WO1991013548A1 - Herbicidal compositions of aroylated 1,3-dicarbonyl or 1,3,5-tricarbonyl cyclohexane herbicides and an antidote system therefor - Google Patents

Abstract

A post-emergence herbicide and antidote herbicidal composition comprising: a) a herbicidally effective amount of an aroylated 1,3,5-cyclohexanetrione compound or an aroylated cyclic 1,3-dicarbonyl compound; and, b) a non-phytotoxic antidotally effective amount of a derivative of 1,8-naphthalic dicarboxylic acid selected from the group consisting of 1,8-naphthalic anhydride, derivatives of 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, derivatives of 1,8-naphthalic dicarboxylic acid, salts thereof and combinations thereof.

Description

HERBICIDAL COMPOSITIONS OF AROYLATED

1,3-DlCARBONYL OR 1,3,5-TRICARBONYL CYCLOHEXANE HERBICIDES

AND AN ANTIDOTE SYSTEM THEREFOR

Field of the Invention

This invention relates to an herbicide and antidote composition and methods of use. More particularly, this invention relates to and describes for the first time certain post-emergent herbicidal compositions comprising substituted aroylated 1,3-dicarbonyl compounds and 1,3,5- tricarbonyl cyclohexane compounds as the herbicides and an antidote in combination therewith which is a derivative of 1,8-naphthalic dicarboxylic acid selected from the group comprising a 1,8-naphthalic anhydride, substituted 1,8- naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, substituted 1,8-naphthalic dicarboxylic acid, salts, esters, and combinations thereof.

Background of the Invention

An herbicide is a compound which adversely controls or modifies plant growth, e.g., killing, retarding, defoliating, desiccating, regulating, stunting, tillering, stimulating and dwarfing. The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. "Plant growth" includes all phases of development from seed germination to natural or induced cessation of life.

Herbicides are generally used to control or eradicate weed pests. They have gained a high degree of commercial success because it has been shown that such control can increase crop yield and reduce harvesting costs.

The most popular methods of herbicide application include: pre-plant incorporation into the soil; pre-emergence surface treatment on seeded soil after seeding;

post-emergence treatment of the plants and soil; and preemergence surface treatment before planting. A manufacturer of an herbicide generally recommends a range of application rates and concentrations calculated to maximize weed control. The range of rates varies from approximately 0.01 to 50 pounds per acre [0.0112 to 56 kilograms per hectare (kg/ha)], and is usually in the range of from 0.1 to 25 pounds per acre (0.112 to 28 kg/ha). The term "herbicidally effective amount" describes an amount of an herbicide compound which adversely controls or modifies plant growth. The actual amount used depends upon several considerations, including particular weed susceptibility, growth stage of weeds, soil and climatic conditions, and overall cost limitations.

An important factor influencing the usefulness of a given herbicide is its selectivity toward crops. In some cases, a beneficial crop is susceptible to the effects of the herbicide. In addition, certain herbicidal compounds are phytotoxic to some weed species but not to others. To be effective, an herbicide must cause minimal damage (preferably no damage) to the beneficial crop while maximizing damage to weed species which infest the locus of the crop.

To preserve the beneficial aspects of herbicide use and to minimize crop damage, many herbicide antidotes have been prepared. These antidotes reduce or eliminate damage to the crop without substantially impairing the damaging effect of the herbicide on weed species. See, for example, U.S. Patents 4,021,224, 4,021,229 and 4,230,874.

The precise mechanism by which an antidote reduces herbicidal crop injury has not been established. An antidote compound may be a remedy, interferent, protectant, or antagonist. As used herein, "antidote" describes a compound which has the effect of establishing herbicide selectivity, i.e., continued herbicidal phytotoxicity to weed species by the herbicide, and reduce phytotoxicity or be non-phytotoxic to the cultivated crop species. The term "antidotally effective amount" describes an amount of an antidote compound which counteracts to some degree a phytotoxic response of a beneficial crop to an herbicide.

Certain aroylated 1,3-dicarbonyl compounds and certain 2-benzoyl-1,3,5-cyclohexanetrione compounds have been found to be very effective herbicides with broad general herbicidal activity against a wide range of plant species. The method of controlling vegetation with the compounds comprises applying an herbicidally effective amount of the compounds, usually with an inert carrier, to the area where herbicidal control is desired. However, the herbicidal aroylated 1,3-dicaabonyl and 1,3,5-cyclohexanetrione compounds have been found in some instances to adversely affect or interfere with the growth of a variety of crops. Therefore, the effective use of these herbicides is further enhanced by, and requires in many instances, the addition of an antidotally effective amount of an antidote compound, said antidote being antidotally effective with the herbicide.

Previous attempts to antidote aroylated 1,3-dicarbonyl herbicides have been tried using an individual or single amide of haloalkanoic acid antidote as a pre-emergence treatment, as described in U.S. Serial No. 07/208,269, filed June 22, 1988. A previous attempt to antidote aroylated 1 , 3 , 5-tricarbonyl cyclohexane herbicides with an individual or single antidote has been tried as described in U.S. Serial No. 07/206,050, filed June 17, 1988.

The present invention provides for an herbicide antidote composition which reduces or eliminates injury.

Description of the Invention

It has now been discovered that certain compounds, when used in compositions in antidotally effective amounts as a post-emergence treatment, are effective antidotes for the continued protection of crops from adverse herbicidal injury or the reduction of adverse herbicidal injury caused by the use of an herbicidally effective amount of an aroylated 1,3-dicarbonyl-containing herbicidal compound or

1,3,5-tricarbonyl cyclohexane herbicidal compound.

Description of the Herbicide Compounds

Aroylated cyclohexanetrione-1,3,5 herbicide compounds of this invention are contained within and correspond to the following general formula

in which R is a group as hereinafter defined (and may generally be an optionally substituted aromatic moiety) and R ¹, R ², R³ and R⁴ are as hereinafter defined. Compounds of this type have been described in a number of references as being useful, for instance, as chemical intermediates and/or pesticides. The undefined remainder of the molecule represented in Formula A, which includes the tricarbonyl group, has a generally cyclical structure. In particular, this cyclical structure is the cyclical 6-member 1,3,5-tricarbonylcyclohexyl group.

Aroylated cyclohexane 1,3, 5-tricarbonyl compounds of this type have the general structure

wherein R is hydrogen; halogen; C₁-C₂ alkyl, C₁-C₂ alkoxy, nitro; cyano; C₁-C₂ haloalkyl; R_aSO_n - wherein n is 0 or 2 and R_a is C₁-C₂ alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;

R¹ is hydrogen or C₁-C₄ alkyl;

R² is hydrogen or C₁-C₄ alkyl; or

R¹ and R² together are C₂-C₅ alkylene;

R³ is C₁-C₄ alkyl;

R⁴ is C₁-C₄ alkyl; or

R³ and R⁴ together are C₂-C₅ alkylene;

R⁵ and R⁶ independently are (1) hydrogen; (2) halogen; (3) C₁-C₄ thioalkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl;

(9) R_bSO_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_eC(O)- wherein R _eis C₁-C₄ alkyl or C₁-C₄ alkoxy; (12) -SO₂NR_c R_d wherein R_c and R_d are as defined; or (13) -N(R_c )C(O)R_d where R_c and R_d are as defined.

Compounds of particular interest are those in which R⁵ is in the 3-posιtιon. In such compounds R⁵ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁-C₄ alkoxy or C₁-C₄ thioalkyl. Also of particular interest are compounds in which R₆ is in the 4-position, wherein R⁶ is halogen, cyano, trifluoromethyl, or R_bSO₂ wherein R_b is C₁-C₄ alkyl, such as methyl, or C₁-C₄ haloalkyl, such as chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁-C₄ 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 term "C₁-C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec- butoxy, isobutoxy and t-butoxy. The term "C₁-C₄ haloalkyl" includes the alkyl groups defined above under C₁-C₄ alkyl in which one or more hydrogen 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. Those skilled in the art will recognize in considering the salts of this invention, that varying degrees of 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 tricarbonylcyclohexane herbicide 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 or their salts to the area where control is desired.

Compounds of this type, with various substituents on either or both of the cyclohexane or phenyl rings, are disclosed in the following copending United States patent application, commonly assigned Serial No. 07/634,408, filed July 31, 1984.

The following is a list of sample compounds as found within the above description of active herbicides.

The aroylated 1,3-dicarbonyl herbicide compounds of this invention are contained within and correspond to the following general formula

in which R is a group as hereinafter defined (and may generally be an optionally substituted aromatic moiety). Compounds of this type have been described in a number of references as being useful, for instance, as chemical intermediates and/or pesticides. The undefined remainder of the molecule represented in Formula B, which includes the dicar- bonyl group, has a generally cyclical structure. In particular, the cyclical structure which is the cyclical 1,3-dicarbonyl group including a 5- to 6-member ring, which may be carbocyclic or heterocyclic which may be further optionally substituted with one or more aromatic groups, alkyl groups, alkyl-S(O)_n groups, OR(R=H, alkyl) groups and others to be described hereinafter.

Aroylated carbocyclic 1,3-dicarbonyl compounds of this type have the general structure

in which R is an optionally substituted aromatic moiety as hereinafter defined and n is 2 or 3, preferably 3. The ring can be saturated (all X and Y groups are hydrogen), or one or more hydrogen atoms may be replaced by aliphatic, aromatic, heterocyclic or alkylene groups, particularly hydrocarbyl groups. Examples of such hydrocarbyl groups are alkyl, particularly lower alkyl, phenyl, and C₂-C₅ alkylene groups such as dimethylene, trimethylene and the like, in which case the compounds have a spiro structure. The carbocyclic ring may be saturated or unsaturated, containing an olefinic bond linking the 4- and 5-carbon atoms.

Aroylated heterocyclic 1,3-dicarbonyl herbicide compounds of this invention have the general formula

in which R is as defined herein and Z is a chain which contains 2 or 3 ring atoms, at least one of which is nitrogen, oxygen or sulfur. Nitrogen atoms in such rings may be unsubstituted or may be substituted by a C₁-C₄ alkyl group. Carbon atoms in such rings may be unsubstituted or may be substituted similarly to those in the carbocyclic compounds described above. Where possible, heterocyclic rings may be saturated or unsaturated.

Examples of heterocyclic 1,3-dicarbonyl structures include, for instance, barbituric acid derivatives, hydroxy- pyrones, 3,5-dioxotetrahydropyrans and -thiopyrans, cyclical oxolactones, cyclical oxothiolactones and oxolactams.

One particular class of herbicide compounds is that in which the dicarbonyl compound is an optionally substituted cyclohexanedione and the aroylating group is a substituted benzoyl moiety. That is, R in Formula C above is substituted phenyl. In general, these compounds have the formula

in which R¹, R², R³, R⁴, R⁵ and R⁶ are independently hydrogen or C₁-C₄ alkyl or

O

R ¹ or R³ is R_aOC- in which

R_a is C₁-C₄ alkyl; phenyl, optionally substituted by from 2 to 5 methyl groups; or R ³ is hydroxyl and R¹,

R² , R⁴ , R⁵ and R⁶ are independently hydrogen or C₁-C₄ alkyl; or in which R¹ and R² , or R³ and R⁴ , taken together are C₂-C₅ alkylene (such compounds have a spiro structure;

R⁷ is halogen (chlorine, bromine, iodine or fluorine) ; cyano; C₁-C₄ alkyl; C₁-C₄ haloalkyl; R_kSO_n in which

R_k is C₁-C₄ alkyl and n = 0, 1 or 2; C₁-C₄ alkoxy; or nitro;

R⁸, R⁹ and R¹⁰ independently are hydrogen or substituents including halogen; C₁-C₄ alkyl; C₁-C₄ alkoxy, trifluoromethoxy; cyano; nitro; C₁-C₄ haloalkyl; C₁-C₄ alkylthio; phenoxy; or substituted phenoxy in which the substituent is halogen or halomethyl or both;

R_b S(O)_n in which n is 0, 1 or 2; and R_b is C₁-C₄ alkyl, C₁-C₄ haloalkyl, phenyl or benzyl,

O

R_CCNH- in which R_c is C₁-C₄ alkyl;

-NR_dR_e in which R_d and R_e independently are hydrogen or C₁-C₄ alkyl;

R_fC(O)- in which R_f is hydrogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₁-C₄ alkoxy;

SO₂NR_g R_h in which R_g and R_h independently are hydrogen or C₁-C₄ alkyl;

or R⁸ and R⁹ taken together form a ring structure with two adjacent carbon atoms of the phenyl ring to which they are attached.

Compounds of this type, with various substituents on either or both of the cyclohexane or phenyl rings are disclosed in: European Patent Application, Publication No. 90262; the following commonly assigned European patent applications, Publication Nos. 186 118, 186 119 and 186 120 (all relating to compounds which are herbicidal); and Japanese Patent Applications (Publication Nos.) 51/13750 and 51/13755 of Nippon Soda K.K., which disclose some compounds of this type as intermediates for herbicides. The disclosures of these documents are hereby incorporated herein by reference.

Some specific types of such aroylated heterocyclic 1,3-dicarbonyl herbicide compounds include:

barbituric acid derivatives such as those of the formula

in which R ¹⁸ and R¹⁹ are hydrogen or C₁-C₄ alkyl and R is substituted phenyl such as

in which R¹⁵ , R¹⁶ and R¹⁷ are as defined hereinafter. Such compounds are described, for instance, in commonly assigned U.S. Patent 4,797,147, issued January 10, 1989, the disclosure of which is hereby incorporated herein by reference;

oxolactams such as those having the formula

in which R¹¹-R¹⁴ and R²⁰ are independently hydrogen or C₁-C₄ alkyl, or R ¹¹ and R¹² together are C₂-C₅ alkylene, t is 0 or

1 and R is substituted phenyl such as

in which R ¹⁵ is halogen; C₁-C₂ alkyl; C₁-C₂ alkoxy; nitro; cyano; C₁-C₂ haloalkyl; or R_mSO_n wherein R_m is C₁-C₂ alkyl and n is 0, 1 or 2; trifluoromethyl or difluoromethyl; or tπfluoromethoxy or difluoromethoxy. Preferably R ¹⁵ is chlorine, bromine, C₁-C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁-C₂ alkylthio or C₁-C₂ alkylsulfonyl; and R^{1 6} and R^{1 7} independently are (1) hydrogen, (2) halogen,

(3) C₁-C₄ alkyl, (4) C₁-C₄ alkoxy, (5) trifluoromethoxy, (6) cyano, (7) nitro, (8) C₁-C₄ haloalkyl, (9) R_bSO_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. Such compounds are disclosed, for instance, in commonly assigned U.S. Pat. 4,808,720, issued February 28, 1989, the disclosure of which is hereby incorporated by reference;

herbicidal oxolactones and oxothiolactones within this invention such as those having the formula

in which R²¹-R²⁴ are independently hydrogen or C₁-C₄ alkyl; or R ²¹ and R²² together are C₂-C₅ alkylene; or R²³ and R²⁴ together are C₂-C₅ alkyl; or R ²¹ and R²³ together form a bond, and R is substituted phenyl such as

in which R¹⁵-R¹⁷ are as defined above; and W is oxygen or sulfur. When R ²¹ and R²³ together form a bond, the compounds contain an unsaturated heterocyclic ring. Such compounds are disclosed, for instance, in commonly assigned U.S. Pat.

4,741,755, issued May 3, 1988, the disclosure of which is hereby incorporated by reference herewith;

dioxotetrahydropyrans and -thiopyrans such as those having the formula

in which R^{2 6} -R^{2 9} are independently hydrogen or C₁-C₄ alkyl or

R ²⁶ and R²⁷ together are C₂-C₅ alkylene, or R²⁸ and R²⁹ together are C₂-C₅ alkylene; W ² is oxygen, sulfur or sulfonyl and R ³⁰ is substituted phenyl such as

in which R ¹⁵-R¹⁷ are as previously defined. Such compounds are described, for instance, in commonly assigned U.S. Pat.

4,728,745, issued March 1, 1988.

Another embodiment of this invention is an herbicidal composition comprising a 2-(2-substituted benzoyl)-4- substituted or unsubstituted phenyl) cyclohexanedione and an antidote with an inert carrier therefor. The 1,3-cyclohex- anedione moiety is preferably substituted with groups hereinafter defined. The benzoyl and cyclohexanedione moieties can be further substituted. Within the scope of this embodiment are compounds in which R in Formula C above is a substituted phenyl. In general, these compounds have the formula

wherein

R¹³⁰ is halogen; C₁-C₂ alkyl; C₁-C₂ alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C₁-C₂ haloalkyl; R_aSO_n- wherein n is 0 or 2; and R_a is C₁-C₂ alkyl;

trifluoromethyl or difluoromethyl. Of particular interest are compounds in which R¹⁴⁰ is chlorine, bromine, C₁-C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁-C₂ alkylthio or C₁-C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R ¹³¹ is hydrogen or C₁-C₄ alkyl;

R ¹³² is hydrogen or C₁-C₄ alkyl; or

R ¹³¹ and R ¹³² together are C₂-C₅ alkylene; R ¹³³ is hydrogen or C₁-C₄ alkyl;

R ¹³⁴ is hydrogen or C₁-C₄ alkyl; or

R ¹³³ and R¹³⁴ together are C₂-C₅ alkylene;

R¹³⁵, R¹³⁶, R¹³⁷ and R¹³⁸ independently are (1) hydrogen; (2) chlorine, fluorine or bromine; (3) C₁-C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl; (9) R_bSO_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; (12) -SO₂NR_c R_d wherein R_c and R_d are as defined; or (13) -N(R_c )C(O)R_d wherein R_c and R_d are as defined; and

R¹³⁹ is hydrogen or C₁-C₄ alkyl.

Preferably R¹³⁵ is in the 3-position and R¹³⁵ and R¹³⁷ are hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁-C₄ alkoxy or C₁-C₄ thioalkyl; or R¹³⁵ and R¹³⁷ are hydrogen and R¹³⁶ and R¹³⁸ are in the 4-position, wherein

R¹³⁶ and R¹³⁸ are halogen, cyano, trifluoromethyl, or R_bSO₂ wherein R_b is C₁-C₄ alkyl or C₁-C₄ haloalkyl.

Compounds of this type are described in commonly assigned U.S. Pat. 4,795,488, issued January 3, 1989.

Another embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-(substituted benzoyl)-cyclohexanedione-1,3 and the aroylating group is a substituted benzoyl moiety and an antidote with an inert carrier therefor. The 4- and 6-positions of the cyclohexanedione-1,3 moiety are preferably substituted with groups hereinafter defined, most preferably with hydrogen or methyl groups. The substituted benzoyl and cyclohexane- dione-1,3 moieties can be further substituted.

Within the scope of this embodiment are the compounds in which R in Formula C above is a substituted phenyl. In general, these compounds have the formula:

wherein

R⁴⁰ is halogen; C₁-C₂ alkyl; C₁-C₂ alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C₁-C₂ haloalkyl; R_aSO_n- wherein n is 0 or 2; and R_a is C₁-C₂ alkyl; trifluoromethyl; or difluoromethyl;

R⁴¹ is hydrogen or C₁-C₄ alkyl;

R⁴² is hydrogen or C₁-C₄ alkyl; or

R⁴¹ and R⁴² together are C₂-C₅ alkylene;

R⁴³ is hydrogen or C₁-C₄ alkyl;

R⁴⁴ is hydrogen or C₁-C₄ alkyl; or

R⁴³ and R⁴⁴ together are C₂-C₅ alkylene;

R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ independently are (1) hydrogen; (2) halogen selected from the group consisting of chlorine, fluorine or bromine; (3) C₁-C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl; (9) R_bSO_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_cR_d wherein R_c and R_d independently are hydrogen or C₁-C₄ alkyl; (11) R_eC(O)- wherein R_e is C₁-C₄ alkyl or C₁-C₄ alkoxy; (12) -SO₂NR_cR_d wherein R_c and R_d are as defined; or (13) -N(R_c)C(O)R_d wherein R_c and R_d are as defined; and

R⁴⁹ is hydrogen or C₁-C₄ alkyl. Of particular interest are compounds in which R⁴⁵ is in the 3-positιon and R⁴⁵ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁-C₄ alkoxy or C₁-C₄ thioalkyl; or

R⁴⁵ is hydrogen; or R⁴⁶ is in the 4-position and R⁴⁶ is halogen, cyano, trifluoromethyl, or R_bSO₂ wherein R_b is C₁-C₄ alkyl, preferably methyl or C₁-C₄ haloalkyl, difluoromethyl or trifluoromethyl.

Compounds of this are described in commonly

assigned U.S. Pat. 4,767,447, issued August 30, 1988.

Another embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-(2-substituted benzoyl)-4-(substituted oxy or substituted thio)-1,3-cyclohexanedione and an antidote with an inert carrier therefor. The 5- and 6-positions of the 1,3-cyclo- hexanedione moiety are preferably substituted with groups hereinafter defined, most preferably with hydrogen or methyl groups. The substituted benzoyl and cyclohexanedione moieties can be further substituted.

Within the scope of this embodiment are compounds having the following structural formula

in which

X is oxy, thio, sulfinyl or sulfonyl;

R⁵⁰ is halogen; C₁-C₂ alkyl; C₁-C₂ alkoxy, preferably methoxy; trifluoromethoxy; difluoromethoxy; nitro;

cyano; C₁-C₂ haloalkyl; R_aSO_n- wherein n is 0 or 2, preferably 2 and R_a is C₁-C₂ alkyl; trifluoromethyl or difluoro- methyl. Preferably R⁵⁰ is chlorine, bromine, C₁-C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁-C₂ alkylthio or C₁-C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R⁵¹ is hydrogen; C₁-C₄ alkyl, phenyl or substituted phenyl;

R⁵¹ is hydrogen or C₁-C₄ alkyl; or

R⁵¹ and R⁵² together are C₂-C₅ alkylene;

R⁵³ is hydrogen, C₁-C₄ alkyl, phenyl or substituted phenyl with the proviso that R⁵¹ and R⁵³ are not both phenyl or substituted phenyl;

R⁵⁴ is hydrogen or C₁-C₄ alkyl;

R⁵⁵ is hydrogen or C₁-C₄ alkyl; or

R⁵⁶ is C₁-C₄ alkyl, C₁-C₄ haloalkyl or phenyl; and R⁵⁷ and R⁵⁸ independently are (1) hydrogen; (2) halogen; (3) C₁-C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl; (9) R_bSO_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_cR_d wherein R_c and R_d independently are hydrogen or C₁-C₄ alkyl; (11) R_eC(O)- wherein R_e is C₁-C₄ alkyl or C₁-C₄ alkoxy; (12) -SO₂NR_cR_d wherein R_c and R_d are as defined; or (13) -N(R_c)C(O)R_d wherein R_c and R_d are as defined.

Compounds of this type are described in commonly assigned U.S. Pat. 4,783,213, issued November 8, 1988.

Another embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-( 2-substituted benzoyl)-4-(substituted imino, oximino or carbonyl) -1,3-cyclohexanedione and a two-part antidote with an inert carrier therefor. The 5- and 6-positions of the 1,3-cyclohexanedione moiety are substituted with groups hereinafter defined, preferably with hydrogen or methyl groups. The benzoyl and imino, oximino or carbonyl moieties can be substituted.

Also embodied within the scope of this invention are novel compounds having the following structural formula

wherein

X is oxygen or NR⁶⁹ wherein R⁶⁹ is hydrogen, C₁-C₄ alkyl, or C₁-C₄ alkoxy;

R⁶⁰ is halogen; C₁-C₂ alkyl; C₁-C₂ alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C₁-C₂ haloalkyl; R_aSO_n- wherein n is 0 or 2, and R_a is C₁-C₂ alkyl;

trifluoromethyl or difluoromethyl. Preferably R⁶⁰ is chlorine, bromine, C₁-C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁-C₂ alkylthio or C₁-C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R⁶¹ is hydrogen; C₁-C₄ alkyl, phenyl or substituted phenyl;

R⁶¹ is hydrogen or C₁-C₄ alkyl; or

R⁶¹ and R⁶² together are C₂-C₅ alkylene;

R⁶³ is hydrogen, C₁-C₄ alkyl, phenyl or substituted phenyl with the proviso that R⁶¹ and R⁶³ are not both phenyl or substituted phenyl;

R⁶⁴ is hydrogen or C₁-C₄ alkyl;

R⁶⁵ is hydrogen or C₁-C₄ alkyl; or

R⁶⁶ is C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R⁶⁷ and R⁶⁸ independently are (1) hydrogen; (2) halogen; (3) C₁-C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl, preferably trifluoromethyl; (9) R_bSO_n- wherein n is the integer 0, 1 or 2, preferably 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_cR_d wherein R_c and R_d independently are hydrogen or C₁-C₄ alkyl; (11) R_eC(O)- wherein R_e is C₁-C₄ alkyl or C₁-C₄ alkoxy; (12) -SO₂NR_cR_d wherein R_c and R_d are as defined; or (13) -N(R_c)C(O)R_d wherein R_c and R_d are as defined. Within this embodiment, preferably R⁶⁷ is in the 3-position and R⁶⁷ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁-C₄ alkoxy or C₁-C₄ thioalkyl; and preferably R⁶⁸ is in the 4-position and R⁶⁸ is halogen, cyano, trifluoromethyl, or R_bSO₂ wherein R_b is C₁-C₄ alkyl, or C₁-C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

Compounds of this type are described in copending, commonly assigned U.S. patent application Serial No.

07/086,267, filed August 20, 1987.

Another embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-(2-sub- stituted benzoyl)-4-(substituted)-1,3-cyclohexanedione and an antidote with an inert carrier therefor. The 5- and 6-positions and the 4-position of the 1,3-cyclohexanedione moiety are preferably substituted with groups hereinafter defined, most preferably with halogen or methyl groups. The benzoyl moiety can be substituted, with the groups as hereinafter recited.

Within the scope of this embodiment are compounds having the following structural formula

in which

R⁷⁰ is halogen; C₁-C₂ alkyl; C₁-C₂ alkoxy, trifluoromethoxy or difluoromethoxy; nitro; cyano; C₁-C₂ haloalkyl; R_aSO_n- wherein n is 0 or 2, and R_a is C₁-C₂- alkyl; trifluoromethyl or difluoromethyl. Preferably R⁷⁰ is chlorine, bromine, C₁-C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁-C₂ alkylthio or C₁-C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;

R⁷¹ is hydrogen; C₁-C₄ alkyl, halogen, phenyl or substituted phenyl;

R⁷¹ is hydrogen or C₁-C₄ alkyl; or

R⁷¹ and R⁷² together are C₂-C₅ alkylene;

R⁷³ is hydrogen, C₁-C₄ alkyl, phenyl or substituted phenyl, with the proviso that R⁷¹ and R⁷³ are not both phenyl or substituted phenyl;

R⁷⁴ is hydrogen or C₁-C₄ alkyl;

R⁷⁵ is hydrogen or C₁-C₄ alkyl;

R⁷⁶ is halogen, nitro, cyano, trifluoromethyl,

-C(O)NR_{b 2} wherein R_b is hydrogen or C₁-C₂ alkyl; and

R⁷⁷ and R⁷⁸ independently are (1) hydrogen; (2) halogen; (3) C₁-C₄ alkyl; (4) C₁-C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁-C₄ haloalkyl; (9)

R_bSO_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_cR_d wherein R_c and R_d independently are hydrogen or C₁-C₄ alkyl; (11) R_eC(O)- wherein R_e is C₁-C₄ alkyl or C₁-C₄ alkoxy; (12) -SO₂NR_cR_d wherein R_c and R_d are as defined; or (13) -N(R_c)C(O)R_d wherein R_c and R_d are as defined. Within this embodiment, preferably R⁷⁷ is in the 3-position and R⁷⁷ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁-C₄ alkoxy or C₁-C₄ thioalkyl, preferably R⁷⁸ is in the 4-position and R⁷⁸ is halogen, cyano, trifluoromethyl, or R_bSO₂ wherein R_b is C₁-C₄ alkyl, or C₁-C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl. Compounds of this type are described in commonly assigned U.S. Pat. 4,781,751, issued November 1, 1988, the disclosure of which is incorporated hereby by reference.

The term "C₁-C₄ 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 term "C₁-C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁-C₄ haloalkyl" includes the alkyl groups defined above under C₁-C₄ alkyl in which one or more hydrogen is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds are included within the scope of the instant invention as discussed above.

One method for production of aroylated dicarbonyl compounds is disclosed in European Patent Application,

Publication No. 90262 and involves the reaction of an optionally substituted 1,3-cyclohexanedione with a substituted benzoyl cyanide. The reaction is carried out in the presence of zinc chloride and triethylamine.

The following TABLES II through XV present a list of sample compounds as found in the above description of active herbicides.

Description of Antidotes

This invention embodies a herbicidal agent with an antidote comprised of (a) the herbicide as described herein- above and (b) effective antidotes therefor. It has been found that such antidote compounds must be selected from a specific range of chemical substances that have been found to be effective as herbicide antidotes for protection of crops from the above-described aroylated 1,3-dicarbonyl and 1,3,5- tricarbonyl cyclohexane herbicides. The effectiveness on crops on which the above-described herbicides are useful can be significantly broadened by the use of the antidote described herein to protect crops from injury therefrom and render the compositions more crop selective while controlling the weed pests. Preferred types of antidotes are 1,8-naphthalic anhydride, its salts, tertiary amine salts and esters.

The 1,8-naphthalic dicarboxylic acid and derivatives thereof suitable for use as an antidote within the present invention include 1, 8-naphthalic anhydride and derivatives thereof, and those compounds having the general formula

in which R and R' are independently an inorganic salt cation, for example, potassium and sodium; hydrogen, a tertiary C₁-C₄ alkyl amine salt cation, such as triethylammonium, C₁-C₆ lower alkyl, C₂-C₆ alkenyl, C₂-C₆ alkoxyalkyl, phenyl, substituted phenyl, benzyl, and substituted benzyl; R'' is H, C₁-C₃ alkyl, Cl, BR and F. Alternatively, the 1,8-napthalic anhydride and derivatives thereof can be substituted as above to produce compounds having the formula

wherein R'' is as described above.

The amount of 1,8-naphthalic anhydride and 1,8- naphthalic dicarboxylic acid, derivatives thereof or salts thereof of the above-described herbicide compositions of this invention and the manner of this utilization and resulting efficacy can vary according to various parameters, such as the particular antidote employed, the crop which is protected, the amount or rate of herbicide applied, the soil and climatic conditions of the agricultural environment in which the mixture is applied. The selection of specific antidotes for use in the herbicide composition, the manner in which it is applied, the determination of activity which is non-phytotoxic but antidotally effective, and the amount necessary to provide this result, can be readily performed in accordance with common practice in the art.

For other descriptions of antidotes and methods of their use, reference is made to U.S. Patents. 3,959,304;

3,989,503; 3,131,509; 3,564,768; 4,137,070; 4,294,764;

4,256,481; 4,415,353; and 4,415,352. The disclosures of these documents are hereby incorporated herein by reference.

The antidotes are applied in non-phytotoxic antidotally effective amounts in conjunction with the herbicide. By "non-phytotoxic" is meant an amount of the antidotes which causes at most minor or no injury to the desired crop species. By "antidotally effective" is meant an antidote used in an amount which is effective as an antidote with the herbicide to decrease the extent of injury caused by the herbicide to the desired crop species. The preferred weight ratio of herbicide to antidotes is from about 0.1:1 to about 30:1. Another preferred weight ratio range is from about 1:1 to about 20:1. An even more preferred weight ratio range is from about 2:1 to about 15:1. The most preferred weight ratio range is from about 6:1 to about 1:4.

The following examples are for illustrative purposes only and are not intended as necessarily representative of the overall testing performed and are not intended to limit the invention in any way. As one skilled in the art is aware, in herbicidal testing, a significant number of factors that are not readily controllable can affect the results of individual tests and render them non-reproducible. For example, the results may vary depending on environmental factors, such as amount of sunlight and water, soil type, pH of the soil, growth stage of plants, temperature, and humidity, among other factors. Also, the depth of planting, the application rate of the herbicide, the application rate of the antidotes, and the ratio of the herbicide-to-antidote application, was well as the nature of crops being tested, can affect the results of the test. Results may vary from crop to crop and within the crop varieties.

TABLES XVIIa, XVIIb, XVIIc, XVIId, XVIIe, XVIIf AND XVIIg

MATERIAL AND METHODS

The following herbicide/antidote tests were conducted with various plant species. The corn hybrids and weed species employed in each test for TABLES XVIIa, XVIIb, XVIIc, XVIId, XVIIe, XVIIf AND XVIIg are as follows: CYPES - Cyperses esculentus (yellow nutsedge)

SETFA - Setaria faberii (giant foxtail)

Corn - DeKalb T1100 CCNT 110

Herbicide compounds and antidotes employed in the tests were sprayed in an acetone-water solution containing 0.5% polyoxyethylene sorbitan monolaurate emulsifier.

Herbicides and antidotes were applied as post-emergence tank mix solutions (POES) with a carrier volume of 25 gal/A. All seeds were seeded in aluminum flats (16x23x7 cm) of which holes were punched in the bottom to allow water drainage.

Seeds were planted 1-3 cm deep, in a sandy loam soil fortified with fertilizer (17-17-17; Garden Valley Fertilizer Co., San Jose, CA 95112) and the fungicide Captan 80W. Approximately 14-16 days after seeding, the plants were sprayed in a linear spray table.

After treatment, all flats were placed into a greenhouse. Greenhouses were maintained at about 25°C day and 20°C night temperatures. All flats were watered on the soil surface. Care was taken in keeping water off the sprayed foliage. After treatment, visual ratings of weed control and crop injury were recorded. Ratings were stated as percentage of control or injury of each individual species as compared with an untreated control. The injury ratings ranged from 0 to 100%, where 0 represents no effect on growth and 100 represents complete kill. Early corn injury ratings were taken at about 10 days after treatment. Final corn injury and weed injury ratings were taken at about 21 days after treatment.

The herbicide used throughout these tests is compound 24D having the formula

FORMULATIONS

A formulation is the incorporation of a formulant in a form which is directly usable on crops and weeds. As defined herein, a "formulant" is the material which is to be formulated. The formulant may be either an antidote compound alone, a combination of antidotes together, or an herbicide and antidote composition as described herein. The purpose of the formulation is to apply the formulant to the locus where it is desired to establish herbicidal selectivity by a convenient method. The "locus" may include soil, seeds, crop, crop seeds, seedlings and vegetation.

The antidotes described herein can be formulated in a number of ways for suitable application: (a) the antidotes can be formulated for application directly to the crop seed; (b) the antidotes and herbicide can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, i.e., as a tank mix, or (c) the antidotes and herbicide may be formulated together in the proper weight ratio.

Useful formulations of the compounds of this invention can be prepared in conventional ways. They include dusts, granules, microcapsules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly to the locus. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to about 99% by weight of active herbicide and antidote ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 2% to about 99.9% solid or liquid inert diluent(s). More specifically, they can contain these ingredients in the following approximate proportions.

* Active ingredient plus at least one surfactant and/or diluent equals 100 weight percent.

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Dusts are free-flowing powder compositions containing the formulant impregnated on a particulate carrier. The particle size of the carriers is usually in the approximate range of 30 to 50 microns. Examples of suitable carriers are talc, bentonite, diatomaceous earth, and pyrophyllite. The composition generally contains up to 50% of formulant. Anti-caking and anti-static agents may also be added. Dusts may be applied by spraying from boom sprayers, hand sprayers or airplanes.

Wettable powders are finely divided compositions comprising a particular carrier impregnated with the formulant and additionally containing one or more surface active agents. The surface active agent promotes rapid dispersion of the powder in an aqueous medium to form stable, sprayable suspensions. A wide variety of surface active agents can be used, for example, long chain fatty alcohols and alkali metal salts of the sulfate fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length. A list of surface active agents suitable for use in agriculture formulations can be found in Wade Van Valkenburg, Pesticide

Formulations (Marcel Dekker, Inc., N.Y., 1973), at pages 79-84.

Granules comprise the formulant impregnated on a particulate inert carrier having a particle size of about 1 to 2 millimeters (mm) in diameter. The granules can be made by spraying a solution of the formulant in a volatile solvent onto the granular carrier. Examples of suitable carriers for the preparation of granules include clay, vermiculite, sawdust and granular carbon. Microcapsules and other slow release formulations are advantageous as formulations to deliver and distribute the active ingredients. Microcapsules consist of fully enclosed droplets or granules containing the active materials in whidh the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period of time. Encapsulated droplets are typically about 1 to 50 microns in diameter. The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain an amount of solvent in addition to the active materials. Encapsulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 mm to 1 centimeter (cm) in diameter. In agricultural usage, the granule size is generally about 1 to 2 mm in diameter. Granules formed by extrusion, agglomeration or prilling are useful in the present invention as well as materials in their naturally occurring form. Examples of such carriers are vermiculite, sintered clay granules, kaolin, attapulgite clay, sawdust and granular carbon.

Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Emulsifiable concentrates consist of an oil solution of the formulant plus an emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives, such as suspending agents and thickeners, may be included in the emulsifiable concentrate.

When the formulant is an antidote and herbicide composition, the proportion of antidote compounds to herbicide compound generally ranges from approximately 0.001 to 30 parts by weight of the antidote compounds per weight of the herbicide compound.

Formulations generally contain several additives in addition to the formulant and carrier or agent. Among these are inert ingredients, diluent carriers, organic solvents, water, oil and water, water-in-oil emulsions, carriers of dusts and granules, and surface active wetting, dispersing and emulsifying agents. Fertilizers, e.g., ammonium nitrate, urea and superphosphate, may be included. Aids to rooting and growth, e.g., compost, manure, humus and sand, may also be included.

Alternatively, the antidote compounds and herbicide and antidote compositions of this invention can be applied to a crop by addition of the formulant 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.

As another alternative, the formulant can be applied to the soil in the form of a solution in a suitable solvent. Solvents frequently used in these formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene and aromatic petroleum fractions rich in methylated naphthalenes. Liquid solutions, like dusts, may be applied by spraying from boom and hand sprayers or airplanes.

EXAMPLE

Dusts: The following substances are used to formula (a) a 5% and (b) a 2% dust:

(a)

5 parts of active substance

95 parts of talc; (b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground, and in this form can be processed to dusts for application.

EXAMPLE

Granulate: The following substances are used to formula a 5% granulate:

5 parts of active substance

0.25 part of epichlorohydrin

0.25 part of cetyl polyglycol ether

3.25 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm) The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is sprayed on kaolin and the acetone is evaporated in vacuo.

EXAMPLE

Wettable powders: The following constituents are used to formula (a) a 70%; (b) a 40%; (c) and (d) a 25% and (e) a 10% wettable powder.

(a)

70 parts of active substance

5 parts of sodium dibutylnaphthylsulfonate

3 parts of naphthalenesulfonic acid/

phenolsulfonic acid/formaldehyde

condensate (3:2:1)

10 parts of kaolin

12 parts of Champagne chalk (b)

40 parts of active substance

5 parts of sodium ligninsulfonate

1 part of sodium dibutylnaphthalenesulfonic acid

54 parts of silicic acid

(c)

25 parts of active substance

4.5 parts of calcium ligninsulfate

1.9 parts of Champagne chalk/

hydroxyethylcellulose mixture (1:1)

1.5 parts of sodium dibutylnaphthalenesulfonate

19.5 parts of silicic acid

19.5 parts of Champagne chalk

28.1 parts of kaolin

(d)

25 parts of active substance

2.5 parts of isooctylphenoxy-polyethyleneethanol

1.7 parts of Champagne chaIk/hydroxyethyl

cellulose mixture (1:1)

8.3 parts of sodium aluminum silicate

16.5 parts of kieselguhr

46 parts of kaolin

(e)

10 parts of active substance

3 parts of a mixture of sodium

salts of saturated fatty alcohol

sulfates

5 parts of naphthalenesulfonic acid/

formaldehyde condensate

82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with the additives and ground in appropriate mills and rollers. Wettable powders of excellent wettability and suspension power are obtained. These wettable powders can be diluted with water to give suspensions of the desired concentration and can be used in particular for treating parts of plants.

EXAMPLE

Emulsifiable concentrate: The following substances are used to formulate a 25% emulsifiable concentrate:

25 parts of active substance

2.5 parts of epoxidized vegetable oil

10 parts of an alkylarylsulfonate/

fatty alcohol polyglycol ether mixture

5 parts of dimethylformamide

57.5 parts of xylene.

By diluting such a concentrate with water, it is possible to prepare emulsions of the desired concentrations, which are especially suitable for leaf application.

Although this invention has been described with respect to specific embodiments, the details of those embodiments are not to be construed as limitations. Various equivalents, changes and modifications may be made without departing from the spirit and scope of this invention, as will be recognized by one skilled in the art to which it pertains, and it is understood that such equivalent embodiments are part of this invention.

Claims

CLAIMS :

1. A post-emergence herbicide and antidote herbicidal composition comprising: a) an herbicidally effective amount of an aroylated 1,3,5-cyclohexanetrione compound or an aroylated cyclic 1,3-dicarbonyl compound; and, b) a non-phytotoxic antidotally effective amount of a derivative of 1,8-naphthalic dicarboxylic acid selected from the group consisting of 1,8-naphthalic anhydride, derivatives of 1,8-naphthalic anhyride, 1,8-naphthalic dicarboxylic acid, derivatives of 1,8-naphthalic dicarboxylic acid, salts thereof and combinations thereof.

2. An herbicidal composition according to Claim 1, wherein said aroylated 1,3,5-cyclohexanetrione compound is of the formula:

wherein R is an optionally substituted aromatic moiety.

3. An herbicidal composition according to Claim 1, wherein said aroylated 1,3,5-cyclohexanetrione compound is of the formula

wherein R is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, nitro, cyano, C₁-C₄ haloalkyl, R_aSO_n- wherein n is 0 or 2 and R_a is C₁-C₂ alkyl, trifluoromethyl or difluoromethyl, or trifluoromethoxy or difluoromethoxy;

R¹ is hydrogen or C₁-C₄ alkyl;

R² is hydrogen or C₁-C₄ alkyl; or

R¹ and R² together are C₂-C₅ alkylene;

R³ is C₁-C₄ alkyl;

R⁴ is C₁-C₄ alkyl; or

R³ and R⁴ together are C₂-C₅ alkylene;

R⁵ and R⁶ independently are hydrogen, halogen, C₁-C₄ thioalkyl, C₁-C₄ alkoxy, trifluoromethoxy, cyano, nitro, C₁-C₄ haloalkyl, R_bSO_n- wherein n is the integer 0, 1 or 2, and R_b is C₁-C₄ alkyl, C₁-C₄ alkyl substituted with halogen or cyano,

phenyl or benzyl, -NR_cR_d wherein R_c and R_d independently are hydrogen or C₁-C₄ alkyl, R_eC(O)- wherein R_e is C₁-C₄ alkyl or

C₁-C₄ alkoxy, -SO₂NR_cR_d wherein R_c and R_d are as defined, or

-N(R_c)C(O)R_d where R_c and R_d are as defined.

4. An herbicidal composition according to Claim 3, wherein R₅ is in the 3-position and is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁-C₄ alkoxy, or C1^-C4 thioalkyl.

5. An herbicidal composition according to Claim 3 wherein R₆ is in the 4-position and is halogen, cyano, trifluoromethyl or R_bSO₂, wherein R_b is C₁-C₄ alkyl or C₁-C₄ haloalkyl.

6. An herbicidal composition according to Claim 1 wherein said aroylated cyclic 1,3-dicarbonyl compound is of the formula:

wherein R is an optionally substituted aromatic moiety, n is 2 or 3, X and Y are independently hydrogen, aliphatic, aromatic, heterocyclic or alkylene groups, and Z is a chain which contains 2 or 3 optionally substituted ring atoms, at least one of which is nitrogen, sulfur or oxygen.

7. An herbicidal composition according to Claim 1, wherein said aroylated cyclic 1,3-dicarbonyl compound is of the formula:

wherein R¹, R², R³, R⁴, R⁵ and R⁶ are independently hydrogen or C₁-C₄ alkyl or

R¹ or R³ is R_aOC- in which

R_a is C₁-C₄ alkyl, phenyl, optionally substituted by from 2 to 5 methyl groups; or R is hydroxyl and R¹, R².

R⁴, R⁵ and R⁶ are independently hydrogen or C₁-C₄ alkyl; or in which R¹ and R², or R³ and R⁴, taken together are C₂-C₅ alkylene and have a spiro structure; R⁷ is halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl,

R_kSO_n in which R_k is C₁-C₄ alkyl and n = 0, 1 or 2, C₁-C₄ alkoxy, or nitro;

R⁸, R⁹ and R¹⁰ independently are hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, trifluoromethoxy, cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄ alkylthio, phenoxy, or substituted phenoxy in which the substituent is halogen or halomethyl or both,

R_bS(O)_n in which n is 0, 1 or 2, and R_b is C₁-C₄ alkyl, C₁-C₄ haloalkyl, phenyl or benzyl,

R_cCNH- in which R_C is C₁-C₄ alkyl, -NR_dR_e in which R_d and R_e independently are hydrogen or C₁-C₄ alkyl,

R_fC(O)- in which R_f is hydrogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₁-C₄ alkoxy,

SO₂NR_gR_h in which R_g and R_h independently are hydrogen or C₁-C₄ alkyl,

or R⁸ and R⁹ taken together form a ring structure with two adjacent carbon atoms of the phenyl ring to which they are attached.

8. An herbicidal composition according to Claims 1, 2, 3, 4, 5, 6 or 7, wherein said derivative of 1,8-naphthalic acid is an anhydride, amine salt, inorganic salt or ester.

9. An herbicidal composition according to Claims 1, 2, 3, 4, 5, 6 or 7 wherein said dicarboxylic acid is a compound of the formula:

wherein R and R' are independently an inorganic salt cation, hydrogen, tertiary C₁-C₄ alkyl amine salt cation, C₁-C₈ alkyl, C₁-C₈ alkenyl, C₂-C₆ alkoxyalkyl, phenyl or substituted phenyl, benzyl or substituted benzyl; and R" is selected from the group consisting of H, C₁-C₃ alkyl, Cl, Br and F.

10. An herbicidal composition according to Claims 1, 2, 3, 4, 5, 6 or 7 wherein said dicarboxylic acid is a compound of the formula: