CERTAIN-2-(2'-ALKYLBENZOYL)-1,3-CYCLOHEXANEDIONES

Abstract: Compounds of the formula wherein R is C₁-C₄ alkyl or CF₃; R¹ is hydrogen or C₁-C₄ alkyl; R² is hydrogen, C₁-C₄ alkyl or Ra-O-- wherein Ra 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: CERTAIN 2-(2'-ALKYLBENZOYL)-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 phenyl or substituted phenyl are described in Japanese Patent Application 84632-1974 as being intermediates for the preparation of herbicidal compounds 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 Nb. 83 102 599.4 was published October 5, 1983 and relates to certain novel 2-(2-substituted benzoyl)- cyclohexane-1,3-diones 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, branine, iodine, C1-C4 alkyl, Cl-C4 alkoxy, nitro or trifluoranethyl. Description of the Invention This invention relates to 2-(2-alkylbenzoyl)-1,3-cyclohexane- diones and their use as herbicides. One embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with C14 alkyl, preferably C1-C2 alkyl, optionally substituted with halogen, more preferably methyl or CF3 and the 4 -position preferably is substituted with an electron withdrawing group, such as halogen, cyano, CF3 or nitro. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. M3re 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, preferably with the groups hereinafter recited. Also embodied within the scope of this invention are novel com- pounds having the following structural formula EMI2.1 where in R is C1-C4 alkyl, preferably C1-C2 alkyl, optionally substituted with halogen, more preferably methyl and R1 is hydrogen or C14 alkyl, preferably C12 alkyl, more preferably methyl, most preferably R1 is hydrogen or methyl; R2 is hydrogen; C1-C4 alkyl, preferably C12 alkyl, more preferably methyl or EMI2.2 wherein Ra is C1-C4 alkyl, most preferably R2 is hydrogen or methyl; or R1 and R2 together are alkylene having 3 to 6 carbon atans; R3 is hydrogen or C1-C4 alkyl, preferably C12 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 C12 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 branine; (3) C1-C4 alkyl, preferably methyl; (4) C1-C4 alkoxy, preferably methoxy; (5) oCF3; (6) cyano; (7) nitro; (8) C1-C4 haloalkyl, more preferably trifluoranethyl; (9) RbSOn- wherein n is the integer 0, 1 or 2, preferably 2; and Rb is (a) C14 alkyl, preferably methyl; (b) Ct-C4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoranethyl or cyano methyl; (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 Rc and Rd are as defined, with the proviso that R7 is not attached to the 6-position. The term "C1-C4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, brine; iodine and fluorine. The term "C1-C4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrcgens replaced by chloro, brans, iodo or fluoro. Preferably, R7 is in the 3-position. fDSt preferably R7 is hydrogen and R8 is hydrogen, chlorine, branine, fluorine, CF3, or wherein Rb is C1-C4 alkyl, preferably methyl. Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention. The canpounds of this invention can have the following four structural formulae because of tautanerism: EMI4.1 wherein R, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined above. The circled proton on each of the four tautaners 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 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 phosphoniun wherein the substituent is an aliphatic or aranatic group. The compounds of this invention and their salts are active herbicides of a general type. That 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 above-described compounds to the area where control is desired. The compounds of the present invention can be prepared by the following two-step general method. The process proceeds via the production of an enol ester intermediate as skown 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 mediun 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> R <tb> 1 <SEP> ) <SEP> Wt <SEP> + <SEP> X < &commat;8 <SEP> > <tb> R5 <SEP> O <SEP> M3derate <SEP> Base <tb> <SEP> R5 <SEP> R6 <tb> <SEP> R4 <SEP> R3 <SEP> R2 <SEP> R1 <SEP> R <tb> <SEP> R5 <SEP> z <tb> <SEP> R6 <tb> wherein R through R8 are as defined and X is halogen, preferably chlorine, C1-C4 alkyl-C(O)-O-, C1-C4 alkoxy-C(O)-O- or EMI6.1 wherein R, R7 and R8 in this portion of the molecule 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 benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are oanbined 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 0 C-50 C until the reaction is substantially complete. The reaction product is worked up by conventional techniques. EMI6.2 <tb> <SEP> R4 <SEP> R3 <SEP> R2 <SEP> R1 <SEP> R <SEP> R2 <SEP> R1 <SEP> R <tb> <SEP> R5 <SEP> S <SEP> o <SEP> &commat; <SEP> 7 <SEP> R3 <SEP> 01IR7 <tb> R6 <SEP> s <SEP> /\ <SEP> t <tb> <SEP> R6 <SEP> Mbderate <SEP> Base <SEP> R4 <SEP> o <tb> <SEP> R5 <SEP> R6 <tb> * = Cyanide source. Moderate base = as defined herein. wherein R through R8 are as defined. 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 moder- ate base and fran 0.01 mole to about 0.5 nole or high2r, preferably around 0.1 mole of the cyanide source (e.g., potassiun cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80 C, preferably about 20µC 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 andVor 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 potassiun 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 trimethyl 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 amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 400C on a small 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 strcsi 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 gamines include trialkylanines such as triethylanine, trialkanol ermines such as triethanolanine, and pyridine. Suitable inorganic bases include potassiun carbonate and trisodiun phosphate. The base is used in an mount 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, dimethylform- anide, 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. The above described substituted benzoyl chlorides can be prepared from 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). EMI8.1 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 Carboxy- lic Acids and Esters, S. Patai, editor, J. Wiley and Sons, Nµw York, N.Y. (1969) and Survey of Organic Synthesis, C.A. Buehler and D. F. Parson, J. Wiley and Sons, (1970). The following are four representative examples 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, brine or iodine. The substituted aromatic halide is allowed to react with manner siun in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques. The following example teachs the synthesis of a representative canpound of this invention. EXAMPLE 1 2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3 cyclohex aned ione EMI10.1 4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mnol) and 4,4,6-trimethyl-1, 3-cyclohexanedione (2.3 g, 15 mmol) were dissolved in 100 ml methylene chloride. The solution was cooled with an ice bath and triethylanine (2.1 ml, 15 itiriol) in 10 ml methylene chloride was added dropwise. The ice bath was then removed and the resulting solution stirred for 30 minutes at roan temperature. The solution was washed with 2N hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K2CO3) and saturated sodium chloride solution (brine), dried over anhydrous magnesiun sulfate (MgSO4) and concentrated under vacuum. The residue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine (3.5 ml, 25 itmol) and 0.4 ml acetone cyanohydrin were added and the solution stirred for two hours at roan temperature while protected by a drying tube (calciun sulfate). After dilution with ether, the solution was washed with 2N EC1 and extracted with 5% R2DO3. The aqueous extract was acidified with concen- trated hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO4) and concentrated under vacuun. The resulting oil was purified on a silica gel colunn (80:20:1 hexane:ethyl acetate: acetic acid - eluent), yielding 1.5 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy. The following is a table of certain selected canpounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application. TABIE I EMI11.1 Comp. No. R R1 R2 R3 R4 R5 R6 R7 R8 nD30 or m.p. 1 CH3 H H H H H H H H 35-42eC 2 CH3 CH3 CH3 H H H H H H 47-S30C 3 CH3 CH3 CH3 H H H H H Br oil 4 CH3 CH3 CH3 H H H H H CN oil 5 CH3 CH3 CH3 H H H H 3N02 H oil 6 CH3 CH3 CH3 H H H H 5-Cl H oil 7 CH3 CH3 CH3 H H H H H CH3S02- oil 8 CH3 CH3 CH3 H H CH3 H H CH3SO2- oil 9 CH3 CH3 CH3 H H H H 3-Cl H oil 10 CH3 CH3 CH3 H H CH3 H H C2H5SO2- oil 11 CH3 CH3 CH3 H H H H H C2H5SO2- oil 12 CH3 CH3 CH3 H H H H H n-C3H7SO2- oil 13 CH3 H H H H H H H CH3SO2- oil 14 CH3 H H H H H H H n-C3H7SO2- oil 15 CH3 CH3 CH3 H H H H H CH3S- oil 16 c2H5 CH3 CH3 H H H H H Br oil 17 CH3 H H H H H H H CN oil 18 CH3 CH3 CH3 H H H H H F oil 19 CH3 H H H H H H H C2H5-SO2- oil 20 CH3 H H H H H H 3-Cl H 65-67 C 21 CH3 H H H H H H <RTI ID=11.8> 3-I H oil 22 CH3 H H H H H H 3-NO2 H oil 23 CH3 H H H H H H 3-CN H 96-101 C 24 CF3 CH3 CH3 H H H H H H oil 25 CF3 H H H H H H H H oil 26 CF3 CH3 CH3 H H H H H Br oil 27 CF3 H H H H H H H Cl 82-88 C 28 CF3 CH3 CH3 H H H H H Cl oil 29 CF3 H H H H H H H C2H5S- oil TABLE I (continued) Comp. No. R R1 R2 R3 R4 R5 R6 R7 R8 nD30 or m.p. 30 CF3 CH3 CH3 H H H H H C2H5802- oil 31 CF3 H H H H H H H CN oil 32 CF3 CH3 CH3 H H H H H CN oil 33a CF3 CH3 CH3 H H CH3 H H Br oil 34 CH3 H H H H H H H CH3 35 CH3 CH3 CH3 H H H H 3-Cl C2H5SO2 115-117 C 36 CH3 H H H H H H 3-Cl C2H5S 2 oil 37 CH3 b) b) H H H H 3-CF3 H oil 38 CH3 c) H i-C3H7 H H H 3-NO2 H 88-108 C 39 CF3 CH3 CH3 H H CH3 H H CH3S oil 40 CF3 CH3 CH3 H H H H H CH3S oil 41 CF3 CH3 CH3 H H CH3 H H CH3SO2- oil 42 CH3 CH3 CH3 H H H H H CF3 oil 43 CH3 H H H H H H H CF3 114-120 C 44 CH3 H H H H H H 3-Cl Cl oil 45 CH3 CH3 CH3 H H H H 3-Cl Cl oil 46 CH3 CH3 CH3 H H H H 3-CF3 H oil 47 CF3 H H H H H H H CH3S oil 48 CF3 CH3 CH3 H H CH3 H H CF3 oil 49 CF3 H H H H H H H CF3 oil 50 CF3 CH3 CH3 H H H H H CF3 oil 51 CH3 H H CH3 H H H H CH3SO2 oil 52 CF3 CH3 CH3 H H CH3 H H C2H5SO2 oil 53 CH3 H H H H H H H Br 94-98 C 54 CH3 H H H H H H d) H oil a) Prepared in Example 1. b) -(CH2)5c) C2H5OC(O)d) 3-N(CH3)COCH3 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. On the day preceding treatment, seeds of eight different weed species are planted in loany sand soil in individual rows using one species per row across the width of a flat. The weeds used are green foxtail (FT) (Setaria viridis), watergrass (wig) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipcmoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), curly dock (CD) (Runex crispus), and yellow 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 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The 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 0.5% (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 lb/acre (4.48 Kg/ha). After treatment, the flats are placed in the greenhouse at a temperature of 70 to 80"F and watered by sprinkling. To weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the s & e age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control. The e results of the tests are shown in the following Table II. TABLE II Pre-Emergence Berbicidal Activity Application Rate -- 4.48 kg/ha Cmpd. No. FT WG WO AMG VL MD CD YNG 1 40 20 0 0 0 0 0 100 2 60 70 0 0 0 0 90 100 3 100 100 50 50 100 100 85 90 4 100 100 90 30 100 85 95 95 5 100 100 80 10 100 100 100 95 6 20 35 25 15 90 85 40 85 7 100 100 90 100 100 100 100 95 8 100 100 90 100 100 100 100 95 9 100 100 0 0 100 80 100 90 10 100 100 100 100 100 100 100 95 11 100 100 70 100 100 100 97 95 12 100 100 60 100 100 100 100 95 13 100 100 60 100 100 100 100 95 14 80 100 50 80 100 100 90 90 15 100 100 80 100 100 100 100 16 50 75 0 25 100 100 95 60 17 100 100 40 100 100 100 100 85 18 100 100 0 20 100 100 80 70 20 70 75 0 25 100 95 100 60 21 50 60 0 0 100 80 80 60 22 100 95 35 25 100 100 90 50 23 95 100 40 20 100 100 90 50 24 100 100 90 0 45 85 80 90 25 100 100 25 60 100 100 100 75 34 35 40 10 0 60 25 0 70 37 50 60 0 0 60 0 50 0 38 35 40 0 0 0 0 0 0 52 85 100 30 95 100 100 - 80 53 100 100 0 85 100 100 - 80 54 100 100 90 25 100 100 - 80 A blank (-) indicates that the weed was not tested. Post-Emergence Herbicide Test: Ihis 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 results of the post-emergence herbicide test are reported in Table III. TABLE III Post-Emergence Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT NG WO AMG VL MD CD WG 1 60 40 20 30 40 40 50 60 2 50 40 10 20 20 20 40 60 3 100 100 85 100 100 100 100 75 4 100 100 95 85 100 95 100 60 5 95 95 100 65 90 25 70 45 6 40 30 0 20 90 25 20 70 7 100 100 100 100 100 100 100 90 8 100 95 100 100 100 100 100 70 9 65 65 0 20 80 65 90 80 10 100 100 100 100 100 100 100 70 11 85 90 90 85 90 80 30 60 12 100 90 65 80 100 100 100 50 13 100 95 100 100 100 100 90 14 100 100 100 100 100 100 100 50 15 25 35 15 30 80 25 20 0 16 100 85 70 75 90 90 50 17 100 100 100 100 100 100 100 18 90 85 85 85 90 95 70 40 20 40 60 10 60 100 100 100 50 21 35 60 10 60 100 100 80 60 22 95 95 35 100 100 100 90 50 23 100 100 40 100 100 100 90 50 24 100 75 100 60 - 100 100 60 25 95 95 90 95 100 100 95 35 34 50 40 0 35 50 70 30 50 37 20 60 0 30 30 50 50 50 38 25 50 0 25 25 50 20 20 52 0 60 50 50 10 50 - 20 53 0 50 0 50 50 50 - 30 54 90 75 60 50 50 80 - 80 A blank (-) indicates the weed was not tested. PreEmergence Multi'Weed Herbicide Test Several canpounds were evaluated at an application rate of 1 or 1/2 lb/acre (1.12 or 0.56 kg/ha) for pre-emergence activity against a larger nunber of weed species. Pre-Emergence Multi-Weed Herbicide Test Several compounds were evaluated at an application rate of 1 or 1/2 ib/acre (1.12 or 0.56 kg/ha) for pre-anergence activity against a larger number of weed species. The process wes generally similar to the pre-energence herbicide test described above except that only 150 or 75 milligrams of test com- pound 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 Branus tectorum (DB) annual ryegrass Lolium nultiflorun (ARG) Johnsongrass Sorghum halepense (JG) broadleaf signalgrass Brachiaria platyphylla (BSG) hemp sesbania Sesbania exaltata (SESB) sicklepod Cassia obtusifolia (SP) cocklebur Xanthium sp. (cB) The results of the test are shown in Tables IV and V. TABLE IV Pre-Emergence ltied Herbicide zest Application Rate - 1.12 kg/ha Cnpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNG CS 19 40 35 60 100 90 30 90 100 100 - 20 100 90 26 25 70 45 95 60 25 85 35 75 - 20 100 95 90 27 45 65 40 100 60 25 80 100 85 100 40 100 95 35 28 80 100 90 100 100 90 100 70 90 100 30 100 95 35 29 90 45 75 100 85 40 90 95 90 100 40 100 95 30 90 95 80 100 90 75 100 100 80 100 60 100 95 31 60 65 75 100 100 55 95 100 100 100 100 100 95 32 90 100 90 100 100 65 85 100 90 100 95 100 85 33 100 100 95 100 100 95 100 100 100 100 25 100 90 35 90 100 100 100 - 90 90 100 90 100 10 100 75 36 90 35 85 100 - 15 80 95 90 100 50 100 95 39 100 100 100 100 100 95 100 100 100 100 100 100 98 40 100 100 80 100 100 70 100 100 100 100 90 100 95 41 100 100 100 100 100 100 100 100 100 100 60 100 98 42 60 100 85 100 100 70 95 100 95 100 10 100 95 50 43 85 100 25 100 60 25 98 100 100 100 100 100 90 100 44 0 80 10 85 0 0 75 0 30 100 0 100 0 10 45 25 100 40 100 60 0 65 60 60 100 50 100 70 0 50 - 100 50 100 35 35 75 100 100 (-) = Not tested. TABLE V Pre-Emergence Mhlti-weed Herbicide Test Application Rate - 0.56 kg/ha Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNG CB 46 0 65 35 75 65 0 0 0 35 100 25 90 80 0 47 - 60 35 100 100 0 90 100 100 100 70 - 100 75 48 - 75 20 90 60 0 15 70 35 90 0 - 20 40 49 - 60 10 100 60 0 50 100 95 100 40 - 90 100 51 - 40 10 95 40 10 50 65 100 100 0 - 95 65 (-) - Not tested. Post-Emergence Multi-Weed Herbicide Zest: This test is con ducted 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-nergence 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-nergence multi-weed herbicide test are reported in Table VI and VII. TABLE VI Post:mergence Multi-Weed Berbic id al Activity Application Rate - 2.24 kg/ha Cmpd. ¯¯¯ DB FT ARG WG JG WD BSG AMG SESB VL SP MD YNG CB 19 100 90 65 100 100 98 100 100 100 100 60 100 70 100 26 60 75 60 95 45 50 90 50 90 100 40 90 60 27 80 70 65 95 100 90 100 100 100 100 85 100 75 28 80 100 75 90 85 80 100 80 80 100 30 100 85 85 29 85 70 55 90 98 90 100 100 100 100 35 100 60 100 30 90 80 40 90 85 80 80 70 100 100 20 100 40 31 100 80 20 100 100 100 100 100 100 100 100 100 85 32 70 90 60 100 100 98 100 100 100 100 100 100 60 33 95 100 80 100 90 100 100 100 100 100 70 100 40 35 70 90 40 100 - 100 100 100 100 100 98 100 30 36 85 100 35 100 - 20 100 100 100 100 100 100 15 39 100 100 85 100 100 100 100 100 100 100 100 100 90 100 40 100 100 30 100 100 100 100 100 100 100 90 100 75 41 100 100 35 90 70 100 90 100 100 100 50 100 70 42 45 100 50 100 70 55 80 100 100 100 70 100 75 100 43 25 80 15 98 35 0 20 100 100 100 100 100 60 95 44 0 15 0 65 0 0 0 70 100 100 40 100 0 100 45 0 75 35 70 35 0 60 50 85 100 50 100 75 70 50 - 40 0 75 45 40 60 100 100 95 30 - 60 100 (-) = Not tested. TABLE VII Post-Emergence Multi-Weed Herbicidal Activity Application Rate - 0.56 wha Onpd. . DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNG cB 46 25 35 20 50 35 35 0 20 75 100 35 95 - 50 47 - 75 25 90 40 25 80 100 100 100 80 - 75 100 48 - 50 35 80 35 40 0 75 100 85 15 - 50 75 49 - 35 0 75 30 0 20 100 100 100 80 - 25 85 51 - 35 0 80 35 20 70 50 95 95 25 - 65 50 (-) = Not tested. The compounds of the present invention are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the canpounds herein defined are formulated into herbicidal positions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, reccgnizing 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 powdery dusts, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. Preferred formulations for pre-emergence herbicidal applications are wettable powders, emulsifiable concentrates and granules. Ihese formulations may contain as little as about 0.5% 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 from about 0.05 to apprcximately 25 pounds per acre, preferably from about 0.1 to about 10 pounds per acre. Wettable powders are in the forum of finely divided particles which disperse readily in water or other dispersants. Ihe wettable powder is ultimately applied to 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. Wettable powders nornally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion. Emulsifiable concentrates are hcmogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aranatic naphthal, isophorone and other nonrvolatile organic solvents. Ebr 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 composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal ccmposition. Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, bentonite clays, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleun 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; polyhydric alcohols; and other types of surface-active agents, many of which are available in comr merce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal canposition. Dusts, which are free-flowing 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 toxicant 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 small 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 oompletely 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 phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid ocmpositions can be applied to the plant by the use of power-dusters, boan and hand sprayers and spray dusters. The ccmpositions can also be applied from 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 conpositions 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 canpositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxk ccmpositions 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 compositions into the soil as the water is absorbed therein. nust canpositions, granular canFositions 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 Ranges 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 sOdium lignosulfonate 7 100% attapulgite clay 12.5 100% EXTRUDED GRANULAR FORMULATIONS herbicidal compound 1-20 herbicidal compound 10 binding agent 0-10 lignin sulfonate 5 diluent(s) 70-99 calcium carbonate 85 100% 100% FLOWABLE FORMULATIONS 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 antifoan agent 0.1-1 silicone defoamer 0.02 solvent 7.95-77.85 water 39.9 100% 100% The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers and other herbicides, pesticides and the like, used as adjuvant or in canbination with any of the abcve-described adjuvants. Other phytotoxic compounds useful in canbina tion with the above-described compounds include, for example, anilides such as 2-benzothiazole-2-yloxy-N-methyl acetanilide, 2-chloro-2' ,6 '-di- methyl-N-(n-propylethyl) cetanilide, 2-chloro-2',6'-diethyl-N-(butoxymethyl) acetanilide; 2,4-dichlorophenoxyacetic acids, 2, 4,5-trichlorophen- oxyacetic acid, 2-methyl-4 -chloroFhenoxyacetic acid and the salts, esters and anides thereof; triazine derivatives, such as 2,4-bis(3-methoxypropyl- amino)-6-methylthio-s-triazine, 2-chloro-4-ethylamino-6-isopropylamino-striazine, and 2-ethylamino-4-isopropyl-amino-6-methyl-mercapto-s-triazine; urea derivatives, such as 3-(3, 5-dichloroFhenyl)-l,l-dimethylurea and 3-(p-chlorophenyl)-1,1-dimethylurea; and acetamides such as N,N-diallyl 6 -chloroacetamide, and the like; benzoic acids such as 3-anino-2,5-dichlorobenzoic acid; thiocarbanates such as S-(1,1-dimethylbenzyl)-piperi- dene-1-carnothioate, 3-(4-chlorophenyl)-methyl diethylcarbothioate, ethyl-1-hexahydro-1,4-azepine-1-carbothioate, S-ethyl-hexahydro-1H-aze pine-1 -carbothioate, Propyl N,N-dipropyl thiocarbanate, S-ethyl N,N-di propyl thiocarbanate, S-ethyl cyclohexylethylthiocarbanate and the like; anilines such as 4-(methylsulfonyl)-2,6-dinitro-N,N-substituted 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-o ne, (#)-butyl-2-[4-[(5-trifluoromethyl)-2-pyridinyl)oxy]- phenoxy]propanate, sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, 3-isopropyl-1H-2,1,3-benzothiadiazine-4(3H)-one-2,2-dioxide, and 4-amino-6-tert-butyl-3(methylthio)-as-triazin-5(4H)-one or 4-amino-6-(1,1dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one and S-(O,O-diisopropyl)-benzene sulfonanide. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additanents include materials in which plant organisns take root and grow such as canpost, manure, humus, sand, and the like.

Claims: WHAT IS CLAIMED IS: 1. A compound of the formula EMI24.1 wherein R is C1-C4 alkyl Optionally substituted with halogen; R1 is hydrogen or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl or EMI24.2 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) RbS3n- 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, with the proviso that R7 is not attached to the 6-position. 2. The compounds of Claim 1 wherein R is methyl or CF3; 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; R5 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) RbSOh- 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) S02NRCRd wherein Rc and Rd are as defined. 3. The compounds of Claim 2 wherein R7 and R8 are independently are hydrogen; chlorine; fluorine; bromine; methyl; methoxy; OCF3; cyano; nitro; trifluoranethyl; RbSOn- wherein n is the integer 2 and Rb is methyl, chioromethyl, trifluoromethyl, cyanomethyl, ethyl, or 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 SO2NRCRd wherein RC and are as defined and R7 is in the 3-position. 4. The compound of Claim 2 wherein R7 is hydrogen and R8 is hydrogen, chlorine, bramine, fluorine, CF3 or RbSO2 wherein Rb is C1-C4 alkyl. 5. The compound of Claim 2 wherein 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 CH3S02- 6. The copound of Claim 2 wherein 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 CH3SO2-. 7. The canpound of Claim 2 wherein 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 C2H2-. 8. The compound of Claim 2 wherein 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 CH3S02-. 9. The compound of Claim 2 wherein 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 methylthio. 10. The compound of Claim 2 wherein 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 cyano. 11. The compound of Claim 2 wherein 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 C2H5S02-. 12. The compound of Claim 2 wherein R is CF3; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is methyl; R6 is hydrogen; R7 is hydrogen; and R8 is bromine. 13. The compound of Claim 2 wherein R is methyl; R1 is hydrogen; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is 3-cyano; and R8 is hydrogen. 14. The compound of Claim 2 wherein R is CF3; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is methyl; R6 is hydrogen; R7 is hydrogen; and R8 is bromine. 15. The compound of Claim 2 wherein R is methyl; R1 is methyl; R2 is methyl; R3 is hydrogen; R4 is hydrogen; R5 is hydrogen; R6 is hydrogen; R7 is 3-nitro; and R8 is hydrogen. 16. The compounds of Claim 2 wherein R7 is hydrogen. 17. The compounds of Claim 3 wherein R7 is hydrogen. 18. The compound of Claim 1 wherein R1 and R2 are hydrogen or both methyl. 19. The compound of Claim 18 wherein R8 is -SO2CH3, -S02CH2C1, CF3, 5O2CH3, cyano, -SO2CH2Cl or -SO2H5. 20. The method of controlling undesirable vegetation comprising applying to the are where control is desired, an herbicidally effective amount of a compound fran Claims 1-19. 21. An herbicidal composition ccmprising an herbicidally active 2-(2-substituted benzoyl)-1 ,3-cyclohexanedione and an inert carrier therefor wherein the 2-benzoyl substituent is C1 -C4 alkyl optionally substituted with halogen. 22. The herbicidal composition of Claim 21 wherein the 2-(2-substituted benzDyl)-1,3-cyclohexanedione is a compound of Claims 1-19. 23. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidal cccaositon comprising an herbicidally active 2-(2-benzoyl)-1,3-cyclohexanedione and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with C1-C4 alkyl, optionally substituted wth halogen. 24. The method of Claim 23 wherein the 2-(2-benzoyl)-1,3- cyclohexanedione has a C1-C4 alkylsulfonyl or C1-C4 haloalkylsulfonyl substitution on the phenyl ring. 25. The method of Claim 24 wherein said alkylsulfonyl or haloalkylsulfonyl substitution is at the 4-position of the phenyl ring. 26. The herbicidal canposition of Claim 21 wherein the 2-(2 benzoyl)-l ,3-cyclohexanedione has a C1-C4 alkylsulfonyl or C1-C4 haloalkylsulfonyl substutition on the phenyl ring. 27. The herbicidal composition of Claim 25 wherein said alkylsulfonyl or haloalkylsulfonyl substitution is at the 4-position of the phenyl ring. 28. The method of Claim 23 wherein the 2-(2-benzoyl)-1,3-cyclo- hexanedione has a C1 -C4 haloalkyl substitution on the phenyl ring. 29. The method of Claim 28 wherein said haloalkyl substitution is at the 4-position on the phenyl ring. 30. The herbicidal composition of Claim 21 wherein the 2-(2 benzoyl)-1,3-cyclohexanedione has a C1-C4 haloalkyl substitution on the phenyl ring. 31. The herbicidal composition of Claim 30 wherein said haloalkyl substitution is at the 4-position of the phenyl ring. 32. The herbicidal canposition of Claim 30 wherein said haloalkyl is CF3. 33. The method of Claim 20 wherein R1 and R2 are hydrogen or both methyl. 34. The method of Claim 33 wherein R8 is -SO2cH3, -SO2CH2Cl, CF3, -SO2CH3, cyano, -SO2CH2Cl or -SO2C2H5. 35. The composition of matter of Claim 22 wherein R1 and R2 are hydrogen or both methyl. 36. The composition of matter of Claim 35 wherein R8 is -S02CH3, -SO2CH2Cl, CF3, -SO2CH3, cyano, -SO2CH2Cl or -SO2C2H5. 37. A process for preparing a compound of the formula EMI28.1 wherein R is C1-C4 alkyl, optionally substituted with halogen; R1 is hydrogen or C1-C4 alkyl; R2 is hydrogen, C1-C4 alkyl or EMI28.2 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) RbSOh- 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) SO2NRCi wherein RC 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 EMI29.1 wherein R1 through R6 are as defined with a substituted benzoyl reactant of the formula EMI29.2 wherein R, R7 and R8 are as defined and X is halogen, C1-C4 alkyl-C(O)-O-, C1 -C4 alkDxy-C(O)-O- or EMI29.3 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 fran an enol ester of the formula EMI29.4 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 from 0.01 mole to about 0.5 mole or higher of a cyanide source to form a canpound of the formula EMI29.5 wherein R1 through R8 are as defined above. 38. The process of Claim 37 wherein X is halogen, the moderate base is tri-C1-C6 alkyl & ine, 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-C5 aliphatic aldehydes; cyanohydrins, zinc cyanide; tri(lower alkyl) silyl cyanides or hydrogen cyanide. 39. The process of Claim 38 wherein X is chlorine, the moderate base is tri-C1-C6 alkylanine, pyridine, sodium carbonate or sodium phosphate and the cyanide source is potassium cyanide, acetone cyanohydrin or hydrogen cyanide.

Inventors: CARTER, CHARLES GARVIE
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1985
Main classification: C07C49
IPC codes: C07C317, C07C323, A01N37, C07C49, C07C315, A01N41, C07C253, C07C313, C07C45, C07C303, C07C205, C07C225, C07C67, C07C69, C07C301, C07C255, C07C311, A01N39, A01N35, C07C201, C07C213, A01N47