Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones

Abstract

Compounds of the formula ##STR1## wherein R.sup.60 is halogen, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, cyano, nitro, S(O).sub.n R wherein R is C.sub.1 -C.sub.4 alkyl and n is the integer 0, 1 or 2; and R.sup.61 through R.sup.66 are hydrogen or certain substituents, their salts, herbicidal compositions containing the compound or salts and the herbicidal use thereof.

Description

Applicants specifically incorporate by reference the contents of the above listed U.S. patent applications.

BACKGROUND OF THE INVENTION

Compounds having the structural formula ##STR2## wherein X can be alkyl, n can be 0, 1, or 2, and R.sub.1 can be phenyl or substituted phenyl are described in Japanese Patent Application No. 84632-1974 as being intermediates for the preparation of herbicidal compounds of the formula ##STR3## wherein R.sub.1, X, and n are as defined above and R.sub.2 is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R.sub.2 is allyl and R.sub.1 is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.

DESCRIPTION OF THE INVENTION

Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.

Embodiment G' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment G have the following structural formula ##STR4## wherein R.sup.60 is hydrogen; halogen; C.sub.1 -C.sub.2 alkyl, preferably methyl; C.sub.1 -C.sub.2 alkoxy, preferably methoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl, preferably trifluoromethyl; R.sup.a SO.sub.n - wherein n is 0 or 2, preferably 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably, R.sup.60 is chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and

R.sup.61 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl;

R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl; or

R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene;

R.sup.63 is C.sub.1 -C.sub.4 alkyl, preferably methyl;

R.sup.64 is C.sub.1 -C.sub.4 alkyl, preferably methyl; or

R.sup.63 and R.sup.64 together are C.sub.2 -C.sub.5 alkylene;

R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n - wherein n is the integer 0, 1 or 2, preferably 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl, preferably methyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl; (c) phenyl; or (d) benzyl; (10) -NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; (12) -SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; or (13) -N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined.

Preferably R.sup.65 is in the 3-position or 5-position. More preferably R.sup.65 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 thioalkyl. Preferably R.sup.66 is in the 4-position. Most preferably R.sup.66 is halogen, cyano, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl or C.sub.1 -C.sub.4 haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C.sub.1 -C.sub.4 haloalkyl" includes the alkyl groups defined above under C.sub.1 -C.sub.4 alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR5## wherein R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 and R.sup.66 are as defined above.

The circled proton on each of the for tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR6## wherein R.sup.6.spsp.0, R.sup.6.spsp.1, R.sup.6.spsp.2, R.sup.6.spsp.3, R.sup.6.spsp.4, R.sup.6.spsp.5 and R.sup.6.spsp.6 are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents and aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees os association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

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 comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of Embodiment G and G' of the present invention can be prepared by the following two-stop 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 reaction (1). ##STR7## wherein R.sup.60 through R.sup.66 and moderate base are as defined and X is halogen, preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)--O--, C.sub.1 -C.sub.4 alkoxy-C(O)--O-- or ##STR8## wherein R.sup.60, R.sup.65 and R.sup.66 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0.degree. C.-50.degree. C. until the reaction is substantially complete. ##STR9## wherein the moderate base and R.sup.60 through R.sup.66 are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50.degree. C., preferably about 20.degree. C. to about 40.degree. 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 amount 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 sodium 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 C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde, propionalidehyde, 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 base 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 40.degree. C. 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 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, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from 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 are useful in this process, depending on the nature of the acid halide 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, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50.degree. 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). ##STR10## wherein R.sup.60, R.sup.65 and R.sup.66 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 examples of the methods described therein. ##STR11## wherein R.sup.60, R.sup.65 and R.sup.66 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. ##STR12## wherein R.sup.60, R.sup.65 and R.sup.66 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. ##STR13## wherein R.sup.60, R.sup.65 and R.sup.66 are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The following example teaches the synthesis of a representative compound of Embodiment G and G' of this invention.

EXAMPLE 1-G,G'

2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione ##STR14##

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohyrdin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K.sub.2 CO.sub.3. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO.sub.4 and concentrated under vacuum, yielding 2.2 g of crude product.

The following are tables of certain selected compounds of Embodiment G' that are preparable according to the procedures described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

TABLE I-G__________________________________________________________________________ ##STR15##Comp. No. R.sup.60 R.sup.61 R.sup.62 R.sup.63 R.sup.64 R.sup.65 R.sup.66 m.p. .degree.C.__________________________________________________________________________ 1G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H 112-117 2G.sup.(a) NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl 76-82 3G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 176-179.degree. 4G CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.2 H.sub.5 gum 5G CF.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 viscous oil 6G NO.sub.2 CH.sub. 3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.2 Cl oil 7G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-F gum 8G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.2 H.sub.5 4-SO.sub.2 C.sub.2 H.sub.5 gum 9G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 gum10G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 gum11G CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-NO.sub.2 H gum12G I CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H gum13G OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum14G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OCH.sub.3 4-Br gum15G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 nC.sub.3 H.sub.7 gum16G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 N(CH.sub.3).sub.2 gum17G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CN 148-150.degree.18G SO.sub.2 CH.sub.3 CH.sub.3 CH.sub. 3 CH.sub.3 CH.sub.3 H H gum19G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 gum20G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum21G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCF.sub.3 gum22G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-OCF.sub.3 gum23G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-Cl 4-SO.sub.2 C.sub.2 H.sub.5 gum24G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-C(O)CH.sub.3 gum25G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2CH.sub.3 129-13126G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 89-9227G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 115-12528G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CN 87-95__________________________________________________________________________ .sup.(a) prepared in Example 1G,G'. TABLE I__________________________________________________________________________ ##STR16##Comp. No. R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 m.p. .degree.C.__________________________________________________________________________29 NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-F 115-11830 NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 119-12331 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SC.sub.2 H.sub.5 oil32 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SC.sub.3 H.sub.7 oil33 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-N(C.sub.2 H.sub.5)COCH.sub.3 4-NO.sub.2 oil34 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-SC.sub.2 H.sub.5 4-SO.sub.2 C.sub.2 H.sub.5 oil35 NO.sub.2 H H CH.sub.3 CH.sub.3 H H 145-14936 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum37 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H glass38 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H glass39 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 4-Cl 5-Cl glass40 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-Cl 5-Cl glass41 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CH.sub.3 76-7942 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H 60-6143 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 5-Br 100-10544 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-NO.sub.2 72-7545 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 5-NO.sub.2 103-10546 NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 5-CH.sub.3 136-13947 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.2 H.sub.5 4-SC.sub.3 H.sub.7 oil48 SCH.sub.3 CH.sub.3 CH.sub.3 CH.sub. 3 CH.sub.3 3-OC.sub.2 H.sub.5 4-SCH.sub.3 oil49 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.2 H.sub.4 OCH.sub.3 4-Br oil50 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.2 H.sub.5 4-SO.sub.2 C.sub.3 H.sub.7 oil51 SOCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OCH.sub.3 4-SOCH.sub.3 135-14252 NO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3 H H 108-11253 NO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 glass54 Cl C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 glass55 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 5-Cl 96-9856 NO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl glass57 Cl C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl glass58 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-Cl 4-Cl 105-11059 Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Br glass60 NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 5-Cl 125-12861 Br CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.3 H.sub.7 4-SC.sub.2 H.sub.5 oil62.sup.(b) NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H 80-8563.sup.(c) NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H oil64.sup.(d) NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-F oil__________________________________________________________________________ .sup.(b) As the sodium salt. .sup.(c) As the triethylammonium salt. .sup.(d) As the potassium salt.

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, seds of seven 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), annula morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea) 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.degree. to 80.degree. F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same 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 results of the tests are shown in the following Tables

TABLE II-G______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD YNS______________________________________ 1G 100 100 90 100 100 100 80 2G 100 100 90 100 100 100 80 3G 100 100 90 100 100 100 80 4G 100 100 90 100 100 100 80 5G 100 100 90 100 100 100 80 6G* 100 100 100 100 100 -- 20 7G 100 100 80 100 100 100 80 8G 85 100 80 100 100 100 80 9G 100 100 80 100 100 100 8010G 100 100 80 100 100 100 8011G 100 100 80 100 100 100 8012G 100 100 80 90 100 100 013G 100 100 70 100 100 100 014G 100 100 75 100 100 100 9015G 100 100 80 100 100 100 9016G 100 100 90 100 100 100 8017G 100 100 80 100 100 100 8018G 100 100 90 85 100 100 8019G 100 100 100 100 100 100 8020G 70 95 10 100 100 100 021G 100 100 100 100 100 100 8022G 100 100 90 100 100 100 8023G 100 100 100 100 100 100 8024G 0 80 0 25 80 70 025G 100 100 80 100 100 100 8026G 100 100 100 80 100 100 8027G 100 100 100 100 100 100 8028G 100 100 90 100 100 100 8029 100 100 100 100 100 100 8030 100 100 100 100 100 100 10031 100 100 100 100 100 100 8032 100 100 100 100 100 100 8033 100 100 85 40 100 100 6034 100 100 100 95 100 100 8047 100 100 100 100 100 100 8048 100 100 100 100 100 100 8049 100 100 100 100 100 100 8050 100 100 100 100 100 100 8051 100 100 100 100 100 100 8052 100 100 100 100 100 100 8053 100 100 100 100 100 100 10058 100 100 100 100 100 100 8060 100 100 100 100 100 100 8062 100 100 100 100 100 100 8063 100 100 100 100 100 100 8064 100 100 100 100 100 100 80______________________________________ A blank (--) indicates that the weed was not tested. *Tested at 0.56 kg/ha.

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 seven different weed species are 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 herbicide test are reported in Table III.

TABLE III-G______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD YNG______________________________________ 1G 100 95 90 90 100 100 80 2G 100 100 100 100 100 100 80 3G 100 100 95 100 100 100 90 4G 100 100 100 100 100 100 90 5G 100 100 100 100 100 100 100 6G* 10 80 50 75 40 -- 0 7G 70 75 70 90 90 80 80 8G 50 80 70 90 90 80 30 9G 70 80 70 90 90 80 3010G 75 80 70 80 60 50 7011G 70 80 70 80 80 80 8012G 100 75 90 75 80 80 8013G 60 70 70 100 100 100 8014G 20 70 40 60 80 80 7015G 90 70 70 75 80 90 7016G 50 70 80 60 80 90 7017G 90 60 70 65 80 80 8018G 30 50 80 95 95 80 7019G 100 100 95 90 100 100 8020G 10 40 5 70 80 90 7021G 95 90 95 95 100 100 7022G 80 90 90 80 100 100 7023G 90 80 80 80 90 80 3024G 0 30 0 40 80 20 025G 0 20 0 10 10 20 026G 80 70 70 80 80 80 7027G 90 90 90 80 80 90 6028G 70 65 50 80 80 80 7029 90 80 60 80 80 80 8030 90 80 80 80 80 80 8031 100 80 80 80 90 80 8032 90 80 80 80 80 80 3033 30 50 60 40 60 30 034 100 100 85 100 100 100 3047 100 100 100 100 100 100 6048 100 100 100 100 100 100 7049 100 100 100 100 100 100 6050 100 100 100 100 100 100 5051 100 100 100 100 100 100 3052 100 100 100 100 100 100 8053 100 100 100 100 100 100 8058 100 100 100 100 100 100 9060 100 90 90 90 100 100 8062 100 80 60 80 90 80 8063 90 80 60 80 90 80 8064 100 80 60 90 90 90 80______________________________________ A blank (--) indicates the weed was not tested. *Tested at 0.56 kg/ha.

Pre-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 0.25 lb/acre (0.275 kg/ha) for pre-emergence activity against a larger number of weed species.

The process was generally similar to the pre-emergence herbicide test described above except that only 37.5 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

Indian mustard (MD) was eliminated in this test and the following weed species were added:

______________________________________Grasses: annual ryegrass Lolium multiflorum (ARG) rox-orange sorghum Sorghum bicolor (SHC) broadleaf signalgrass Brachiaria platyphylla (BSG) hemp sesbania Sesbania exaltata (SESB) nightshade Solanum sp. (SP) cocklebur Xattiium sp. (CB)______________________________________

The results of this 0.275 kg/ha test are shown in Table IV-G.

POST-EMERGENCE MULTI-WEED HERBICIDE TEST

Several compounds were evaluated at an application rate of 0.25 lb/acre (0.275 kg/ha) for post-emergence activity against the larger number of weed species that are used in the pre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide test described above except that only 37.5 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

The results of this 0.275 kg/ha test are shown in Table V-G.

TABLE IV-G__________________________________________________________________________Pre-Emergence Multi-Weed Herbicidal ActivityApplication Rate - 0.275 kg/haCmpd.No. FT ARG WG SHC WO BSG AMG SESB VL SP YNS CB__________________________________________________________________________35 0 0 0 0 0 0 0 0 20 0 0 036 100 0 100 40 40 70 100 90 100 0 90 3537 100 80 100 100 100 90 100 100 100 50 100 10038 100 60 100 90 100 75 85 100 100 25 95 10039 95 100 100 90 100 50 100 100 100 20 10 10040 100 70 100 60 50 15 90 100 100 10 40 2041 95 0 70 25 0 0 95 70 75 25 75 7042 65 15 95 25 10 40 40 50 100 0 90 3043 100 20 85 100 100 70 100 100 100 0 90 10044 0 0 100 30 50 20 75 100 100 0 20 1045 50 0 0 10 0 0 80 0 100 0 15 4046 100 10 100 75 0 30 100 100 100 0 100 10054 5 40 100 40 30 90 98 90 100 0 50 1055 25 5 100 95 80 85 100 60 100 0 80 2056 98 20 95 90 60 50 90 20 100 0 70 3057 0 0 90 75 5 10 80 20 100 0 10 20__________________________________________________________________________ (--) = Not Tested. TABLE VI-A__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate - 0.25 kg/haCmpd.No. FT ARG WG SHC WO BSG AMG SESB VL SP YNS CB__________________________________________________________________________35 0 0 15 0 10 0 0 20 35 0 0 036 100 0 85 35 35 85 100 100 100 25 35 10037 90 15 90 25 90 85 100 85 100 60 40 10038 100 20 70 30 60 70 95 90 95 10 70 10039 40 80 90 25 95 90 100 90 80 35 35 --40 60 70 90 15 75 70 75 85 50 10 50 7541 80 0 90 0 0 35 80 75 75 50 30 8542 30 0 75 25 10 25 75 90 90 10 40 7543 90 0 98 35 95 95 100 100 95 20 20 10044 10 0 25 10 15 0 10 30 20 10 0 045 40 0 60 25 0 0 40 30 15 0 0 1046 100 0 95 10 0 0 85 95 100 0 95 --54 80 15 75 25 75 85 90 95 90 20 30 9055 95 5 80 25 90 85 95 100 100 0 50 10056 100 10 95 50 90 75 100 95 100 50 30 --57 80 0 50 10 0 10 80 100 100 10 15 60__________________________________________________________________________ (--) = Not Tested.

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recogizing 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 or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight 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 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 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 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 normally 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 homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile 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 composition is to be appoied, 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 relatively coarse particles, are usually applied witout dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, 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 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typically wetting, dispersing or emulsifying agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The sufface-active agent, when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredients 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 are to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided 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 can be applied to the plants in the convenient 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 from airplanes as a dust or a spray or by rope wick applications 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 can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at lest 1/2 inch below the soil surface. It is not necessary that the phytotoxic composition be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions 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. Dust compositions, granular compositions 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. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

__________________________________________________________________________General Formula with Ranges Specific Formula__________________________________________________________________________EMULSIFIABLE CONCENTRATE FORMULATIONSHerbicidal compound 5-55 herbicidal compound 24surfactant(s) 5-25 proprietary blend of oil- 10solvent(s) 20-90 soluble sulfonates and 100% polyoxyethylene ethers polar solvent 27 petroleum hydrocarbon 39 100%WETTABLE POWDER FORMULATIONSherbicidal compound 3-90 herbicidal compound 80wetting agent 0.5-2 sodium dialkyl naphthalene 0.5dispersing agent 1-8 sulfonatediluent(s) 8.5-87 sodium lignosulfonate 7 100% attapulgite clay 12.5 100%EXTRUDED GRANULAR FORMULATIONSherbicidal compound 1-20 herbicidal compound 10binding agent 0-10 lignin sulfonate 5diluent(s) 70-99 calcium carbonate 85 100% 100%FLOWABLE FORMULATIONSherbicidal compound 20-70 herbicidal compound 45surfactant(s) 1-10 polyoxyethylene ether 5suspending agent(s) 0.05-1 attagel 0.05antifreeze agent 1-10 propylene glycol 10antimicrobial agent 1-10 1,2-benzisothiazoline-3-one 0.03antifoam agent 0.1-1 silicone defoamer 0.02solvent 7.95-77.85 water 39.9 100% 100%__________________________________________________________________________

When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate.

Claims

1. Compounds of the formula ##STR17## wherein R.sup.60 is hydrogen; halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl; or R.sup.a SO.sub.n - wherein n is 0 to 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;

R.sup.61 is hydrogen or C.sub.1 -C.sub.4 alkyl;

R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl; or

R.sup.61 and R.sup.62 together are R.sub.2 -C.sub.5 alkylene;

R.sup.63 is C.sub.1 -C.sub.4 alkyl;

R.sup.64 is C.sub.1 -C.sub.4 alkyl; or

R.sup.63 and R.sup.64 together are C.sub.2 -C.sub.5 alkylene;

R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n - wherein n is the integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) -SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; and (13) -N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined and their salts.

2. The compounds of claim 1 wherein R.sup.60 is chlorine, hydrogen, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R.sup.61, R.sup.62, R.sup.63 and R.sup.64 are methyl; R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n - wherein n is the integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; or (13) -N-(R.sup.c)C(O)R.sup.d are as defined.

3. The compounds of claim 2 wherein R.sup.65 and R.sup.66 are independently are hydrogen; chlorine; fluorine; bromine; methyl; C.sub.1 -C.sub.4 alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R.sup.b SO.sub.n - wherein n is the integer 0 or 2 and R.sup.b is methyl, chloromethyl, trifluoromethyl; ethyl or n-propyl, R.sup.e C(O)- where R.sup.e is C.sub.1 -C.sub.4 alkyl; or SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined and R.sup.65 is in the 3-position or 5-position and R.sup.66 is in the 4-position.

4. The compounds of claim 2 wherein R.sup.65 is hydrogen and R.sup.66 is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl.

5. The compound of claim 2 wherein R.sup.60 is nitro, R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is hydrogen.

6. The compound of claim 2 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is 4-chlorine.

7. The compound of claim 2 wherein R.sup.60 is chlorine; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 CH.sub.3.

8. The compound of claim 2 wherein R.sup.60 is methyl; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 C.sub.2 H.sub.5.

9. The compound of claim 2 wherein R.sup.60 is trifluoromethyl; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-trifluoromethyl.

10. The compound of claim 2 wherein R.sup.60 is nitro, R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 CH.sub.3.

11. The compound of claim 2 wherein R.sup.60 is hydrogen; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.6 is 4-trifluoromethylthio.

12. The compound of claim 2 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-cyano.

13. The compound of claim 2 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 -n-C.sub.3 H.sub.7.

14. The compound of claim 2 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is 4-trifluoromethyl.

15. The compound of claim 2 wherein R.sup.60 is chlorine; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is 3-ethoxy; and R.sup.66 is 4-SO.sub.2 CH.sub.2 CH.sub.3.

16. The compounds of claim 2 wherein R.sup.65 is hydrogen.

17. The compounds of claim 3 wherein R.sup.65 is hydrogen.

18. An herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione compound of the formula ##STR18## wherein R.sup.60 is hydrogen; halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; cyano; C.sub.1 -C.sub.2 haloalkyl; or R.sup.a SO.sub.n - wherein n is 0 or 2 and R.sup.a is nitro; alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoro-C.sub.1 -C.sub.2 methoxy;

R.sup.61 is hydrogen or C.sub.1 -C.sub.4 alkyl;

R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl; or

R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene;

R.sup.63 is C.sub.1 -C.sub.4 alkyl;

R.sup.64 is C.sub.1 -C.sub.4 alkyl; or

R.sup.63 and R.sup.64 together are C.sub.2 -C.sub.5 alkylene;

R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n - wherein n is the integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) -SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; and (13) -N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined and their salts and an inert carrier therefor.

19. The composition of claim 18 wherein R.sup.60 is hydrogen, chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R.sup.61, R.sup.62, R.sup.63 and R.sup.64 are methyl; R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n - wherein m is the integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; or (13) -N-(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined.

20. The composition of claim 19 wherein R.sup.65 and R.sup.66 are independently are hydrogen; chlorine; fluorine; bromine; methyl; C.sub.1 -C.sub.4 alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R.sup.b SO.sub.n - wherein n is the integer 0 or 2 and R.sup.b is methyl, chloromethyl, trifluoromethyl, ethyl, or n-propyl; R.sup.e C(O)- where R.sup.e is C.sub.1 -C.sub.4 alkyl; or SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined and R.sup.65 is in the 3-position or 5-position and R.sup.66 is in the 4-position.

21. The composition of claim 19 wherein R.sup.65 is hydrogen and R.sup.66 is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl.

22. The composition of claim 19 wherein R.sup.60 is nitro, R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is hydrogen.

23. The composition of claim 19 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is 4-chlorine.

24. The composition of claim 19 wherein R.sup.60 is chlorine; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 CH.sub.3.

25. The composition of claim 19 wherein R.sup.60 is methyl; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 C.sub.2 H.sub.5.

26. The composition of claim 19 wherein R.sup.60 is trifluoromethyl; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-trifluoromethyl.

27. The composition of claim 19 wherein R.sup.60 is nitro, R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 CH.sub.3.

28. The composition of claim 19 wherein R.sup.60 is hydrogen; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is 4-trifluoromethylthio.

29. The composition of claim 19 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-cyano.

30. The composition of claim 19 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen and R.sup.66 is 4-SO.sub.2 -n-C.sub.3 H.sub.7.

31. The composition of claim 19 wherein R.sup.60 is nitro; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is hydrogen; and R.sup.66 is 4-trifluoromethyl.

32. The composition of claim 19 wherein R.sup.60 is chlorine; R.sup.61 is methyl; R.sup.62 is methyl; R.sup.63 is methyl; R.sup.64 is methyl; R.sup.65 is 3-ethoxy; and R.sup.66 is 4-SO.sub.2 CH.sub.2 CH.sub.3.

33. The compositions of claim 19 wherein R.sup.65 is hydrogen.

34. The compositions of claim 20 wherein R.sup.65 is hydrogen.

35. Compounds of the formula ##STR19## wherein R.sup.60 is hydrogen; halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl; or R.sup.a SO.sub.n - wherein n is 0 or 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;

R.sup.61 is hydrogen or C.sub.1 -C.sub.4 alkyl;

R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl; or

R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene;

R.sup.63 is C.sub.1 -C.sub.4 alkyl;

R.sup.64 is C.sub.1 -C.sub.4 alkyl; or

R.sup.63 and R.sup.64 together are C.sub.2 -C.sub.5 alkylene;

R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n - wherein n is the integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) -NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) -SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; and (13) -N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined.