WO1991013547A1 - Compositions herbicides de 1,3-dicarbonyle ou de 1,3,5-tricarbonyle cyclohexane aroyles et systeme d'antidote en deux parties relatif a ces compositions - Google Patents

Compositions herbicides de 1,3-dicarbonyle ou de 1,3,5-tricarbonyle cyclohexane aroyles et systeme d'antidote en deux parties relatif a ces compositions Download PDF

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Publication number
WO1991013547A1
WO1991013547A1 PCT/US1991/001708 US9101708W WO9113547A1 WO 1991013547 A1 WO1991013547 A1 WO 1991013547A1 US 9101708 W US9101708 W US 9101708W WO 9113547 A1 WO9113547 A1 WO 9113547A1
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alkyl
hydrogen
phenyl
substituted
independently
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PCT/US1991/001708
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English (en)
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James L. Ahle
Ferenc M. Pallos
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Ahle James L
Pallos Ferenc M
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Publication of WO1991013547A1 publication Critical patent/WO1991013547A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides

Definitions

  • This invention relates to an herbicide and two- part antidote composition and methods of use. More particularly, this invention relates to and describes for the first time certain herbicidal compositions comprising substituted aroylated 1,3-dicarbonyl compounds and 1,3,5-tricarbonyl cyclohexane compounds as the herbicides and a two-part antidote combination therefor comprising a first antidote compound which is a derivative of 1,8-naphthalie dicarboxylic acid selected from the group consisting of 1,8-naphthalic anhydride, substituted 1,8-naphthalic anhydride, 1,8-naphthalie dicarboxylic acid, substituted 1,8-naphthalie dicarboxylic acid, salts, esters and amides thereof and combinations thereof and optionally as a second antidote compound, an amide of haloalkanoic acid.
  • a first antidote compound which is a derivative of 1,8-na
  • An herbicide is a compound which adversely controls or modifies plant growth, e.g., killing, retarding, defoliating, desiccating, regulating, stunting, tillering, stimulating and dwarfing.
  • 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 on the plant and soil; and pre-emergence 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, soil and climatic conditions and overall cost limitations.
  • a beneficial crop is susceptible to the effects of the herbicide.
  • certain herbicidal compounds are phytotoxic to some weed species but not to others.
  • 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.
  • herbicide antidotes 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.
  • an antidote compound may be a remedy, interferent, protectant, or antagonist.
  • 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.
  • 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.
  • the herbicidal aroylated 1,3-dicarbonyl 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.
  • the present invention addresses this problem and provides for a herbicide/two-part antidote composition which reduces or eliminates both early and late injury.
  • Aroylated cyclohexanetrione-1,3,5 herbicide compounds of this invention are contained within and correspond to the following general formula
  • R is a group as hereinafter defined (and may generally be an optionally substituted aromatic moiety) and R 1 ,
  • R 2 , R 3 and R 4 are as herei.nafter 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
  • R is hydrogen; halogen; C 1 -C 2 alkyl, C 1 -C 2 alkoxy, nitro; cyano; C 1 -C 2 haloalkyl; R a SO n - wherein n is 0 or 2 and R a is C 1 -C 2 alkyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy;
  • R 1 is hydrogen or C 1 -C 4 alkyl
  • R 2 is hydrogen or C 1 -C 4 alkyl
  • R 1 and R 2 together are C 2 -C 5 alkylene
  • R 3 is C 1 -C 4 alkyl
  • R 4 is C 1 -C 4 alkyl
  • R 3 and R 4 4ogether are C 2 -C 5 alkylene
  • R 5 and R 6 independently are (1) hydrogen; (2) halogen; (3)C 1 -C 4 thioalkyl; (4) C 1 -C 4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl; (9) R b SO n - wherein n is the integer 0, 1 or 2; and
  • R b is (a) C 1 -C 4 alkyl
  • R 5 is in the 3-position.
  • R 5 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 thioalkyl.
  • R 6 is in the 4-position, wherein R 6 is halogen, cyano, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, such as methyl, or C 1 -C 4 haloalkyl, such as chloromethyl, difluoromethyl or trifluoromethyl.
  • C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tbutyl.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • C 1 -C 4 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secbutoxy, isobutoxy and t-butoxy.
  • C 1 -C 4 haloalkyl includes the alkyl groups defined above under C 1 -C 4 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. 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 disclosure of which is hereby incorporated herein by reference.
  • aroylated 1,3-dicarbonyl herbicide compounds of this invention are contained within and correspond to the following general formula
  • 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.
  • Aroylated carbocyclic 1,3-dicarbonyl compounds of this type have the general structure
  • 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 C 2 -C 5 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
  • 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 C 1 -C 4 alkyl group.
  • Carbon atoms in such rings may be unsubstituted or may be substituted similarly to those in the carbocyclic compounds described above.
  • heterocyclic rings may be saturated or unsaturated.
  • heterocyclic 1,3-dicarbonyl structures include, for instance, barbituric acid derivatives, hydroxypyrones, 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
  • R 1 R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or C 1 -C 4 alkyl or
  • R 1 or R 3 is R a OC- in which
  • R a is C 1 -C 4 alkyl; phenyl, optionally substituted by from 2 to 5 methyl groups; or R is hydroxyl and R 1 R 2 , R 4 , R 5 and R 6 are independently hydrogen or C 1 -C 4 alkyl;- or in which R 1 and R 2 , or R 3 and R 4 , taken together are C 2 -C 5 alkylene (such compounds have a spiro structure;
  • R 8 , R 9 and R 10 independently are hydrogen or substituents including halogen; C 1 -C 4 alkyl; C 1 -C 4 alkoxy, trifluoromethoxy; cyano; nitro; C 1 -C 4 haloalkyl ; C 1 -C 4 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
  • R C CNH- in which R c is C 1 -C 4 alkyl
  • R d and R e independently are hydrogen or C 1 -C 4 alkyl
  • R f C(O)- in which R f is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy;
  • R 8 and R 9 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
  • Some specific types of such aroylated heterocyclic 1,3-dicarbonyl herbicide compounds include:
  • barbituric acid derivatives such as those of the formula
  • R 18 and R 19 are hydrogen or C 1 -C 4 alkyl and R is substituted phenyl such as
  • R 15 , R 16 and R 17 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;
  • oxolactams such as those having the formula in which R 11 -R 14 and R 20 are independently hydrogen or C 1 -C 4 alkyl, or R 11 and R 12 together are C 2 -C 5 alkylene, t is 0 or
  • R is substituted phenyl such as
  • R 15 is; halogen; C 1 -C 2 alkyl; C 1 -C 2 alkoxy; nitro; cyano; C 1 -C 2 haloalkyl; or R m SO n wherein Rm is C 1 -C 2 alkyl and n is 0, 1 or 2; trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy.
  • R 15 is chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl, cyano, nitro, C 1 -C 2 alkylthio or C 1 -C 2 alkylsulfonyl; and R 16 and R 17 independently are (1) hydrogen, (2) halogen,
  • herbicidal oxolactones and oxothiolactones within this invention such as those having the formula
  • R 21 -R 24 are independently hydrogen or C 1 -C 4 alkyl; or R 21 and R 22 together are C 2 -C 5 alkylene; or R 23 and R 24 together are C 2 -C 5 alkyl; or R 21 and R 23 together form a bond, and R is substituted phenyl such as
  • R 15 -R 17 are as defined above; and W is oxygen or sulfur.
  • R 21 and R 23 together form a bond the compounds contain an unsaturated heterocyclic ring.
  • Such compounds are disclosed, for instance, in commonly assigned U.S. Pat.
  • dioxotetrahydropyrans and -thiopyrans such as those having the formula
  • R 26 -R 29 are independently hydrogen or C 1 -C 4 alkyl or
  • R 26 and R 27 together are C 2 -C 5 alkylene, or R 28 and R 29 together are C 2 -C 5 alkylene;
  • W 2 is oxygen, sulfur or sulfonyl and
  • R 30 is substituted phenyl such as
  • R 15 -R 17 are as previously defined.
  • Such compounds are described, for instance, in commonly assigned U.S. Pat.
  • Another embodiment of this invention is an herbicidal composition
  • 1,3-cyclohexanedione moiety is preferably substituted with groups hereinafter defined.
  • the benzoyl and cyclohexanedione moieties can be further substituted.
  • R 130 is halogen; C 1 -C 2 alkyl; C 1 -C 2 alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C 1 -C 2 haloalkyl; R a SO n - wherein n is 0 or 2; and R a is C 1 -C 2 alkyl; trifluoromethyl or difluoromethyl.
  • R 140 is chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl, cyano, nitro, C 1 -C 2 alkylthio or C 1 -C 2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;
  • R 131 is hydrogen or C 1 -C 4 alkyl
  • R 132 is hydrogen or C 1 -C 4 alkyl
  • R 131 and R 132 together are C 2 -C 5 alkylene
  • R 133 is hydrogen or C 1 -C 4 alkyl
  • R 134 is hydrogen or C 1 -C 4 alkyl
  • R 133 and R 134 together are C 2 -C 5 alkylene
  • R 135 , R 136 , R 137 and R 138 independently are (1) hydrogen; (2) chlorine, fluorine or bromine; (3) C 1 -C 4 alkyl; (4) C 1 -C 4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl; (9) R b SO n - wherein n is the integer 0, 1 or 2; and
  • R b is (a) C 1 -C 4 alkyl
  • R 139 is hydrogen or C 1 -C 4 alkyl.
  • R 135 is in the 3-position and R 135 and R 137 are hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 thioalkyl; or R 135 and R 137 are hydrogen and R 136 and R 138 are in the 4-position, wherein
  • R 136 and R 136 are halogen, cyano, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • Another embodiment of this invention is an herbicidal composition
  • an herbicidally active 2-(substituted benzoyl)-cyclohexanedione-1,3 and the aroylating group is a substituted benzoyl moiety and a two-part 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 cyclohexanedione-1,3 moieties can be further substituted.
  • R 40 is halogen; C 1 -C 2 alkyl; C 1 -C 2 alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C 1 -C 2 haloalkyl; R a SO n - wherein n is 0 or 2; and Ra is C 1 -C 2 alkyl;
  • R 41 is hydrogen or C 1 -C 4 alkyl
  • R 42 is hydrogen or C 1 -C 4 alkyl
  • R 41 and R 42 together are C 2 -C 5 alkylene
  • R 43 is hydrogen or C 1 -C 4 alkyl
  • R 44 is hydrogen or C 1 -C 4 alkyl
  • R 43 and R 44 together are C 2 -C 5 alkylene
  • R 45 , R 46 , R 47 and R 48 independently are (1) hydrogen; (2) halogen selected from the group consisting of chlorine, fluorine or bromine; (3) C 1 -C 4 alkyl; (4) C 1 -C 4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl; (9) R b SO n - wherein n is the integer 0, 1 or 2; and
  • R b is (a) C 1 -C 4 alkyl
  • R c and R d are as defined; and R 49 is hydrogen or C 1 -C 4 alkyl.
  • R 45 is in the 3-position and R 45 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 thioalkyl; or
  • R 45 is hydrogen; or R 46 is in the 4-position and R 46 is halogen, cyano, trifluoromethyl, or R b -SO 2 wherein R 46 is C 1 -C 4 alkyl, preferably methyl or C 1 -C 4 haloalkyl, difluoromethyl or trifluoromethyl.
  • Another embodiment of this invention is an herbicidal composition
  • the 5- and 6-positions of the 1,3-cyclohexanedione 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.
  • X is oxy, thio, sulfinyl or sulfonyl
  • R 50 is halogen; C 1 -C 2 alkyl; C 1 -C 2 alkoxy, preferably methoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C 1 -C 2 haloalkyl; R a SO n - wherein n is 0 or 2, preferably 2 and R a is C 1 -C 2 alkyl; trifluoromethyl or difluoromethyl.
  • R 50 is chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl, cyano, nitro, C 1 -C 2 alkylthio or C 1 -C 2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;
  • R 51 is hydrogen; C 1 -C 4 alkyl, phenyl or substituted phenyl;
  • R 51 is hydrogen or C 1 -C 4 alkyl
  • R 51 and R 52 together are C 2 -C 5 alkylene
  • R 53 is hydrogen, C 1 -C 4 alkyl, phenyl or substituted phenyl with the proviso that R 51 and R 53 are not both phenyl or substituted phenyl;
  • R 54 is hydrogen or C 1 -C 4 alkyl
  • R 55 is hydrogen or C 1 -C 4 alkyl
  • R 56 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or phenyl;
  • R 57 and R 58 independently are (1) hydrogen; (2) halogen; (3) C 1 -C 4 alkyl; (4) C 1 -C 4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl; (9) R b SO n - wherein n is the integer 0, 1 or 2; and
  • R b is (a) C 1 -C 4 alkyl
  • Another embodiment of this invention is an herbicidal composition
  • 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.
  • X is oxygen or NR 6 9 wherein R 69 is hydrogen, C 1 -C 4 alkyl, or C 1 -C 4 alkoxy;
  • R 60 is halogen; C 1 -C 2 alkyl; C 1 -C 2 alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C 1 -C 2 haloalkyl; R a SO n - wherein n is 0 or 2, and R a is C 1 -C 2 alkyl; trifluoromethyl or difluoromethyl.
  • R 60 is chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl, cyano, nitro, C 1 -C 2 alkylthio or C 1 -C 2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;
  • R 61 is hydrogen; C 1 -C 4 alkyl, phenyl or substituted phenyl;
  • R 61 is hydrogen or C 1 -C 4 alkyl
  • R 61 and R 62 together are C 2 -C 5 alkylene
  • R 61 is hydrogen, C 1 -C 4 alkyl, phenyl or substituted phenyl with the proviso that R 61 and R 63 are not both phenyl or substituted phenyl;
  • R 64 is hydrogen or C 1 -C 4 alkyl;
  • R 65 is hydrogen or C 1 -C 4 alkyl
  • R 66 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl
  • R 67 and R 68 independently are (1) hydrogen; (2) halogen; (3) C 1 -C 4 alkyl; (4) C 1 -C 4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl, preferably trifluoromethyl; (9) R b SO n - wherein n is the integer 0, 1 or 2, preferably 2; and
  • R b is (a) C 1 -C 4 alkyl
  • R 67 is in the 3-position and R 67 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 thioalkyl; and preferably R 68 is in the 4-position and R 68 is halogen, cyano, trifluoromethyl, or R b SO 2 wherein R 68 is C 1 -C 4 alkyl, or C 1 -C 4 haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.
  • Another embodiment of this invention is an herbicidal composition
  • the 5- and 6-positions and the 4-position of the 1,3-cyclo hexanedione 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.
  • R 70 is halogen; C 1 -C 2 alkyl; C 1 -C 2 alkoxy, trifluoromethoxy or difluoromethoxy; nitro; cyano; C 1 -C 2 haloalkyl; R a SO n - wherein n is 0 or 2, and R a is C 1 -C 2 alkyl;
  • R 70 is chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl, cyano, nitro, C 1 -C 2 alkylthio or C 1 -C 2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl;
  • R 71 is hydrogen; C 1 -C 4 alkyl, halogen, phenyl or substituted phenyl;
  • R 71 is hydrogen or C 1 -C 4 alkyl
  • R 71 and R 72 together are C 2 -C 5 alkylene
  • R 73 is hydrogen, C 1 -C 4 alkyl, phenyl or substituted phenyl, with the proviso that R 71 and R 73 are not both phenyl or substituted phenyl;
  • R 74 is hydrogen or C 1 -C 4 alkyl
  • R 75 is hydrogen or C 1 -C 4 alkyl
  • R 76 is halogen, nitro, cyano, trifluoromethyl
  • R b is hydrogen or C 1 -C 2 alkyl
  • R 77 and R 78 independently are (1) hydrogen; (2) halogen; (3) C 1 -C 4 alkyl; (4) C 1 -C 4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1 -C 4 haloalkyl;
  • R b is (a) C 1 -C 4 alkyl
  • R 77 is in the
  • R 77 is hydrogen, chlori.ne, fluorine, trifluoromethyl, cyano, C 1 -C 4 alkoxy or C 1 -C 4 thioalkyl, preferably R 78 is in the 4-position and R 78 is halogen, cyano, trifluoromethyl, or R b SO 2 wherein R b is C 1 -C 4 alkyl, or C 1 -C 4 haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.
  • C 1 -C 4 alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t- butyl.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • C 1 -C 4 alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy.
  • C 1 -C 4 haloalkyl includes the alkyl groups defined above under C 1 -C 4 alkyl in which one or more hydrogen is replaced by chlorine, bromine, iodine or fluorine.
  • This invention embodies a herbicidal agent with a two-part antidote system comprised of (a) the herbicide as described hereinabove and (b) a combination of 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 in combination as herbicide antidotes for continued early and late protection of the above-described aroylated 1,3-dicarbonyl and 1,3,5-tricarbonyl cyclohexane herbicides.
  • antidote combination described herein to protect one or more crops from early and late injury therefrom and render the compositions more crop selective while controlling the weed pests.
  • Preferred types of antidotes are amides of haloalkanoic acids used in combination with 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
  • R and R' are independently an inorganic salt cation, for example, potassium and sodium; hydrogen, a tertiaryC 1 -C 4 alkyl amine salt cation, such as triethylammonium, C 1 -C 6 lower alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkoxyalkyl, phenyl, substituted phenyl, benzyl, and substituted benzyl; R'' is H, C 1 -C 3 alkyl, Cl, BR and F.
  • the 1,8-napthalic anhydride and derivatives thereof can be substituted as above to produce compounds having the formula
  • R '' is as described above.
  • Amides of haloalkanoic acids have the generalized formula in which R is a mono- or poly-haloalkyl group.
  • the halogens may be variously chloro, bromo or iodo; chloro and bromo are the preferred halogens, and the preferred group for R in these compounds is dichloromethyl, Cl 2 CH-, i.e., the compounds are amides of dichloroacetic acid and amides of dibromopropionic acid.
  • the nitrogen is further substituted by at least one other functional group.
  • This class of compounds also includes those in which the nitrogen forms a portion of a heterocyclic ring with substituents, as will be described below.
  • Such useful antidotes include amides of haloalkanoic acids having the formula , ;
  • n 1 or 2
  • Y is chlorine or bromine
  • R 8' and R 9 ' are independently C 1 -C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 4 alkylene substituted with phenyl, dialkoxyalkyl wherein the alkoxy and alkyl groups each have 1-4 carbon atoms and R 8' and R 9 ' taken together are C 1 -C 4 alkyleneoxyaIkylene, or alkyl- enethioalkylene substituted with a spiro 5- to 6-membered heterocyclic ring, phenyl, alkyl, alkoxyalkyl, or alkylthio- alkyl.
  • antidotes include those wherein n is 1 or 2, R 8' and R 9' are independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, dialkoxyethyl, cyclic acetal or C 1 -C 2 alkylene substituted with phenyl. Further embodiments include those antidotes wherein n is 2, and R 8' and R 9 ' are independently C 1 -C 4 alkyl, C 2 -C 4 alkenyl, dimethoxyethyl, dioxolanylmethyl or benzyl.
  • 4,021,224 is N,N-diallyl dichloroacetamide.
  • dichlormid It is generally known commercially as dichlormid and is included as an antidote in several commercial products containing thiolcarbamate herbicides.
  • Another class of amides of haloalkanoic acids is that in which the nitrogen atom is contained in an oxazolidine or thiazolidine ring.
  • R is dichloromethyl, and these oxazolidines and thiazolidines have the general formula
  • R 80 , R 81 , R 82 , R 83 , R 84 and R 85 are independently hydrogen, lower alkyl, alkoxyalkyl, alkylthioalkyl, lower alkylsulfonylmethyl or -phenyl, or R 80 and R 81 taken together form an alkylene group, preferably a butylene, pentylene or hexylene group optionally substituted by one or two methyl groups and X is oxygen or sulfur.
  • R 80 , R 81 , R 82 , R 83 , R 84 and R 85 are independently hydrogen, lower alkyl, alkoxyalkyl, alkylthioalkyl, lower alkylsulfonylmethyl or -phenyl, or R 80 and R 81 taken together form an alkylene group, preferably a butylene, pentylene or hexylene group optionally substituted by one or two methyl groups and X is oxygen or sulfur.
  • Compounds of these types
  • R 80 methyl
  • R 82 ethyl
  • R 80 and R 81 taken together are alkylene are disclosed for instance in British Patents 1,512,540 and 2,023,582 and Hungarian Patent 181,621. The disclosure of which is hereby incorporated herein by reference.
  • a third type of haloalkanoic acid amide is disclosed generally in U.S. Pat. 4,294,764 and has the general formula in which R 86 may be one of a number of alkyl, alkenyl or alkynyl moieties; R 87 R 88 , R 89 and R 90 are independently hydrogen or methyl; and n is 0 or 1.
  • R 86 may be one of a number of alkyl, alkenyl or alkynyl moieties; R 87 R 88 , R 89 and R 90 are independently hydrogen or methyl; and n is 0 or 1.
  • a representative compound of this type is the compound N-(1,3-dioxolan-2-yl- methyl)-N-(2-propeny1)-2,2-dichloroacetamide, which has the formula
  • R 95 represents the group -C-R 98 in which R 98 is a C 1 -C 3 haloalkyl containing from 1 to 3 halogen atoms or a phenyl group option-ally substituted;
  • R 96 represents a hydrogen atom, a methyl or a phenyl;
  • R 97 represents a C 1 -C 8 alkyl group, a C 5 -C 6 cycloalkyl group, a cyclohexylmethyl group, a phenyl group optionally substituted, a benzyl group optionally substituted, an allyl or propargyl group; and n is zero or one.
  • a representative antidote of that group is:
  • the amount of a given amide of haloalkanoic antidote utilized in combination with 1,8-naphthalie anhydride and 1,8-naphthalie 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 antidotes are applied in non-phytotoxic antidotally effective amounts in conjunction with the herbicide.
  • non-phytotoxic is meant an amount of the antidotes which causes at most minor or no injury to the desired crop species.
  • 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 0.1:1:1 to about 30:1:1. Another preferred weight ratio range is from about 1:1:1 to about 20:1:1. An even more preferred weight ratio range is from about 2:1:1 to about 15:1:1. The most preferred weight ratio is about 1:2:2.
  • 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.
  • 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.
  • 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.
  • Herbicidal and antidotal compounds of this invention were tested using the following methods:
  • the herbicide and antidotes sprayed in the tests were applied in an acetone-water solution containing 0.5% polyoxy- ethylene sorbitan monolaurate emulsifier. All herbicides and antidotes were applied post-emergence in tank mix solutions at a carrier volume of 234 l/ha (25 gal/A) approximately 14-16 days after planting. All seeds were seeded in 31x21x8 cm metal trays that had holes for drainage. Seeds were planted 1-3 cm deep in a sandy loam soil fortified with
  • HAA haloalkanoic acid amides
  • the first HAA is used in TABLES XVII and XVIII exclusively while both are used in Table XIX.
  • a formulation is the incorporation of a formulant in a form which is directly usable on crops and weeds.
  • 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 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
  • Active ingredient plus at least one surfactant and/or diluent equals 100 weight percent.
  • 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
  • compositions generally contains up to 50% of formulant.
  • Anticaking 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.
  • surface active agents suitable for use in agriculture formulations can be found in Wade Van Valkenburg, Pesticide Formulations
  • 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.
  • 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 which 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Dusts The following substances are used to formula (a) a 5% and (b) a 2% dust:
  • Granulate The following substances are used to formula a 5% granulate:
  • 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.
  • 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.
  • Emulsifiable concentrate The following substances are used to formulate a 25% emulsifiable concentrate:

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Abstract

Herbicide post-germination et composition herbicide servant d'antidote en deux parties comprenant: a) une quantité efficace en tant qu'herbicide d'un composé de 1,3,5-cyclohexanetrione aroylé ou d'un composé de 1,3-dicarbonyle cyclique aroylé, et; b) une quantité efficace non phytotoxique en tant qu'antidote d'un antidote en deux parties consistant en un amide d'acide dichloroacétique et un dérivé d'acide 1,8-naphtalique dicarboxylique choisi parmi le groupe composé d'anhydride 1,8-naphtalique, de dérivés d'anhydride 1,8-naphtalique, d'acide 1,8-naphtalique dicarboxylique, de dérivés d'acide 1,8-naphtalique dicarboxylique, de sels de ces derniers et de mélanges de ces derniers. L'invention comprend également des procédés d'utilisation de ces compositions.
PCT/US1991/001708 1990-03-14 1991-03-13 Compositions herbicides de 1,3-dicarbonyle ou de 1,3,5-tricarbonyle cyclohexane aroyles et systeme d'antidote en deux parties relatif a ces compositions WO1991013547A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5491124A (en) * 1993-06-25 1996-02-13 Sandoz Ltd. Herbicidal compositions comprising chloroacetamide and triketone herbicides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702759A (en) * 1970-05-27 1972-11-14 Gulf Research Development Co Herbicide resistant corn seed method
EP0298679A2 (fr) * 1987-07-06 1989-01-11 Ici Americas Inc. Compositions herbicides à base de 1,3,5-tricarbonyl-cyclohexanes acylés herbicides et d'antidotes
EP0298680A2 (fr) * 1987-07-06 1989-01-11 Zeneca Inc. Compositions herbicides à base d'herbicides 1,3-dicarbonyliques acylés et d'antidotes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702759A (en) * 1970-05-27 1972-11-14 Gulf Research Development Co Herbicide resistant corn seed method
EP0298679A2 (fr) * 1987-07-06 1989-01-11 Ici Americas Inc. Compositions herbicides à base de 1,3,5-tricarbonyl-cyclohexanes acylés herbicides et d'antidotes
EP0298680A2 (fr) * 1987-07-06 1989-01-11 Zeneca Inc. Compositions herbicides à base d'herbicides 1,3-dicarbonyliques acylés et d'antidotes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5491124A (en) * 1993-06-25 1996-02-13 Sandoz Ltd. Herbicidal compositions comprising chloroacetamide and triketone herbicides
US5545607A (en) * 1993-06-25 1996-08-13 Sandoz Ltd. Herbicidal compositions comprising metolachlor and triketone herbicides

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