R⁴ is hydrogen or C₁-C₄ alkyl; R⁵ is hydrogen or C₁-C₄ alkyl; R⁶ is hydrogen or C₁-C₄ alkyl; and R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁-C₄ alkyl; (4) C₁-C₄ alkoxy; (5) OCF₃; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl; (9) R b SO n - wherein n is the integer 0, 1 or 2; and R b is (a) C₁-C₄ alkyl; (b) C₁-C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR c R d wherein R c and R d independently are hydrogen or C₁-C₄ alkyl; (11) R e C(O)-wherein R e is C₁-C₄ alkyl or C¹-C₄ alkoxy; or (12) SO₂NR c R d wherein R c and R d are as defined with the proviso that R⁷ is not attached to the 6-position, are effective as herbicides.

Description: CERATIN 2-(2'-SUBSTITUTED BENZOYL)-1,3-CYCLOHEXANEDIONES Background of the Invention Compounds having the structural formula EMI1.1 wherein X can be an alkyl, n can be 0, 1, or 2, and R1 can be enyl or substituted phenyl are described in Japanese Patent Application 84632-1974 as being intermediates for the preparation of herbicidal canpounds of the formula EMI1.2 wherein R1, X, and n are as defined above and R2 is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R2 is allyl and R1 is phenyl, 4-chlorophenyl or 4-methoxyphenyl. The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity. European Patent Application Nt. 83 102 599.4 was published October 5, 1983 and relates to certain novel 2- (2-substituted benzoyl)- cyclohexane-l,3diones as herbicides. The compounds have the following structural formula EMI1.3 wherein R and R1 are hydrogen or C1-C4 alkyl; R2 is chlorine, bromine, or iodine; R3 is hydrogen or halogen; and R4 is hydrogen, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 alkoxy, nitro or trifluoranethyl. Description of the Invention This invention relates to 2-(2-benyl)-1, 3-cyclohexanediones and their use as herbicides. One embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-(2-C1-C4 alkylthio, C1-C4 alkylsulfinyl or C14 alkylsulfonyl bezoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, prefer- ably with the groups hereinafter recited. Also embodied with the scope of this invention are navel compounds having the structural formula EMI2.1 wherein n is the integer 0, 1 or 2, preferably 2; R is C1-C4 alkyl, preferably methyl; R1 is hydrogen or C1-C4 alkyl, preferably C1-C2 alkyl, more preferably methyl, most preferably R1 is hydrogen @@ methyl; R2 is hydrogen; C1-C4 alkyl, preferably C1-C2 alkyl, more preferably methyl or EMI2.2 wherein Ra is C-C4 alkyl, most preferably R2 is hydrogen or methyl; or R1 and R2 together are alkylene having 3 to 6 carbon atoms; R3 is hydrogen or C1-C4 alkyl, preferably C1-C2 alkyl, more preferably methyl; most preferably R3 is hydrogen or methyl; R4 is hydrogen or C1-C4 alkyl, preferably C1-C2 alkyl, more preferably methyl; most preferably R4 is hydrogen or methyl; R5 is hydrogen or C1-C4 alkyl, preferably C1-C2 alkyl, more preferably methyl; most preferably R5 is hydrogen or methyl; R6 is hydrogen or C1-C4 alkyl, preferably C1-C2 alkyl, more preferably methyl, most preferably R6 is hydrogen; R7 and R8 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C1-C4 alkyl, preferably methyl; (4) C1-C4 alkoxy, preferably methoxy; (5) OCF3; (6) cyano; (7) nitro; (8) C1-C4 haloalkyl, more preferably trifluoromethyl; (9) RbSOn- wherein n is the integer 0, 1 or 2, preferably 2; and Pb is (a) C1-C4 alkyl, preferably methyl; (b) C1-C4 alkyl substituted with halogen or cyano, preferably chloranethyl, trifluoromethyl or cyano methyl; (c) phenyl; or (d) benzyl; (10) iNRCRd wherein Re and Rd independently are hydrogen or C1-C4 alkyl; (11) ReC(O)- wherein Re is C1-C4 alkyl or C1-C4 alkoxy; or (12) -SO2NRcRd wherein Rc and Rd are as defined, with the proviso that R7 is not attached to the 6-position. Preferably, R7 is in the 3-position. Most preferably R7 is hydrogen or 3-chlorine and R8 is hydrogen, chlorine, bromine, fluorine, CF3, or RbS02 wherein fib is C1-C4 alkyl, preferably methyl. The term "C1-C4" alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The ten "halogen" includes chlorine, branine, iodine and fluorine. The term "C-C4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, nrbutoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, brano, iodo or fluoro. Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention. The compounds of this invention can have the following four structural formulae because of tautanerian: EMI4.1 wherein n, R, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined above. The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: EMI4.2 wherein n, R, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined above. Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithiun, sodiun, and potassiun, organic cations such as substituted ammonium, sulfoniun or phosphonium wherein the substitutent is an aliphatic or aranatic group. The compounds of this invention and their salts are active herbicides of a general type. Ihat is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention canprises applying an herbicidally effective anount of the abcve-described compounds to the area where control is desired. The compounds of the present invention can be prepared by the following two or three step general method. The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reacton (1). EMI5.1 <tb> <SEP> R2 <SEP> R1 <SEP> SR <tb> <SEP> R3 <SEP> < <SEP> 0 <SEP> o <SEP> 1 <SEP> 27 <SEP> Moderate <tb> 1) <SEP> , <SEP> "8 <SEP> Base <SEP> f <tb> R4 <SEP> / <SEP> \ <SEP> 0 <tb> <SEP> R5 <SEP> R6 <tb> <SEP> R4 <SEP> R3 <SEP> R2 <SEP> R1 <SEP> SR <tb> <SEP> R5%IYR78 <tb> <SEP> R6 <SEP> 0 <tb> wherein moderate base, and R through R8 are defined herein, and and n X is halogen, preferably chlorine, C14 alkyl-C(O)-O-, C1-C4 alkoxy-C(O)-O- or EMI5.2 wherein R, R7 and R8 in this pertion of the moledule are identical with those in the reactant shown above, and the moderate base is as defined, preferably tri-C1-C6 alkylanine, pyridine, alkali metal carbonate or alkali metal phosphate. Generally, in step (1) mole amounts of the dione and substituted benyl reactant are used, along with a mole amount or excess of the base. The two reactants are canbined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at O-C-50*C until the reaction is substantially complete. EMI6.1 <tb> <SEP> R <SEP> R3 <SEP> R2 <SEP> R1 <SEP> SR <SEP> R2 <SEP> 81 <SEP> SR <tb> <SEP> R5 <SEP> R3 <SEP> O?/78 <tb> 2) <SEP> R6 <SEP> R4 <SEP> <tb> <SEP> R6 <SEP> M3derate <SEP> / <SEP> \ <tb> <SEP> Base <SEP> R5 <SEP> R6 <tb> * = Cyanide source as defined herein. Moderate Base = As defined herein. Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassiun cyanide or acetonecyano- hydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially canplete at a tnperature below 50-C, preferably about 20 C to about 40-C, and the desired product is recovered by conventional techniques. The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion. The process is conducted in the presence of a catalytic anount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base. Preferred cyanide sources are alkali metal cyanides such as sodiun and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C25 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trim methyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin. The cyanide source is used in an anount up to about 50 mole percent based on the enol ester. It may be used in as little as about 7 mole percent to produce an acceptable rate of reaction at about 400C on a snall scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred. The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylanines such as triethylanine, trialkanol spines such as triethanolanine, and pyridine. Suitable inorganic bases include potassium carbonate and trisodium phosphate. The base is used in an amount of fran about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole. When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers. A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1, 2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimetylform- amide, and methyl isobutyl ketone (MIBK). In general, depending on the nature of the reactants and the cyanide source, the rearrangment may be conducted at temperatures up to about 50 C. EMI8.1 wherein n is 1 or 2. Generally in step (3), a mole of the reaction product of step (2) is reacted with a slight mole or two mole excess of of an oxidizing agent such as m-chloroperbenzoic acid atter being dissolved in a solvent such as methylene chloride. After completion of the reaction, the resulting mixture is stripped under vacuum. The residue is purified by silica gel chranatography to yield the desired product. The above described substituted benzoyl chlorides can be prepared fran the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L.F. Fieser and M. Fieser, pp. 767-769 (1967). EMI8.2 wherein R, R7 and R8 are as previously defined. The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C.A. Buehler and D.F. Pearson, J. Wiley and Sons, (1970). The following are three representative exanples of the methods described therein. EMI9.1 wherein R, R7 and R8 are as previously defined. In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques.. EMI9.2 wherein R, R7 and R8 are as previously defined. In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. EMI9.3 wherein R, R7 and R8 are as defined and X is chlorine, bromine or iodine. In reaction (c) the substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benaDic acid is isolated by conventional techniques. The following exanples teach the synthesis representative canpounds of this invention. EXAMPLE 1 2-(2 '-Methylthiobenzoyl)-4, 4, 6=trimethyl-1, 3syclohexanedione EMI10.1 2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and 4,4,6-trimethylcyclohexanedione (5.0 g, 39 itmol) were dissolved in methylene chloride. Triethylamine (7.0 ml, 50 mmol) was added dropwise and the resulting solution stirred for one hour at room temperature. The solution was washed with 2 normal hydrochloric acid (2N HCl), 5% potassiun carbonate solution (5% K2CO3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (2.5 equivalents) and acetone cyanohydrin (0.4 ml) were added and the solution stirred for 45 minutes at roan temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K2CO3. The aqueous extract was acidified with hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO4) and concentrated under vacuun. The residue was purified by trituration with ether, yielding 5.0 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance Spectroscopy (rrnr), infrared spectroscopy (ir) and mass spectroscopy (ms). EXAMPLE 2 2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione EMI10.2 The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9 umol) was dissolved in 40 ml methylene chloride. m-Chloroperbenzoic acid (3.5 g, 16 rrmol) was added and the resulting solution was stirred for 45 minutes. The solution was concentrated under vacuum. Purification of the residue by silica gel chromatography yielded 1.7 g of a viscous oil which was identified as the desired compound by rmr, ir and ms. EXAMPLE 3 2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl 1,3-cyclohexanedione EMI11.1 2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3cyclohexanedione (5.0 g, 14 mnol) (which was prepared according to the method of Example 1) was dissolved in 50 ml methylene chloride. A solution of m-chloroperbenzoic acid (2.4 g - 80%, 14 rrmol) in 50 ml methylene chloride was added dropwise and the resulting solution was stirred for three hours at roan temperature. After concentration under vacuun, the residue was dissolved in ether and washed with 1% hydrochloric acid. A 5% oopper(II) acetate solution was added to the ether fraction, followed by hexane. The liquid phase was decanted and the remaining gumny solid stirred with 6N BCl and ether. The ether layer was dried (MgSO4) and concentrated to give 4.7 of a thick yellow solid. Purification on a centrifugally accelerated thin layer chromatograph (4 mm silica gel, 50:50:1 hexane:ethyl acetate acetic acid - eluent) yielded 2.4 g of a viscous oil which was identified as the desired compound by nmr, ir and ms. The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound nunbers are assigned to each compound and are used throughout the remainder of the application. TABLE I EMI12.1 Comp. No. n R R1 R2 R3 R4 R5 R6 R7 R8 m.p. 1 0 CH3 H H H H H H H H 79-81 C 2 0 CH3 CH3 CH3 H H H H H H oil 3a) 0 CH3 CH3 CH3 H H CH3 H H H oil 4b) 2 CH3 CH3 CH3 H H CH3 H H H oil 5 0 C2H5 CH3 CH3 H H H H H H oil 6 2 C2H5 CH3 CH3 H H H H H H oil 7 0 CH3 H H H H H H 3-Cl Cl 59-64 C 8 2 CH3 H H H H H H 3-Cl Cl 116-119 C 9 0 CH3 H H H H H H H CF3 102-106 C 10 2 CH3 H H H H H H H CF3 oil 11 0 CH3 CH3 CH3 H H H H H CF3 49-53 C 12 2 CH3 CH3 CH3 H H H H 8 CF3 oil 13c) 1 CH3 CH3 CH3 H H H H H CF3 oil 14 0 CH3 H H H H H H 3-Cl -SCH3 105-107 C 15 1 CH3 H H H H H H 3-Cl -S(O)CH3 oil 16 0 CH3 H H H H H H H -SO2n-C3H7 oil 17 0 CH3 H H H H H H H -SCH3 101-1030C 18 2 CH3 H H H H H H H -SO2n-C3H7 oil 19 2 CH3 H H H H H H H -SO2CH3 194-1960C 20 0 CH3 H H H H H H 3-CH3 H 40-42-C 21 2 CH3 H H H H H H 3-CH3 H 80-86-C a) Prepared in Example 1. b) Prepared in Example 2. c) Prepared in Example 3. Herbicidal Screening Tests As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner. Pre-emergence herbicide test. Cn the day preceding treatment, seeds of eight different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipanoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), curly dock (CD) (RLnlex crispus), and yellcw nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants. using an analytical balance, 600 milligrans (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. me paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.58 (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 Ib/acre (4.48 Kg/ha). After treatment, the flats are placed in the greenhouse at a temperature of 70 to 800F and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the sane age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing canplete control. The e results of the tests are shown in the following Table II. TABLE II Pre-Emergence Herbicidal Activity Application Rate - 4.48 kg/ha Qnpd. No. FT WG WO AMG VL MD CD YNG 1 0 0 0 0 0 0 0 20 2 25 30 30 0 70 0 40 30 3 25 20 0 0 0 0 0 0 4 100 100 90 60 100 100 100 90 5 50 60 40 50 50 60 90 50 6 100 95 50 40 40 60 99 70 16 80 100 50 60 100 90 90 90 20 100 100 30 15 100 100 90 85 21 100 100 - 30 100 95 100 80 A blank (-) indicates that the weed was not tested. Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the eight different weed species are planted 1012 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants. The e results of the post-emergence herbicide test are reported in Table III. TABLE III Pre-Emergence Herbicidal Activity Application Rate - 4.48 Wha Onpd. No. FT WG WO AMG VL MD CD YNG 1 20 20 10 20 40 40 20 40 2 0 60 60 50 70 30 0 15 3 20 20 0 10 0 20 0 20 4 85 90 100 45 75 30 80 65 5 55 50 60 50 75 85 65 6 70 70 50 60 80 70 90 16 95 95 40 100 100 100 100 90 20 95 75 35 40 95 75 35 80 21 80 70 30 45 80 90 50 70 A blank (-) indicates the weed was not tested. Pre-Emergence Multi-Weed Herbicide lest: Several compounds were evaluated at an application rate of 2 or 1 acre (2.24 or 1.12 kg/ha) for presnergence activity against a larger number of weed species. The process was generally similar to the pre-emergence herbicide test described above except that only 300, 150 or 37.5 milligrans of test canpound were weighed out and the application rate was 40 gallons per acre. Redroot pigweed (PW) and curly dock (CD) were eliminated in this test and the following weed species were added: Grasses: downy brane Bromus tectorum (DB) annual ryegrass Lolium multiflorum (ARG) Johnsongrass Sorghum halepense (JG) broadleaf signallgrass Brachiaria platyphyfla (BSG) hemp sesbania Sesbania exaltata (SESB) sicklepod Cassia obtusifolia (SP) The results of the test are shown in Tables IV and V. TABLE IV Pre-Emergence Multi-weed Herbicide Test Application Rate - 2.24 kg/ha Qnpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNG 17 95 85 35 100 85 25 90 100 100 100 40 100 95 18 0 0 0 50 20 0 15 60 45 100 0 100 TABLE V Pre-Eergence Multi-weed Herbicide Test Application Rate - 1.12 kg/ha Qnpd. No. DB FT ARG G w; JG WO BSG AMG SESB VL SP ND YNG 7 30 70 20 100 75 0 90 100 95 100 100 100 90 8 95 95 45 100 98 25 90 100 95 100 90 100 90 9 10 70 40 100 20 0 80 100 85 100 40 100 95 10 100 100 10 100 40 0 90 100 100 100 80 100 100 11 90 100 90 100 100 65 100 100 90 100 30 100 65 12 100 100 80 100 100 85 90 100 100 100 85 100 90 13 0 100 10 100 100 80 70 80 90 100 70 100 80 15 0 10 0 90 0 0 15 35 30 100 10 85 75 19 100 90 0 100 20 10 40 95 100 100 100 100 65 Post-Emergence Multi-Weed Herbicide Test: This test is conducted in an identical manner to the testing procedure for the postemergence herbicide test, except the seeds of the eight weed species used in the pre-emergence multi-weed herbicide test were used and the seeds were planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants. The results of the post-emergence multi-weed herbicide test are reported in Tables VI and VII. TABLE VI Post-Emergence Mal tiwe ed Berbicidal Activity Application Rate - 2.24 kggha Qnpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP ND YNG 17 80 100 55 95 90 20 60 100 100 100 75 100 70 18 0 100 0 98 20 0 10 70 60 100 10 100 45 TABLE VII Post-Emergence Multi-Weed Herbicidal Activity Application Rate - 1.12 Wha Qnpd. ?b. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNG 7 25 30 0 70 60 20 90 75 95 85 50 100 35 8 80 80 20 70 70 40 80 50 80 80 60 60 35 9 0 30 0 75 15 25 100 95 100 100 60 100 25 10 60 80 20 70 35 25 80 75 90 90 70 100 45 11 45 100 20 100 100 40 50 100 100 100 20 100 35 12 70 60 30 100 100 80 98 90 100 100 70 98 40 13 25 100 10 100 100 85 100 80 100 100 10 90 25 15 30 65 10 90 50 30 20 85 80 98 30 65 15 19 20 60 10 90 10 15 90 100 100 70 100 40 85 The canpounds of the present invention are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds herein defined are formulated into herbicidal canpositions, by admixture, in herbicidally effective amounts, with the aflju- vants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds may be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as as solutions or as any of several other knows types of formulations, depending upon the desired mode of other known types of formulations, depending upon the desired mode of application. Preferred formulations for pre-nergence herbicidal applications are wettable powders, snulsifi- able concentrates and granules. These formulations may contain as little as about 0.58 to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies fran about 0.05 to approximately 25 pounds per acre, preferably fran about 0.1 to about 10 pounds per acre. Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied ts the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wµttable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a snall anount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion. Emulsifiable concentrates are hamogeneous liquid cempositions which are dispersible in water or other dispersant, and may consist entirely of the active canpound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aranatic naphthal, isophorone and other nonvolatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the ccmposition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal compOsition. Granular formulations wherein the toxicant is carried on rela- tively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for gran- ular formulations include sand, fuller's earth, bentonite clays, vermucul ite, perlite and other organic or inorganic materials which absorb or which may be coated with the toeicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such heavy aranatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as destrins, glue or synthetic resins. Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodiun salts; polyhyssric alcohols; and other types of surface-active agents, many of which are available in canmerce. The surface-active agent, when used, normally canprises fran 0.1% to 15% by weight of the herbicidal composition. Dusts, which are frec flcwqng admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application. Pastes, which are homogeneous suspensions of a finely divided solid toy cant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain snall amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected. Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is comç & tely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finelydivided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used. The e phytotoxic canpositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied fran airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic composi- tions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the canpositions into the soil as the water is absorbed therein. Dust compositions, granular canpositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. EMULSIFIABLE CONCENTRATE FORMULATIONS General Formula with Bangers Specific Formula Herbicidal compound 5-55 herbicidal compound 54 surfactant(s) 5-25 proprietary blend of oil- 10 solvent(s) 20-90 soluble sulfonates and 100% polyoxyethylene ethers polar solvent 27 petroleum hydrocarbon 9 100% WETTABLE POWDER FORMULATIONS herbicidal compound 3-90 herbicidal compound 80 wetting agent 0.5-2 sodiun dialkyl naphthalene 0.5 dispersing agent 1-8 sulfonate diluent(s) 8.5-87 sodiun lignosulfonate 7 100% attapulgite clay 12.5 100% EXTRUDED GRANULAR FORMULATIONS herbicidal compound 1-20 herbicidal compound 10 birding agent 0-10 lignin sulfonate 5 diluent(s) 70-99 calcium carbonate 85 100% 100% FLOWABLE FORMULATIONS <RTI ID=20.7> herbicidal compound 20-70 herbicidal compound 45 surfactant(s) 1-10 polyoxyethylene ether 5 suspending agent( s) 0.05-1 attagel 0. 05 antifreeze agent 1-10 propylene glycol 10 antimicrobial agent 1-10 BIT 0.03 antifoam agent 0.1-1 silicone defoaner 0.02 solvent 7.95-77.85 water 39.9 100% 100% The phytotoxic canpositions of this invention can also contain other additanents, for example, fertilizers and other herbicides, pesticides and the like, used as adjuvant or in canbination with any of the above-described adjuvants. Other phytotocic compounds useful in combinat- tion with the above-described canpounds include, for example, anvil ides such as 2-benzothiazole-2-yloxy-N-methyl acetanilide, 2-chloro-2',6'-dimethyl-N-(n-propylethyl) acetanilide, 2-chloro-2',6'-diethyl-N-(butoxymethyl) acetanil ide; 2,4-d ichlorophenaKyacetic acids, 2,4, 5-trichlorophen- oxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and rides thereof; triazine derivatives, such as 2,4-bis(3-methoxypropylamino)-6-methylthio-s-triazine, 2-chloro-4-ethylamino-6-isoproyplamino-striazine, and 2-ethylamino-4-isopropyl-amino-6-methyl-mercapto-s-triazine; urea derivatives, such as 3-(,5-dichlorophenyl)-1,1-dimethylurea and 3-(p-chlorophenyl)-1,1-dimethylurea, and acetanides such as N,N-diallyl &alpha; -chloroacetamide, and the like; benzoic acids such as 3-amino-2,5-di- chlorobenaoic acid; thiocarbanates such as S- (1, 1-dimethylbenzyl)-piperidene-1-carbothioate, 3-(4-chlorophenyl)-methyl diethylcarbothioate, ethyl-1-hexahydro-1,4-azepine-1-carbothioate, S-ethyl-hexahydro-1H-azepine-1-carbothioate, S-propyl N,N-dipropylthiocarbamate, S-propyl N,N-di n-propylthiccarbanate, S-ethyl cyclohexylethylthiocarbamate and the like; anilines such as 4-(methylsulfonyl)-2,6-dinitro-N,Nsubstituted aniline, 4-trifluoromethyl-2,6-dinitro-N,N-di-n-propyl aniline, 4-trifluoromethyl2,6-dinitro-N-ethyl-N-butyl aniline, 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoic acid, 2-[1-(ethoxyimino)butyl]-5-[2-ethylthio)propyl]-3-hydroxy2-cyclohexene-1-one, (#)-butyl-2-[4-[(5-trifluoromethyl)-2-pyridinyl)oxy]- phenoxy]propanate, sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2fluoromethyl)phenoxy]-2-nitrobenzoate, 3-isopropyl-1H-2,1,3-benzothiadiazine-4(3H)-one-2,2-dioxide, and 4-amino-6-tert-butyl-3-(methylthio)-astriazine-5(4H)-one or 4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4 triazin-5 (4H )-one and S-(O,O-diisopropyl)-benzene sulfonamide. Fertil izers useful in ccmbination with the active ingredients include, for exanple, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organists take root and grow such as post, manure, humus, sand, and the like.

Claims: WHAT IS CLAIMED IS: 1. A compound of the formula EMI22.1 wherein n is the integer 0, 1 or 2; R is C1-C4 alkyl; R1 is hydrogen or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl or EMI22.2 wherein Ra is C1-C4 alkyl; or R1 and R2 together are alkylene having 3 to 6 carbon atans; R3 is hydrogen or C1-C4 alkyl; R4 is hydrogen or C1-C4 alkyl; R5 is hydrogen or C1-C4 alkyl; R6 is hydrogen or C14 alkyl; and R7 and R8 independently are (1) hydrogen; (2) halogen; (3) C1-C4 alkyl; (4) C1-C4 alkoxy; (5) OCF3; (6) cyano; (7) nitro; (8) C14 haloalkyl; (9) RbSOn- wherein n is the integer 0, 1 or 2; and Rb is (a) C1-C4 alkyl; (b) C1-C4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NRCRd wherein RC and Rd independently are hydrogen or C1-C4 alkyl; (11) ReC(O)- wherein Re is C1-C4 alkyl or C1-C4 alkoxy; or (12) SO2NRCRd wherein Re and Rd are as defined, with the proviso that R7 is not attached to the 6-position. 2. The compounds of Claim 1 wherein n is 2; R is methyl; R1 is hydrogen or methyl; R2 is hydrogen or methyl; R3 is hydrogen or methyl; R4 is hydrogen or methyl; R5 is hydrogen or methyl; R6 is hydrogen or methyl; R7 and R8 independently are (1) hydrogen; (2) halogen; (3) C1-C4 alkyl; (4) C1-C4 alkoxy; (5) OCF3; (6) cyano; (7) nitro; (8) C1-C4 haloalkyl; (9) RSOn- wherein n is the integer 0, 1 or 2; and Rb is (a) C1-C4 alkyl; (b) C1-C4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NRcRd wherein Re and Rd independently are hydrogen or C1-C4 alkyl; (11) ReC(O)- wherein Re is C1-C4 alkyl or C1-C4 alkoxy; or (12) SO2NRcRd wherein Re and Rd are as defined. 3. The compound of Claim 2 wherein R7 and R8 are independently are hydrogen; chlorine; fluorine; branine; methyl; methoxy; OCF3; cyano; nitro; trifluoranethyl; RbSOn- wherein n is the integer 2 and Rb is methyl, chloranethyl, trifluoranethyl, cyananethyl, ethyl, or n-propyl; -NRcRd wherein Rc and Rd independently are hydrogen or C1-C4 alkyl; ReC(O)- where Re is C1-C4 alkyl or C1-C4 alkoxy or S02NRCRy wherein Rc and are as defined and R7 is in the 3-position. 4. The compounds of Claim 2 wherein R7 is hydrogen and R8 is hydrogen, chlorine, branine, fluorine, CF3 or RbSO2 wherein Pb is C1-C4 alkyl. 5. The ccmpound of Claim 2 wherein n is two;-R is methyl; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is hydrogen; and R8 is hydrogen. 6. The compound of Claim 2 wherein n is two; R is methyl; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is methyl; R6 is hydrogen; R7 is hydrogen; and R8 is hydrogen. 7. The compound of Claim 2 wherein n is zero; R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is 3-chlorine; and R8 is chlorine. 8. The canpound of Claim 2 wherein n is two; R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrc3en; R7 is 3-chlorine; and R8 is chlorine. 9. The compOund of Claim 2 wherein n is zero; R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is hydrogen; and R8 is trifluoromethyl. 10. The compound of Claim 2 wherein n is two; R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is hydrogen; and R8 is trifluoromethyl. 11. The compound of Claim 2 wherein n is zero; R is methyl; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is hydrogen; and R8 is trifluoromethyl. 12. The compound of Claim 2 wherein n is two; R is methyl; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is hydrogen; and R8 is trifluoramethyl, 13. The compound of Claim 2 wherein n is one; R is methyl; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is hydrogen; and R8 is trifluoromethyl. 14. The conpound of Claim 2 wherein n is zero; R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is 3-chlorine; and R8 is methylthio. 15. The compound of Claim 2 wherein n is one; R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is 3-chlorine; and R8 is CH3S(O)-. 16. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound of Claims 1-15. 17. An herbicidal camposition comprising an herbicidally active 2-(2-C1-C4 alkylthio, C14 alkylsulfinyl or C1-C4 alkylsulfonyl benzoyl) 1 ,3-cyclohexanedione and an inert carrier therefor. 18. The herbicidal copposition of Claim 17 wherein the 2-(2-C1-C4 alkylthio, C1-C4 alkylsulfinyl or C14 alkylsulfonyl benzoyl)1,3-cyclohexanedione is a compound of Claims 1-15. 19. A process for preparing a compound of the formula EMI25.1 wherein R is C1-C4 alkyl; R is C1-C4 alkyl, optionally substituted with halogen; R1 is hydrogen or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl or EMI25.2 wherein Ra is C1-C4 alkyl; or R1 and R2 together are alkylene having 3 to 6 carbon atoms; R3 is hydrogen or C1-C4 alkyl; R4 is hydrogen or C1-C4 alkyl; R5 is hydrogen or C1-C4 alkyl; R6 is hydrogen or C1-C4 alkyl; and R7 and R8 independently are (1) hydrogen; (2) halogen; (3) C1-C4 alkyl; (4) C1-C4 alkoxy; (5) OCF3; (6) cyano; (7) nitro; (8) C1-C4 haloalkyl; (9) RbSOn- wherein n is the integer 0, 1 or 2; and Rb is (a) C1-C4 alkyl; (b) C14 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) QNRCRd wherein Rc and Rd independently are hydrogen or C14 alkyl; (11) ReC(O)- wherein Re is C1-C4 alkyl or C1-C4 alkoxy; or (12) So2NRCRd wherein Re and Rd are as defined, with the proviso that R7 is not attached to the 6-position comprising (a) reacting a dione of the formula EMI25.3 wherein R1 through R6 are as defined with a substituted benzoyl reactant of the formula EMI25.4 wherein R, R7 and R8 are as defined and X is halogen, C1-C4 alkyl-C(O)-O-, C14 alkoxy-C(O)-O- or EMI26.1 wherein R, R7 and R8 in this portion of the molecule are identical with those in the reactant shown above with at least a mole of a moderate base to from an enol ester of the formula EMI26.2 wherein R through R8 are as defined and in step (2) reacting a mole of the enol ester intermediate with 1 to 4 moles of a moderate base, and fran 0.01 mole to about 0.5 mole or higher of a cyanide source to form a 2-C-C4 alkylthiobenzoyl compound of the formula EMI26.3 wherein R1 through R8 are as defined above and optionally oxidizing the 2-C1-C4 alkylthiobenzoyl compound with a mole or two moles of an oxidizing agent to form a compound of the formula EMI26.4 where R through R8 are as defined and n is the integer 1 or 2. 20. The process of Claim 19 wherein X is halogen, the moderate base is tri-C1-C6 alkylamine, pyridine, alkali metal carbonate or alkali metal phosphate and the cyanide source alkali metal cyanide, cyanohydrins of methyl C1-C4 alkyl ketones, cyanohydrins of benzaldehyde or C2-Cs aliphatic aldehyzes; cyanohydrins, zinc cyanide; tri(lower alkyl) silyl cyanides or hydrogen cyanide. 21. The process of Claim 20 wherein X is chlorine, the moderate base is tri-C1-C6 alkylamine, pyridine, sodium carbonate or sodium phosphate and the cyanide source is potassitzn cyanide, acetone cyanohydrin or hydrogen cyanide.

Inventors: CARTER, CHARLES GARVIE, LEE, DAVID LOUIS, MICHAELY, WILLIAM JAMES
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1985
Main classification: C07C149
IPC codes: C07C317, A01N41, C07C315, C07C313, C07C67, C07C323, A01N25, A01N35, A01N37, C07C49, C07C311