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GB1567300A - Synthesis of biocidal 2-aryl-1,3-cycloalkane-diones and their enol esters - Google Patents

Synthesis of biocidal 2-aryl-1,3-cycloalkane-diones and their enol esters Download PDF

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Publication number
GB1567300A
GB1567300A GB12103/78A GB1210378A GB1567300A GB 1567300 A GB1567300 A GB 1567300A GB 12103/78 A GB12103/78 A GB 12103/78A GB 1210378 A GB1210378 A GB 1210378A GB 1567300 A GB1567300 A GB 1567300A
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compound
cyclohexanedione
dimethyl
alkyl
group
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Union Carbide Corp
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Union Carbide Corp
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Priority claimed from US05/781,985 external-priority patent/US4209532A/en
Priority claimed from US05/781,781 external-priority patent/US4422870A/en
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Publication of GB1567300A publication Critical patent/GB1567300A/en
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    • C07C59/40—Unsaturated compounds
    • C07C59/76—Unsaturated compounds containing keto groups
    • C07C59/84—Unsaturated compounds containing keto groups containing six membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/753—Unsaturated compounds containing a keto groups being part of a ring containing ether groups, groups, groups, or groups

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  • Life Sciences & Earth Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The new compounds of formula I, whose symbols are defined in Claim 1, possess remarkable herbicidal activity and ovicidal activity against acarians. They are obtained especially by cyclisation of a compound of formula III in which R8 represents H or an alkyl group. <IMAGE>

Description

(54) SYNTHESIS OF BIOCIDAL 2-ARYL-1, 3-CYCLOALKANEDIONES AND THEIR ENOL ESTERS (71) We, UNION CARBIDE CORPORATION, a Corporation organised and existing under the laws of the State of New York, United States of America, of 270 Park Avenue, New York, State of New York 10017, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to 2-aryl-l,3-cyclohexane compounds and to their alkali metal salts, ammonium salts and enol ester derivatives. This invention is also directed to methods of preparing the compounds of this invention. In another aspect this invention provides miticidal, mite ovicidal, post-emergent herbicidal and pre-emergent herbicidal compositions comprising an acceptable carrier and a pesticidally effective amount of a compound of this invention as well as to a method of controlling mites and plant pests which comprises subjecting the mites, the eggs of mites and the plant pests to a pesticidally effective amount of a compound of this invention.
More particularly, this invention provides compounds of the general formula:
wherein: Z, Z', Z" and Z"' are each individually a hydrogen atom or a haloalkyl, polyhaloalkyl, halogen, alkyl, alkoxy, cyano, nitro, alkyl-thio, alkanoyl, amido, amino, alkylsulfinyl or alkylsulfonyl group: Y is a hydrogen atom or
R is a hydrogen atom or a halogen, alkyl, alkenyl, alkynyl, bicycloalkyl, bicyloalkenyl, cycloalkyl, cycloalkenyl, phenyl, phenylalkyl, naphthyl or naphthylalkyl group all of which, other than the hydrogen and halogen atoms, may be substituted with one or more alkyl, cyano, nitro, alkoxy, halogen, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl or dialkylamino substituents; R1 is an alkyl, polyhaloalkyl or haloalkyl group or a halogen atom and R2, R3, R4, Rss Re and R7 are each individually a hydrogen atom or either a substituted or unsubstituted alkyl or phenyl, group wherein the permissible substituents are one or more alkyl, cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino substituents; or any two R2, R3, R4, R5, Re or R, substituents together may form an alkylene or alkenylene chain containing from 2 to 20 carbon atoms completing a 3, 4, 5, 6 or 7 membered ring structure; with the proviso that the R1, R2, R3, R4, R5, R6, R7, Z, Z', Z", and Z"' groups individually do not contain more than ten aliphatic carbon atoms and R does not contain more than thirty aliphatic carbon atoms.
The following miticidally, mite ovicidally or herbicidally active compounds are illustrative of compounds within the purview of the above generic formula and which can be conveniently prepared by the process of this invention simply by selecting appropriate reactants for use in the procedures described below: 2 - (2' - Chlorophenyl) - 3 - (7 - phenylheptanoyloxy) - 5,5 - dimethyl - 2 - cyclo hexenone 2 - (2' - Chlorophenyl) - 3 - (2',6' - dichlorohexanoyloxy) - 2 - cyclohexenone 2 - (2',4' - Dibromophenyl) - 3 - (hexanoyloxy) - 2 - cyclohexenone 2 - (2' - Chlorophenyl) - 3 - (2 - ethylhexanoyloxy) - 2 - cyclohexenone 3 - (2' - Isopropylphenyl) - 4 - acetoxy - spiro[5.51undec - 3 - en - 2 - one 2 - (2' - Chlorophenyl) - 3 - benzoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2' - Bromophenyl) - 3 - (4' - chlorobenzoyloxy) - 5,5 - dimethyl - 2 - cyclo hexenone 2 - (2' - Chlorophenyl) - 3 - (5' - diethylaminophenylcarbonyloxy) - 5,5 - dimethyl 2 - cyclohexenone 2 - (2' - Chlorophenyl) - 3 - (4' - chlorophenylcarbonyloxy)5,5 - dimethyl - 2 - cyclo hexenone 2 - (2' - Chlorophenyl) - 3 - (4' - methylthiophenylcarbonyloxy) - 5,5 - dimethyl - 2 cyclohexenone 2 - (2' - chloro - 5' - Nitrophenyl) - 3 - (4' - dimethylaminophenylcarbonyloxy)- 5,5, - dimethyl - 2 - cyclohexanone 2 - (2' - Chlorophenyl) - 3 - (trifluoroacetoxy) - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2' - Chlorophenyl) - 3 - (acetoxy) - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2' Trifluoromethyl - 4' - nitrophenyl) - 3 - chlorocarbonyloxy - 5,6 - dimethyl 2 - cyclohexenone 2 - (2' - ethyl - 4' - nitrophenyl) - 3 - chlorocarbonyloxy - 5,6 - dimethyl -2- cyclo hexenone 2 - (2' - Methyl - 6' - nitrophenyl) - 3 - naphthylcarbonyloxy -4,4- diethyl -2 - cyclo hexenone 2 - (2' - 4' - Dimethylphenyl) - 3 - hexanoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - (2 - ethylhexanoyloxy) - 5,5 - dimethyl - 2 - cyclo hexenone 2 - (2',3' - Dimethylphenyl) - 3 - stearoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',5' - Dichlorophenyl) - 3 - acetoxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',4' - Dibromophenyl) - 3 - isobutyrloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',6' - Dichlorophenyl) - 3 - hexanoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',6' - Dichlorophenyl) - 3 - (2 - ethylhexanoyloxy) - 5,6 - dimethyl - 2 - cyclo hexenone 2 - (2',5' - Dichlorophenyl) - 3 - stearoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',3' - Dimethylphenyl) - 3 - benzoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - phenylcarbonyloxy - 4,6 - dimethyl - 2 - cyclo hexanone Piperidinium salt of 2 - (2',5' - dimethylphenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione I - Adamantanammonium salt of 2 - (2' - chlorophenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione Pyridinium salt of 2 - (2' - methylphenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione Morpholinium salt of 2 - (2',4' - dichlorophenyl)- 5,5 - dimethyl - 1,3 - cyclohexane dione Benzyldimethylammonium salt of 2 - (2',4' - dimethylphenyl) - 5,5 - dimethyl - 1,3 cyclohexanedione Dicyclohexylammonium salt of 2 - (2' - chlorophenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione N,N - diethylanilinium salt of 2 - (2',4' - dimethylphenyl) - 5,5 - dimethyl - 1,3 cyclohexanedione 2 - Picolinium salt of 2 - (2',4' - dichiorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione Piperazinium salt of 2 - (2',5' - dimethylphenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione Imidazolium salt of 2 - (2' - chlorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',4' - dimethylphenyl) - 5 - methyl - 5 - ethyl - 1,3 - cyclohexanedione 2 - (2',4' - dichlorophenyl) - 5,5 - diethyl - 1,3 - cyclohexanedione 2 - (2' - methyl - 4' - methoxyphenyl) - 5 - methyl - 5 - isobutyl - 1,3 - cyclohexane- dione 2 - (2' - methyl - 4' - chlorophenyl) - 5 - methyl - 5 - isopropyl - 1,3 - cyclohexane dione 2 - (2' - Ethyl - 6' - ethoxyphenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',6' - Diethylphenyl) - 5,5 - ditrifluoromethyl - 1,3 - cyclohexanedione 2 - (2' - Methyl - 6' - (methylsulfinyl)phenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione 2 - (2' - Trichloromethyl - 6' - cyanophenyl) - 5,6 - dimethyl - 1,3 - cyclohexane dione 2 - (2',6' - Dimethyl - 4' - t - butylphenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 3 - (2',4',6' - Triethylphenyl) - spiro - [5,5]undecane - 2,4 - dione Trimethylammonium salt of 2 - (2' - ethyl - 6' - ethoxy) - 5,5 - dimethyl - 1,3 - cyclo hexanedione 3 - (2' - Methylphenyl) - spiro [5,5] undecane - 2,4 - dione 5 - Phenyl - 2 - (2',4',6' - trimethylphenyl)- 1,3 - cyclohexanedione 2 - (2' - Methyl - 4',6' - dichlorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Nitro - 4',6' - Dibromophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 5 - (4' - Chlorophenyl) - 2 - (2',4',6' - trimethylphenyl) - 1,3 - cyclohexanedione 5 - (3' - Bromophenyl) - 2 - (2',4',6' - trimethylphenyl) - 1,3 - cyclohexanedione 5 - (2' - Methylthiophenyl) - 2 - (2',4',6' - trichlorophenyl) - 1,3 - cyclohexanedione 5 - (4' - Methoxyphenyl) - 2 - (2',4',6' - trimethylphenyl) - 1,3 - cyclohexanedione 5 - (3' - ,B - methoxyethylphenyl) - 2 - (2',4',6' - trimethylphenyl) - 1,3 - cyclohexane- dione 2 - (2',4',6' - Trimethylphenyl) - 4 - (4' - methylphenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione 2 - (2',4',6' - Trimethylphenyl) - 4 - phenyl - 5,5 - dimethyl - 1,3 - cyclohexane dione 2 - (2',4',6' - Trimethylphenyl) - 4 - (4' - chlorophenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione 2 - (2',4',6' - Trimethylphenyl) - 4 - methoxy - 5,5 - dimethyl - 1,3 - cyclo hexanedione 2 - (2',4',6' - Trimethylphenyl) - 4,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',4',6' - Trimethylphenyl) - 4 - (4' - dimethylaminophenyl) - 5 - methyl - 1,3 cyclohexanedione 5 - (4' - Dimethylaminophenyl) - 2- (2',6' - dimethylphenyl) - 4 - methyl - 1,3 - cyclo hexanedione 2 - (2' - N - methylcarbamoyl - 6' - methylphenyl) - 4 - (4' - methoxyphenyl) - 5,6 dimethyl - 1,3 - cyclohexanedione 2 - (2',6' - Dimethylphenyl) - 4 - (4' - methylthiophenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione 2 - (2' - Methyl - 3',6' - dicyanophenyl) - 6 - (methylthioethyl) - 1,3 - cyclohexane- dione 5 - (4' - Methylsulfinylphenyl) - 4,6 - dimethyl - 2 - (2',6' - Dimethylphenyl) - 1,3 cyclohexanedione 2 - (2',4' - Difluorophenyl) - 3 - (2',4' - dichlorophenylcarbonyloxy) - 5,5 - dimethyl 2 - cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - (4' - dimethylaminophenylcarbonyloxy - 5,5 - di methyl - 2 - cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - (4' - chlorophenylcarbonyloxy) - 5,6 - dimethyl - 2 cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - (2' - ethylthiophenylcarbonyloxy) - 5,5 - dimethyl 2 - cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - trifluoroacetoxy - 5,5 - dimethyl - 2- cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - dimethylaminoacetoxy - 4,5 - dimethyl - 2 - cyclo hexenone 2 - (2',4' - Dimethylphenyl) - 3 - methylthioacetoxy - 5,5 - dimethyl - 2 - cyclo hexenone 2 - (2',4' - Dimethylphenyl) - 3 - methylsulfonylacetoxy - 5,5 - dimethyl - 2 - cyclo hexenone 2 - (2',4' - Dimethylphenyl) - 3 - (2 - cyclohexenylcarbonyloxy) - 5,5 - dimethyl - 2 cyclohexenone 2 - (2' - Trichloromethyl - 4' - nitrophenyl) - 3 - (2',4 - dicyanohexanoyloxy) - 4 (2' - chloroethyl) - 2 - cyclohexenone 2 - (2' - Chloro - 4' - nitrophenyl) - 3 - (2' - nitroethanoyloxy) - 4,5 - diethyl - 2 cyclohexenone 2 - (2' - Chloro - 6' - methoxy - 4' - nitrophenyl) - 3 - pentanoyloxy - 6 - (2' - cyano ethyl) - 2 - cyclohexenone 2 - (2' - Chlorophenyl) - 3 - acetoxy - 5,5 - dimethyl - 2 - cyclohexenone 2 - (2' - Chlorophenyl) - 3 - (cyclopropylcarbonyloxy) - 4,5 - dimethyl - 2 - cyclo hexenone 2 - (2' - Bromophenyl) - 3 - (2 - ethylhexanoyloxy) - 5,6 - dimethyl - 2 - cyclo hexenone 2 - (2',4',6' - Trimethylphenyl) - 3 - (4' - cyanobenzoyloxy) - 4 - methyl - 2 - cyclo hexenone 2 - (2' - Methylphenyl) - 3 - ethanoyloxy - 5 - (3' - ethylsulfinylphenyl) - 2 - cyclo hexenone 2 - (2' - Methylphenyl) - 3 - (4' - methoxyphenylcarbonyloxy) - 5,5 - dimethyl - 2 cyclohexenone 2 - (2',6' - Dimethylphenyl) - 3 - (2',4' - dicyanophenylcarbonyloxy) - 5,5 - dimethyl 2 - cyclohexenone 2 - (2',4' - Dimethylphenyl) - 3 - (3' - nitrophenylcarbonyloxy) - 5,5 - dimethyl - 2 cyclohexenone 2 - (2' - Methyl - 4' - chlorophenyl) - 3 - (trifluoroacetoxy) - 5,5 - dimethyl -2- cyclo hexenone 2 - (2',4' - Dimethylphenyl) - 3 - (3' - methylthiobenzoyloxy) - 5,5 - dimethyl - 2 cyclohexenone 2 - (2' - Methylphenyl) - 3 - (2' - methylsulfinylbenzoyloxy) - 5,5 - dimethyl - 2 cyclohexenone 2 - (2' - Methylphenyl) - 3 - (4' - methylsulfonylphenylcarbonyloxy) - 5,5 - dimethyl 2 - cyclohexenone 2 - (2',4',6' - Trimethylphenyl) - 3 - cyclopropylcarbonyloxy - 5,5 - dimethyl - 2 cyclohexenone 2 - (2',4',6' - Trimethylphenyl) - 3 - (2 - cyclohexenylcarbonyloxy) - 5,5 - dimethyl 2 - cyclohexenone 2 - (2' - Methylphenyl) - 3 - propynoyloxy - 5,5 - dimethyl - 2 - cyclohexenone 4 - Acetoxy - 3 - (2',4' - dimethylphenyl) - bicyclo[3.2.l]oct - 3 - en - 2 - one 4 - (2 - Ethylhexanoyloxy) - 3 - (2' - chlorophenyl) - spiro[5.5]undec - 3 - en - 2 - one 2 - Hexanoyloxy - 3 - (2',4' - dichlorophenyl) - bicyclo[4.4.0]dec - 2 - en - 4 - one 3 - Isobutyryloxy - 4 - (4' - chlorophenyl) - 2 - (2',5' - dimethylphenyl) - 2 - cyclo hexenone 2 - (2',4',6' - Trimethylphenyl) - 1,3 - cyclohexanedione 2 - (2' - Cyano - 4',6' - dichlorophenyl) - 1,3 - cyclohexanedione 2 - (2' - Isopropyl - 6' - cyanophenyl) - 4,6 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Trifluoromethyl - 6' - methyl) - 4 - trichloromethyl - 1,3 - cyclohexane dione Triethylammonium salt of 2 - (2',4' - dimethylphenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione Pyrrolidinium salt of 2 - (2',4' - dichlorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione N - Methylpiperdinium salt of 5 - (2' - Methoxyphenyl) - 2 - (2',4',6' - trimethyl phenyl) - 1,3 - cyclohexanedione Trimethylammonium salt of 2 - (2',6' - Dimethylphenyl) - 4 - (4' - methylthio phenyl) - 5,6 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Chloro - 4' - methoxyphenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Methyl - 4' - cyanophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Methyl - 4' - trifluoromethylphenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Trifluoromethyl - 4' - methoxyphenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione 2 - (2' - Trifluoromethyl - 4' - chlorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Trifluoromethyl - 4' - cyanophenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione 2 - (2',4' - Dimethylphenyl) - 5 - phenyl - 1,3 - cyclohexanedione 2 - (2' - Methylphenyl) - 5 - (2' - methylsulfonylmethyl) - 1,3 - cyclohexanedione 2 - (2' - Methylphenyl) - 5 - (2' - chlorophenyl) - 1,3 - cyclohexanedione 2 - (2' - Methylphenyl) - 5 - (4' - nitrophenyl) - 1,3 cyclohexanedione 2 - (2' - Methylphenyl) - 5 - (4' - cyanophenyl) - 1,3 - cyclohexanedione 2 - (2',4' - Dimethylphenyl)- 5 - (2' - methylphenyl) - 1,3 - cyclohexanedione 2 - (2',4' - Dimethylphenyl) - 4 - (4' - trifluoromethylphenyl) - 1,3 - cyclohexane dione 2 - (2',4' - Dimethylphenyl) - 5 - (2' - chlorophenyl) - 1,3 - cyclohexanedione 2 - (2',4' - Dichlorophenyl) - 6 - (2' - methylthiophenyl) - 1,3 - cyclohexanedione 2 - (2',4' - Dichlorophenyl) - 5 - (4' - methylphenyl) - 1,3 - cyclohexanedione 2 - (2',4' - Dichlorophenyl) - 5 - (4' - methoxyphenyl) - 1,3 - cyclohexanedione 3 - (2' - Methylphenyl) - spiro [5.51undecane - 2,4 - dione 3 - (2',4' - Dimethylphenyl) - spiro[5.5]undecane - 2,4 - dione 3 - (2' - Chlorophenyl) - spiro[5.5lundecane - 2,4 - dione 3 - (2',4' - Dichlorophenyl) - spiro[5.5]undecane - 2,4 - dione 2 - (2',4' - Dimethylphenyl) - 4,5 - diethyl - 1,3 - cyclohexanedione 2 - (2',4' - Difluorophenyl) - 6 - methyl - 1,3 - cyclohexanedione 2 - (2' - methyl - 5' - cyanophenyl) - 6 - methoxymethyl - 1,3 - cyclohexanedione 2 - 2',4' - Dibromophenyl) - 4 - (4' - methylthiophenyl) - 5 - methyl - 1,3 - cyclo hexanedione 2 - (2',4' - Dichlorophenyl) - 6 - (4' - dimethylaminophenyl) - 1,3 - cyclohexanedione 2 - (2' - Trifluoromethyl - 5 - cyanophenyl) - 6 - methylsulfinylethyl - 1,3 - cyclo hexanedione 2 - (2' - chloro - 4' - methoxyphenyl) - 4,6 - dimethyl - 1,3 - cyclohexanedione The pyridinium salt of 2 - (2',4' - Dibromophenyl) - 6 - methoxymethyl - 1,3 - cyclo hexanedione The N - methylmorpholinium salt of 2 - (2' - methylphenyl) - 4,6 - diethyl - 1,3 cyclohexanedione 5 - (2',4' - Dimethylphenyl) - 2 - (2',4',6' - trichlorophenyl) - 1,3 - cyclohexanedione 5 - (2',4' - Dichlorobutyl) - 2 - (2' - ethoxy - 3',5',6' - trifluorophenyl) - 1,3 - cyclo hexanedione 5 - (Methylthiomethyl) - 2 - (2' - chloro - 6' - cyanophenyl) - 1,3 - cyclohexanedione 5 - (2' - Dimethylaminophenyl) - 2 - (2',6' - dimethylphenyl) - 1,3 - cyclohexane dione 2 - (2' - Nitro - 3' - methylthio - 6' - trichloromethylphenyl) - 5,5 - dimethyl - 1,3 cyclohexanedione 2 - (2' - methyl - 5' - cyano - 6' - nitrophenyl) - 4,6 - dimethyl - 1,3 - cyclohexane- dione 2 - (2',4' - Dichloro - 6' - trifluoromethylphenyl) - 4 - (2' - chloroethyl) - 1,3 - cyclo hexanedione 3 - (2' - Chloro - 6' - fluorophenyl) - spiro[5.51undecane - 2,4 - dione 2 - (2' - Chloro - 4' - nitro - 6' - cyanophenyl) - 5,5 - propyl - 1,3 - cyclohexanedione 2 - (2',6' - Dichloro - 4' - nitrophenyl) - 5 - (2' - cyanoethyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - methoxy - 4' - nitrophenyl) - 5,5 - dimethyl - 1,3 - cyclo hexanedione 2 - (2' - Chloro - 6' - cyano - 4' - nitrophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Bromo- 6' - methoxyphenyl) - 1,3 - cyclohexanedione 2 - (2' - Methyl - 6' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Trifluoromethyl - 6' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2',6' - Dichloro - 4' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - methoxy - 4' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - cyano - 4' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 4',6' - dinitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Methyl - 4',6' - dinitrophenyl) - 1,3 - cyclohexanedione 4 - (4' - Chlorophenyl) - 2, (2' - chloro - 4' - nitrophenyl) - 1,3 - cyclohexanedione 5 - (4' - Cyanophenyl) - 2 - (2' - chloro - 6' - methoxy - 4' - nitrophenyl) - 1,3 - cyclo hexanedione 5 - (2',4' - Dichlorophenyl) - 2 - (2',4' - dichloro - 6' - nitrophenyl) - 1,3 - cyclo hexanedione 5 - (3' - Nitrophenyl) - 2 - (2' - chloro - 4' - nitrophenyl) - 1,3 - cyclohexanedione 5 - Phenyl - 2 - (2' - methyl - 6' - chloro - 4' - nitrophenyl) - 1,3 - cyclohexanedione 3 - (2' - Chloro - 6' - nitrophenyl) - spiro[5*5] undecane - 2,4 - dione 3 - (2',6' - Dichloro - 4' - nitrophenyl) - spiro[5.5] undecane - 2,4 - dione 2 - (2' - Trifluoromethyl - 4' - aminophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',4' - Dichloro - 6' - aminophenyl) -5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',6' - Dichloro - 4' - aminophenyl) - 5,6 - dimethyl - 1,3 - cyclohexanedione 2 - (2' Chloro 6' - nitro - 4' - aminophenyl) - 5,5 - dimethyl - 1,3 - cyclohexane dione 5 - (4' - Chlorophenyl) - 2 - (2' - chloro - 6' - methoxy - 4' - aminophenyl) - 1,3 cyclohexanedione 5 - (4' - Chloro - 6' - nitrophenyl) - 2 - (2' - bromo -4' - methylsulfinyl - 6' - cyano phenyl) - 1,3 - cyclohexanedione 3 - (2' - Chloro - 6' - aminophenyl) - spiro [5.5] undecane - 2,4 - dione 2 - (2',6' - Dichloro - 4' - aminophenyl) - 1,3 - cyclohexanedione 2 - (2' - Methyl - 6' - nitrophenyl) - 5 - methoxymethyl - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - nitrophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Methyl - 6' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - methoxyphenyl) - 5,6 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - methoxyphenyl) - 4,4 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Methyl - 3' - nitro - 6' - methoxyphenyl) - 4,5 - dimethyl - 1,3 - cyclohexane- dione 2 - (2' - Chloro - 6' - methoxyphenyl) - 1,3 - cyclohexanedione 2 - (2' - Methyl - 4' - nitro - 6' - methoxyphenyl) - 1,3 - cyclohexanedione 2 - (2' - Bromo -4' - nitro -6' - iodophenyl) -4,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Bromo - 4' - aminophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',6' - Dibromophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2' - Bromo - 6' - aminophenyl) - 1,3 - cyclohexanedione 2 - (2' - Bromo - 5' - chloro - 6' - fluorophenyl) - 1,3 - cyclohexanedione 2 - (2',4' - Dichlorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2'4 - Dichloro - 6' - tribromomethylphenyl) - 1,3 - cyclohexanedione 2 - (2',4',6' - Trifluorophenyl) - 5,5 - dimethyl - 1,3 - cyclohexanedione 2 - (2',4',6' - Tribromophenyl) - 1,3 - cyclohexanedione 3 - (2' - Chloro - 6' - bromophenyl) - spiro[5.5] undecane - 2,4 - dione 3 - (2',4',6' - Trimethylphenyl) - spiro[5.5] undecane - 2,4 - dione 3 - (2',4',6' - Trichlorophenyl) - spiro[5.5] undecane - 2,4 - dione 2 - (2' - Methyl - 6' - cyano - 5' - nitrophenyl) - 5,5 - dimethyl - 1,3 - cyclohexane- dione 2 - (2' - Methyl - 6' - cyano - 4' - nitrophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 6' - cyanophenyl) - 1,3 - cyclohexanedione 2 - (2' - Chloro - 4' - cyanophenyl) - 6 - trichloromethyl - 1,3 - cyclohexanedione 2 - (2',6' - Dichloro - 4' - cyanophenyl) - 1,3 - cyclohexanedione S - (2',4' - Dimethoxyphenyl) - 2 - (2',6' - dimethylphenyl) - 1,3 - cyclohexanedione 5 - (2' - Cyanopropyl) - 6 - methyl - 2 - (2',6' - dimethylphenyl) - 1,3 - cyclohexane- dione 5-(3' - Ethylsulfinylphenyl) - 2 - (2',6' - dichlorophenyl) - 1,3 - cyclohexanedione 3 - (2',4' - Dimethylphenyl) - bicyclo [3.2.1] octane - 2,4 - dione 3 - (2',4' - Dichlorophenyl) - bicyclo [4.4.0] decane - 2,4 - dione All compounds within the purview of the above generic formula exhibit miticidal, mite ovicidal, pre-emergent herbicidal and post-emergent herbicidal activity to a lesser or greater extent. Some of these compounds exhibit very high levels of miticidal, mite ovicidal or herbicidal activity in extremely small dosages while others require larger dosages to be pesticidally effective. In general, the compounds of this invention that exhibit the highest order of herbicidal activity also exhibit the highest order of miticidal and mite ovicidal activity. Miticidal and mite ovicidal activity is greatest in those compounds having a hydrogen, alkyl, alkoxy, cyano, trihalomethyl or halogen substituent at one of the ortho positions of the 2-phenyl group and an alkyl or halogen substituent at the other ortho position of the 2-phenyl group. Especially active compounds are those in which the ortho substituents are relatively small groups such as methoxy, ethoxy, methyl, ethyl, or halogen groups.
It has also been found that some of the pesticidal compositions of this invention exhibit excellent fumigant properties. In addition, these compounds are relatively non-toxic to mammals when used in amounts sufficient to kill mites, mite eggs or plant pests.
In addition to their utility as miticides, mite ovicides and herbicides, 2-aryl-1,3cyclohexanedione compounds of this invention are also useful as intermediates in the preparation of other pesticidally active compounds. For example, 2 - (2' chloro - 6' - methoxy - 4' nitrophenyl) - 5,5 - dimethyl - 1, 3 - cyclohexanedione can be reacted with 2-ethylhexanoyl chloride in the presence of pyridine as solvent and acid acceptor to form 3 - (2 - ethylhexanoyloxy) - 2 - (2' - chloro - 6' - methoxy - 4' nitrophenyl) - 5,5 - dimethyl - 2 - cyclohexenone, the corresponding pesticidally active enol ester compound. The 2-aryl-l, 3-cyclohexanedione compounds of this invention can also be reacted with other chemical species containing electron deficient reaction sites as for example organic anhydride compounds such as acetic anhydride.
Preferred because of their higher levels of miticidal, mite ovicidal and herbicidal activity and because of their utility as intermediates in the preparation of other pesticidally active compounds are the compounds of this invention in which, Y is a hydrogen atom or
Z, Z', Z" and Z"' are each individually a hydrogen atom or an alkyl, alkoxy, cyano, halogen or trihalomethyl group; R1 is an alkyl group or a halogen atom; R2, R3, R4, R5, Re and R7 are each individually a hydrogen atom or an alkyl group; The most active and particularly preferred compounds of this invention are those in which: Z, Z', Z" and Z"' are each individually a hydrogen atom or a methyl, methoxy, cyano or halogen atom; R is a linear or branched chain alkyl group containing from I to 30 carbon atoms or a hydrogen atom R, is a methyl group or a halogen atom; R2, R3, R4, Re, Re and R7 are each individually a hydrogen, atom or a methyl or ethyl group.
The 2-aryl-l,3-cyclohexanedione enol ester compounds of this invention can be conveniently prepared by a variety of methods. Two preferred methods which utilize the 2-aryl-1,3-cyclohexanedione parent compound as the precursor are illustrated by the general reaction schemes set forth below in which R, R1, R2, Re, Re, RE, Re R7, Z, Z', Z" and Z"' are as described above and X is a halogen, hydroxyl or group except as noted:
METHOD I
In the reaction illustrated in METHOD I, one equivalent of the corresponding 2-aryl-cyclohexane-l,3-dione compound is reacted with an appropriately substituted acid, acid halide or anhydride compound in the presence of at least one equivalent of an acid acceptor, preferably in an inert solvent.
The acid acceptor utilized in the reactions of METHOD I can be either an organic or an inorganic base. Examples of organic bases that are useful as acid acceptors in the conduct of these reactions are aromatic or heterocyclic tertiary amine compounds such as pyridine or N,N-dimethylaniline, linear tertiary amines, such as triethylamine, pyridine, trimethylamine or 1,4-diazobi cyclo[2.2.2] octane; or alkali metal alkoxides, such as for example, sodium methoxide or sodium ethoxide. Bases such as sodium carbonate, sodium hydroxide or potassium hydroxide are suitable examples of the inorganic bases that are useful as acid acceptors. Preferred organic acid acceptors are tertiary amines such as triethylamine, pyridine or trimethylamine.
In general, any organic solvent that is inert to the reactants or reaction conditions may be employed in the reaction of METHOD I. Examples of organic solvents which are generally suitable for use in the conduct of these reactions are saturated, unsaturated and aromatic hydrocarbons, e.g. hexane, cyclohexane, octane, cyclohexene, dodecane, naphtha, decalin, kerosene, cycloheptane, benzene, toluene, xylene, or naphthalene; ethers such as dioxane, tetrahydrofuran, diethyl ether, tetrahydropyran, 1,2-dimethoxybenzene, 1,2dimethyl benzene, the dialkyl ethers of ethylene glycol, of propylene glycol or chlorinated aliphatic hydrocarbons, such as for example, chloroform, dichloromethane, methylene dichloride, I,l-dichloroethane or carbon tetrachloride.
The 2-aryl-l ,3-cyclohexanedione compounds of this invention can be conveniently prepared by a variety of methods. Two preferred methods for preparing the compounds of this invention are illustrated by the reaction schemes set below in which R1, R2, R3, R4, R5, R6, R7, Z, Z', Z'' and Z''' are as described above and R6 is an alkyl group except as noted: METHOD II
z R METHOD III X 0 R2 R4 R6 ZI / I cH2-c C C C Ib, + Base I I I R3 R3 R5 R7 Zft Z t Z R1 ZI II Preferably, the reactions illustrated in METHODS II and III are carried out by contacting equivalent amounts of the reactants in a suitable solvent. In the conduct of the reaction of METHOD III types and quantities of the solvent employed are not critical. Examples of suitable inert solvents are ethanol, methanol, dimethylformamide, dimethylsulfoxide, methylene chloride, benzene, xylene, toluene, dioxane, dimethoxyethane, and tetrahydrofuran.
The reaction illustrated in METHOD II can be conducted in any solvent that is chemically inert to the reactants and to the reaction conditions, and in which the acid catalyst is soluble. Examples of these solvents are water and carboxylic acids, such as acetic acid and butonic acid. The preferred reaction solvents are water and acetic acid.
The cyclization reaction illustrated in METHOD II is conducted in the presence of a strong mineral acid catalyst. Examples of mineral acids that are useful in the conduc base. Examples of bases that are useful in the conduct of this reaction are the alkali metal alkoxides, as for example, sodium methoxide, sodium ethoxide or potassium tert-butoxide; the alkali metal alkylides; or the alkali metal hydrides such as sodium hydride, and lithium hydride. The preferred base in the conduct of this reaction is sodium hydride.
Alternative procedures for preparing a more limited class of 2-aryl- 1, 3cyclohexanedione compounds are illustrated by the general reaction schemes set forth below in which Rr, R2, R3, Re, Re, R6, R7, Z, Z', Z" and Z"' are as described above and X is a fluorine or chlorine atom, except as noted: METHOD IV
In METHOD IV, R, is an alkyl group and Z, Z', Z" and Z"' are substituents other than the nitro group.
METHOD V
In Method V, Z' is an alkylsulfonyl or nitro group; or Z' may also be an alkyl or alkoxy group when either R or Z"' is a nitro group.
The procedure illustrated in METHOD IV involves the photosensitized decomposition of a 2-diazocycloalkane-l, 3-dione compound in an aromatic solvent, in the presence of a photosensitizer, preferably benzophenone. In this procedure an appropriately substituted 2-diazocycloalkane-1, 3-dione compound is photochemically decomposed to form the corresponding triplet carbene which, in turn, reacts with a suitable aromatic solvent to form the desired 2-arylcycloalkane 1, 3-dione compound. The photolysis reaction is carried out using ultraviolet radiation having a wavelength of greater than 290 nanometers. The ultraviolet radiation can be obtained from any conventional ultraviolet radiation source known to those skilled in the photolysis art. Examples of suitable sources for generating ultraviolet radiation are high and low pressure mercury arc lamps, germacidal lamps, and "black" lights.
Preferably the reaction illustrated in METHOD V is carried out by contacting equivalent amounts of the reactants in an appropriate solvent, in the presence of at least an equivalent of either an organic or an inorganic base. Examples of suitable reaction solvents, are dimethylformamide, dimethylsulfoxide, and hexamethylphosphoramide. Examples of bases that may be utilized in the conduct of this reaction are alkali metal carbonates or bicarbonates, such as for example, sodium bicarbonate or potassium carbonate; alkali metal hydrides, such as lithium hydride, sodium hydride or potassium hydride, or alkali metal alkoxides or hydroxides, such as sodium hydroxide, sodium methoxide or potassium tertbutoxide. The preferred base is anhydrous potassium carbonate.
The reactions of METHODS I to V are neither temperature nor pressure sensitive and may be conducted over a broad temperature and pressure range to yield the desired product. In general, these reactions can be conducted at a temperature of from -300C to 2000C. For convenience these reactions are conducted at autogeneous or atmospheric pressure.
The alkali metal and ammonium salts of the compounds of this invention can be conveniently prepared in accordance with conventional methods. For example, the alkali metal and ammonium salts can be prepared by treating the corresponding 2-aryl-l, 3-cyclohexanedione compound with an alkali metal alkoxide, or ammonia, or an amine respectively.
The 6-aryl-5-ketopolyalkylhexanoic acid compounds utilized as reactants in the reaction illustrated in METHOD II can be conveniently prepared by reacting an appropriately polysubstituted benzyl cyanide compound with a suitable polyalkyl glutaric acid derivative in the presence of base to form the corresponding 6-aryl-6-cyano-5-ketopolyalkylhexanoic acid ester compound which, in turn, is hydrolyzed under acidic conditions to the desired reactant.
The 6-aryl-5-ketopolyalkylhexanoic acid ester compounds utilized as reactants in the reaction illustrated in METHOD III can be conveniently prepared by esterifying the 6-aryl-5-ketopolyalkylhexanoic acid reactant of METHOD II via conventional esterification techniques.
The 2-diazo-l, 3-cyclohexanedione compounds utilized as reactants in the reaction of Method IV can be prepared by treating an appropriately substituted cyclohexanedione-l, 3-dione compound with a sulfonyl azide in the presence of an acid acceptor, such as for example, a trialkylamine, as described in more detail in H. Stetter and K. Kiehr, Chem. Ber., 98 1181 (1965), M. Regitz and P. Stodler, Liebigs Ann. Chem., 687, 214 (1967) and references cited therein. The cyclohexane1, 3-dione compound, in turn, can be prepared by conventional methods, as for example by condensing an appropriately substituted a,-unsaturated ketone with diethyl malonate in the presence of a base catalyst as described in more detail in K.
W. Rosenmund, H. Herzberg and H. Scutt, Chem. Ber., 87, 1258 (1954), C. K.
Shuang and Y. L. Tien, Chem. Ber., 69, 27 (1936) and references cited therein.
The substituted aryl, cyclohexanedione, acid halide, acid and anhydride compounds employed as reactants in the reactions illustrated in METHOD I and V are shown classes of compounds that can be either obtained from commercial sources or prepared in accordance with conventional methods known to those skilled in the synthetic arts.
The following specific Examples are presented more particularly to illustrate the process of this invention and its use in preparing the compounds of this invention.
EXAMPLE I.
Preparation of 2-(2 '-Chloro4 '-nitrophenyl)-5 .5-dimethyl-l 3-cyclohexanedione A solution containing 42.05 g (0.300 mol) of 5,5-dimethyl-l,3- cyclohexanedione and 100 g (0.718 g-atom) of anhydrous potassium carbonate in 300 ml of dry dimethylformamide was heated to 75"C. under nitrogen and stirred for one hour. The 3,4-dichloronitrobenzene, 57.60 g (0.300 mol) was dissolved in 100 ml dimethylformamide and added dropwise to the reaction mixture while stirring and maintaining the temperature of the reaction mixture at 75.or. A deep red-colored solution formed, and when the addition was complete the reaction temperature was raised to 1000C and held at this temperature for 3 hours. Most of the dimethylformamide was removed by vacuum distillation. The residue was poured into 2 1 of ice water and extracted three times with 500 ml of benzene.
Nitrogen was then passed through the aqueous solution while warming to remove dissolved benzene. The aqueous solution was cooled in an ice bath and acidified to give a tacky precipitate, which, upon warming solidified and was collected by suction filtration. The product was recrystallized from acetone to give 31.7 g (36%) of 2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl- 1, 3-cyclohexanedione as a white powder, m.p. 250253 C.
Calculated for C,4H14CINO4. 1/2HzO: C, 55.18; H, 4.96;N, 4.60 Found: C, 55.53; H, 4.73; N, 5.09 EXAMPLE II.
Preparation of 2-(2'-Chloro-4'-aminophenyl)-5.5-dimethyl-1, 3-cyclohexanedione A solution of 20.0 g (0.067 mol) of 2-(2'-chloro-4'-nitrophenyl)-5,5-dimethyl1,3-cyclohexanedione in 150 ml of concentrated ammonium hydroxide and 150 ml of ethanol was stirred at room temperature while passing hydrogen sulfide gas through the solution at such a rate that all of the H2S was absorbed. When the solution was saturated with H2S, the temperature was raised to the reflux point and H2S continuously passed slowly through the refluxing solution for 24 hours. The reaction mixture was filtered to remove sulfur, and the filtrate evaporated under reduced pressure. To the residue was added 300 ml of 0.25N NaOH, and the solution filtered once more. The filtrate was cooled and carefully acidified to pH=4 with 6N HCI. 2-(2'-Chloro-4'-aminophenyl)-5,5-dimethyl-l, 3-cyclohexanedione was collected by suction filtration.
Yield: 13.3 g (74%), m.p. 218--219"C.
Calculated for: C14H16ClNO2.H2O: C, 61.20; H, 6.24; N, 5.10 Found: C, 60.44; H, 5.83; N, 5.32 EXAMPLE III.
Preparation of 2-(2 '-Chlorophenyl)-5,5-dimethyl-1, 3-cyclohexanedione 2 - (2' - Chloro - 4,' - aminophenyl) - 5,5 - dimethyl - 1, 3 - cyclohexanedione (9.66 g. 0.0364 mol) was added to 7.0 ml of water, and the mixture stirred and heated almost to boiling. An additional 15.0 ml of HCl was added and the mixture cooled to 0 -5 C. A solution of 3.22 g (0.0467 mol) of sodium nitrite in 9.0 ml of water was added dropwise while the reaction mixture was stirred and maintained at 0 -5 C. When the addition of the sodium nitrite solution was complete, the reaction mixture was stirred at 0 -5 C. for one hour.
The diazonium salt solution prepared above was added in portions to 161 ml of 50% hypophosphorous acid at 0 C., with stirring and cooling. The reaction mixture was stirred for 12 hours and filtered to give 8.55 g of a tan solid. This material was chromatographed through 250 g of silica gel (0.063-0.2 mm) eluting a gradient from pure benzene to 70:30 benzene-ethyl acetate. A total of 7.12 g of reaction product was obtained from the chromatography and recrystallized from benzeneethyl acetate to give 6.85 g (75%) of 2-(2'-Chlorophenyl)-5,5-dimethyl-1, 3cyclohexanedione as white crystals, m.p. 191--1920C.
Calculated for C,4H,5C102: C, 67.07; H, 6.03 Found: C, 67.04; H, 6.00.
EXAMPLE IV.
Preparation of 2-(2 ',4 '-Dichlorophenyl)-5,5-dimethyl-1, 3-cyclohexanedione A fresh sample of cuprous chloride was prepared by slowly adding a solution of 2.09 g of sodium bisulfite and 1.38 g of NaOH in 20 ml of water to a solution of 9.86 g CuSO4 . 5H2O and 2.75 g NaC in 100 ml of hot water. The suspension of CuCI was cooled to room temperature, and washed several times with water while exercising care to avoid exposure of the cuprous chloride to air.
A suspension of 5.00 g (0.0188 mol) of 2-(2'-chloro-4'-aminophenyl)-5,5 dimethyl-1,3-cyclohexanedione in 75 ml of water containing 4.0 ml of concentrated HCI was stirred and heated almost to boiling for 10 min., then cooled to 100C and an additional 7 ml of conc. HCI added and the solution cooled to 0--50C A solution of 2.00 g (0.0282 mol) of sodium nitrite in 6.0 ml of water was added dropwise to the amine hydrochloride solution while maintaining the temperature at 0--5"C. When all the NaNO2 solution had been added, the diazonium salt solution was stirred for 30 min. at OOC.
The diazonium salt solution was added, in small portions to a solution of the cuprous chloride in 40 ml of conc. HCI at OOC. When all of the diazonium salt solution had been added, the reaction mixture was stirred overnight at room temperature and filtered to give 6.22 g of a tan solid, m.p. 175-178 C. This crude product was chromatographed through silica gel (0.063-0.2 mm) using a benzenethyl acetate gradient from pure benzene to 70:30 benzene-ethyl acetate to give 3.51 g (65%) of 2-(2',4'-Dichlorophenyl-5,5'-dimethyl-1,3-cyclohexanedione as a white, crystalline solid, m.p. 208.5-210 C.
Calculated for: C,4H,4C1202: C, 58.97; H, 4.95 Found: C, 59.06; H, 4.82 EXAMPLE V.
Preparation of 2-(2 ',6 '-Dichloro-4 '-nitrophenyl)-5,5-dimethyl-1 ,3-cyclohexanedione A solution of 30.98 g (0.221 mol) of 5,5-dimethyl-1,3-cyclohexanedione and 76.36 g (0.553 mol) of anhydrous potassium carbonate in 300 ml of dimethylformamide was heated to 750C. with stirring under N2 for one hour. The 3,4,5-trichloronitrobenzene (50.0 g, 0.2212 mol) was dissolved in 100 ml of dimethylformamide and added to the reaction mixture, while stirring and maintaining the temperature at 750C. A deep red-colored solution was formed, and when the addition was complete the temperature was raised to 1000 C. and the mixture stirred over night at this temperature. Most of the dimethylformamide was removed by vacuum distillation, and 2 1 of water was added to the residue. The aqueous solution was extracted three times with 500 ml portions of benzene, then N2 was passed through the aqueous solution while warming to remove dissolved benzene. The solution was cooled in an ice bath and acidified with 6N HC1 to give 63.8 g (87%) of 2-(2',6 '-dichloro4'-nitrophenyl)-5,5-dimethyl- 1 ,3-cyclohexanedione as a tan powder, m.p. 288--290"C.
Calculated for C,4H,3CL2NO4: C, 50.93; H, 3.97; N, 4.24 Found: C, 50.09; H, 3.79; N, 4.26 EXAMPLE VI.
Preparation of z-(2',6'-Dichloro-4 '-aminophenyl)-5,5-dimethyl-l .3-cyclohexanedione A solution of 20.0 g (0.0606 mol) of 2-(2',6'-dichloro-4'-nitrophenyl)-5,5dimethyl-l,3-cyclohexanedione in 150 ml conc. NHOH and 150 ml of ethanol was stirred at room temperature while passing H2S gas through the solution at such a rate that all of the H2S was absorbed. After the solution was saturated with H2S, it was refluxed 24 hours while continuously passing H2S slowly through the solution.
The reaction mixture was cooled to room temperature, the precipitated sulfur removed by filtration, and the filtrate evaporated to dryness under reduced pressure. To the residue was added 300 ml of 0.25N NaOH, and the solution filtered once more. The filtrate was cooled and acidified to pH=4 with 6N HCI. A tan solid formed which was collected by filtration to give 11.2 g when dry. This material was washed with methylene chloride to give 8.2 g (45%) of 2-(2',6'-dichloro-4'aminophenyl)-5,5-dimethyl 1 3-cyclohexanedione as a white powder, m.p. 2430d.
Calculated for C,4H15C,2NO2: C, 56.02; H, 5.04; N, 4.67 Found: C, 56.34; H, 4.95; N, 4.67.
EXAMPLE VII.
Preparation of 2-(2 '.6 '-D ichlorophenyl)-5,5-dimethyl-1 .3-cyclohexanedione The 2 - (2',6' - dichloro - 4' - aminophenyl) - 5,5 - dimethyl - 1,3 cyclohexanedione (5.00 g, 0.0167 mol) was added to 3.5 ml of concentrated HCI in 75 ml of water, and the mixture stirred and heated almost to boiling. The suspension was cooled to 100C and an additional 7.5 ml of conc. HCI was added.
The mixture was cooled to 0--50C. and a solution of 1.44 g (0.0209 mol) of sodium nitrite in 3.5 ml. of water was added dropwise while the reaction mixture was stirred and maintained at 0--50C. When addition of the sodium nitrite solution was complete, the reaction mixture was stirred at 0 C for one hour.
The diazonium salt solution prepared above was added in portions to 75 ml of 50% hypophosphorous acid at 0 C with stirring and cooling. The reaction mixture was stirred for 2 hours and filtered to give 5.03 g of brown powder. This material was recrystallized from benzene-chloroform to give 2.69 g of a light tan solid m.p.
227--229"C. The residue from the mother liquor (1.70 g) was chromatographed through silica gel (0.063--0.2 mm) to give 0.84 g of a white solid, m.p. 228--232"C.
Total yield of 2-(2',6'-Dichlorophenyl)-5,5-dimethyl-1,3-cyclohexane-1,3-dione was 3.53 g (74%).
Calculated for: C,4H'4C1202: C, 58.97; H, 4.95 Found: C, 58.64; H, 4.86 EXAMPLE VIII.
Preparation of 2-(2',4',6'-Trimethylphenyl)-cyclohexane-1,3-dione A solution of 5.00 g (0.036 mol) of 2-diazocyclohexane-1,3-dione in 500 ml of mesitylene (dry, distilled) containing 32.8 g (0.18 mol) benzophenone was degassed with nitrogen for one hour and irradiated with a 200 watt mercury arc lamp fitted with a borosilicate glass filter until the complete disappearance of the diazo band (4.68 u) in the infrared was observed. The reaction was also monitored by thin layer chromatography (90:10 ethyl acetate-benzene) and irradiation continued until no diazoketone at R,=0.31 could be seen. The irradiation required 11 hours. The mesitylene was extracted with 0.25N sodium hydroxide until a small aliquot showed no cloudiness upon acidification. The combined base extracts were washed twice with 200 ml portions of ether, and acidified (pH 3-5) with 1N HCI. The aqueous solution was extracted three times with 75 ml portions of chloroform, dried over anhydrous MgSO4, and the solvent stripped to give 5.06 g of a tan solid.
This solid was chromatographed through 250 g silica gel (0.063-0.2 mm) eluting with a gradient from pure benzene to 80:20 benzene-ethyl acetate. A total of 2.60 g (31 4) of a white solid (homogeneous by thin layer chromatography) was obtained and recrystallized from diisopropyl ether to give 1.96 g of 2-(2',4',6' Trimethylphenyl)-cyclohexane-l ,3-dione as white crystals, mp 196-198 C.
Calculated for: C15H18O2: C, 78.23; H, 7.88 Found: C, 77.94; H, 8.20 EXAMPLES IX AND X.
Preparation of 2-(2'-4'-Dimethylphenyl)-5,5-dimethylcyclohexane-1,3-dione and 2-(2',6' dimethylphenyl)-5 ,5-diinethylcyclohexane-1 .3-dione A solution of 5.00 g (0.0301 mol.) of 2-diazo-5,5-dimethylcyclohexane-l ,3dione in 500 ml of m-xylene containing 27.4 g (0.15 mol) of benzophenone was degassed with nitrogen for one hour and irradiated overnight with a 200 watt mercury arc lamp fitted with a borosilicate glass filter. The photolysis mixture was extracted with 0.25N NaOH, the combined base extracts washed with ether and acidified with chloroform, dried over anhydrous MgSO4 and the solvent removed to leave 3.61 g of a tan solid. Irradiation was repeated using 7.00 g (0.042 mol) of 2 diazo-5,5-dimethylcyclohexane-l ,3-dlone and 38.38 g (0.21 mol) of benzophenone in 500 ml of m-xylene. Workup gave 5.48 g of tan solid.
The combined crude products (9.09 g) were chromatographed through silica gel (0.063-0.2 mm) using benzene-ethyl acetate as eluent. The column was eluted with (1) 500 ml benzen (2) 500 ml of 95.5 benzene-ethyl acetate (3) 1000 ml of 90:10 benzene-ethyl acetate and (4) 1000 ml of 80:20 benzene-ethyl acetate. After collecting 2 liters of solvent, the column was attached to an automatic fraction collector and 15 ml fractions collected. Tubes 1--94 contained small amounts of a yellow oil. Tubes 95-150 contained a light yellow solid which showed one component (Rf 0.55 in 50:50 hexane-ethyl acetate) by thin layer chromatography and weighed 2.18 g. This material was recrystallized from benzene to give 1.17 g of 2.(2',4'-Dimethylphenyl)-5,5-dimethyl 1 ,3-cyclohexanedione as a white powder, mp 167--169"C.
Calculated for: C16H20O2: C, 78.65; H, 8.25 Found: C, 78.68; H, 8.12 This compound was shown to be 2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3- cyclohexanedione.
Tubes 15 1-230 were combined to give 2.0 g of white solid showing one component (Rf 0.57 in 50:50 hexane-ethyl acetate by thin layer chromatography.
This material was recrystallized from benzene to give 1.90 g of 2-(2',6' Dimethylphenyl)-5,5-dimethyl-l ,3-cyclohexanedione as white crystals, mp 177-186 C.
Calculated for: C,8H2002: C, 78.65; H, 8.25 Found: C, 78.28; H, 8.21 This compound was shown to be 2-(2',6'-Dimethylphenyl)-5,5-dimethyl-l,3 cyclohexanedione.
EXAMPLE XI.
Preparation of 2-Diazo-5-phenylcyclohexane-1,3-dione A solution of 20.0 g (0.106 mol) of 5-phenylcyclohexane-1,3-dione in 75 ml ethanol was cooled to -10"C and stirred magnetically under nitrogen. To the mixture was added 10.75 g (0.106 mol) of triethylamine. The tosyl azide (20.95 g 0.106 mol) was added all at once, and the mixture stirred for one hour at 0--50C.
The solvent was removed under vacuum at a temperature less than 40"C. To the residue was added 200 ml ether, and the mixture extracted with a solution containing 3.1 g potassium hydroxide in 200 ml of water. The ethereal solution was dried over anhydrous MgSO4 filtered and the solvent removed to give a yellow solid which was recrystallized from ethanol-hexane to give 8.38 g (32%) of 2-diazo-5 phenylcyclohexane-l,3-dione as yellow crystals, mp 122--124"C.
EXAMPLE XII.
Preparation of 2-(2',4',6'-Trimethylphenyl)-5-phenylcyclohexane-1,3-dione A solution of 7.0 g (0.0327 mol) of 2-diazo-5-phenylcyclohexane-1,3-dione and 29.77 g (0.163 mol) of benzophenone in 500 ml of mesitylene was degassed for one hour with nitrogen and irradiated with a 200 watt mercury arc lamp fitted with a borosilicate glass filter overnight. The photolysis mixture was extracted with 0.25N sodium hydroxide, the combined base extracts washed with ether, acidified with 1N HCI, and extracted with chloroform. The chloroform solution was dried over anhydrous MgSO4, and the solvent stripped to give 5.7 g of tan solid. This material was purified by column chromatography on silica gel (0.063--0.2 mm) using benzene-ethyl acetate to give 5.7 g (57%) of a white solid. This was recrystallized from benzene-ethyl acetate to give 4.08 g (41%) of 2-(2',4',6'-Trimethylphenyl)-5- phenylcyclohexane-l,3-dione as a white crystalline solid, mp. 215--216"C.
Calculated for' C21H22O2: C, 82.32; H, 7.24 Found: C, 82.38; H, 7.14 EXAMPLE XIII.
Preparation of 22 '.6 '-D imethyl4 '-t-butylphenyl)-5.5-dimethvl-l ,3-cyclohexanedione A solution of 7.00 g (0.042 mol) of 2-diazo-5,5-dimethylcyclohexane-l ,3-dione in 300 ml of 5-t-butyl-m-xylene and 250 ml chlorobenzene containing 38.38 g (0.21 mol) of benzophenone was irradiated overnight with a 200 watt mercury arc lamp fitted with a borosilicate glass filter after degassing for 1 hour under nitrogen. The photolysis mixture was extracted with 0.25N NaOH, washed with ether, acidified with IN HCI, and extracted with chloroform. The chloroform was dried over anhydrous MgSO4 and stripped to give a crude yellow solid. The photolysis was repeated and the combined crude product from these reactions was chromatographed through silica gel (0.063-0.2 mm) using benzene-ethyl acetate.
The solid obtained from the chromatography was recrystallized from benzene to give 2.76 g (11%) of 2-(2',6'-dimethyl-4'-tbutylphenyl)-5,5-dimethyl-l,3 cyclohexanedione as white crystals, mp 244h9 C.
Calculated for: C20H28O2: C, 79.95; H, 9.39 Found: C, 79.76; H, 9.45 EXAMPLE XIV.
Preparation of 2-Diazodecalin-l ,3-dione A solution of 10.0 g (0.0768 mol) of decalin-1,3-dione in 50 ml of ethanol was magnetically stirred under nitrogen and cooled to -10"C. To the solution was added 7.77 g (0.0768 mol) of triethylamine followed by 15.14 g (0.0768 mol) of ptoluenesulfonylazide added all at once. The mixture was stirred for one hour at 0 C, and the solvent removed at reduced pressure at a temperature of less than 40"C. To the residue was added 200 ml of ether, and the ether removed to yield a yellow solid. This was recrystallized from ethanol to give 5.23 g of yellow crystals, mp 81--830C.
EXAMPLE XV.
Preparation of 2-(2'-Methylphenyl)-decalin-1,3-dione A solution of 7.0 g (0.0364 mol) of 2-diazodecalin-1,3-dione and 33.18 g (0.182 mol) of benzophenone in 500 ml of toluene was degassed for one hour with nitrogen and irradiated with a 200 watt mercury arc lamp fitted with a borosilicate glass filter overnight. The photolysis mixture was extracted with 0.25N NaOH, the combined base extracts washed with ether, acidified with 1M HCl and extracted with chloroform. The chloroform extracts were dried over anhydrous MgSO4, and the solvent removed to give 4.56 g of a yellow crude product. This was purified by column chromatography through silica gel (0.063-.2 mm) with benzene-ethyl acetate. The solid obtained was recrystallized from benzene to give 1.85 g (20?o) of 2-(2'-Methylphenyl)-decalin-1,3-dione as white crystals, mp 165-1670C.
Calculated for: C17H20O2: C, 79.65: H, 7.86 Found: C, 79.82; H, 7.43 EXAMPLE XVI.
Preparation of Ethyl 6-62',4'-Dimethylphenyl)-6-cyano-5-keto-3,3-dimethurlhexanoate A clean, dry 500 ml 3-neck flask was equipped with a reflux condenser, mechanical stirrer, addition funnel and nitrogen inlet. The flask was charged with 70 ml of absolute ethanol followed by 6.00 g (0.26 g-atom) of sodium, and the reaction mixture stirred and heated until all the sodium had dissolved. The temperature of the reaction mixture was then raised to the reflux point, and a mixture of 29.04 g (0.20 mol) of 2,4-dimethylbenzyl cyanide and 64.88 g (0.30 mol) of diethyl 3,3-dimethyl glutarate added, dropwise, over a 2 hour period through the addition funnel. When the addition was complete, the reaction mixture was maintained at reflux for 12 hrs. At the end of this time, approximately 2/3 of the ethanol was distilled off, and the reaction mixture refluxed for 2 hrs. more, then cooled to room temperature and poured into 600 ml of an ice water mixture.
The basic aqueous solution was extracted twice with 300 ml of ether, and then acidified (pH=3) with 6N HCI. An oil formed, and the aqueous acid solution was extracted twice with 250 ml portions of ether. The ether phase from the extraction of the aqueous acid was washed twice with water, dried over anhydrous MgSO4, and stripped to leave 52.83 g (84%) of ethyl 6-(2',4'-Dimethylphenyl)-6-cyano-5keto-3,3-dimethylhexanoate as a clear, colorless, very viscous oil. This oil was not purified, but was characterized by infrared and nuclear magnetic resonance spectrometry.
IR (neat, , principal absorptions): 2.8-3.2 (OH, enol); 4.55 (C#N); 5.85, 6.02, 6.19 (C=O); 6.3 (C=C); 7.45, 8.25, 9.85, 12.25.
NMR (CDCl3, #): 1.20 (multiplet, 9H); 2.33 (multiplet, 8H; 2.68 (multiplet, 2H); 4.17 (quartet, 2H); 4.90 and 12.0 (singlet, 1H); 7.05 (multiplet, 3H).
EXAMPLE XVIII.
Preparation of 2-(2',4'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione and 6-(2',4' Dimethylphenyl)-5-keto-3,3-dimethylhexanoic acid A one-neck round bottom flask was charged with 52.50 g (0.17 mol) of ethyl 6 (2',4'-dimethylphenyl)-6-cyano-3,3-dimethylhexanoate, 250 ml of concentrated hydrochloric acid, 250 ml of glacial acetic acid, and 100 ml of water. The reaction mixture was stirred and refluxed for 48 hours. After 12 hours and 24 hrs. of refluxing, an additional 100 ml of conc. HCI and 100 ml glacial HOAC were added.
After 48 hours, the mixture was stripped to dryness under reduced pressure. To the residue were added 150 ml of water and 150 ml of ethyl ether, and the mixture shaken vigorously. A white, crystalline precipitate formed, and this was removed by suction filtration to give 13.20 g (32%) of 2-(2',4'-Dimethylphenyl)-5,5-dimethyl1,3-cyclohexanedione as a white, crystalline solid, m.p. 167-168.5!C.
Calcd. for C16H20O2: C, 78.65; H, 8.25 Found: C, 78.68: H, 8.12 The ether layer was separated from the filtrate, washed once with water, dried over anhydrous MgSO4 and stripped to give 29.04 g (65%) of 6-(2',4'dimethylphenyl)-5-keto-3,3-dimethylhexanoic acid as a viscous yellow oil. This oil was not purified, but was characterized by infrared and nuclear magnetic resonance spectrometry.
IR (CHCl3, , (principal absorptions): 2.9--4.3 (OH); 5.90 (C=O) NMR (CDCl3, d): 1.10, singlet, 6H); 2.20 (singlet, 3H); 2.30 (singlet, 3H); 2.50 (singlet, 2H); 2.62 (singlet, 2H); 3.70 (singlet, 2H); 7.08 (singlet, broad, 3H).
EXAMPLE XVIII.
Preparation of 2-(2'-Chlorophenyl)-1,3-cyclohexanedione A 500 ml round bottom flask charged with 10.0 g (0.0416 mol) of 6-(2'chlorophenyl)-5-ketohexanoic acid and 100 ml of 72% sulfuric acid. The reaction mixture was stirred and heated to 120 C. for 5 hours (oil bath), then poured into 600 ml of an ice water mixture. A tacky, white solid formed, and this was extracted into 300 ml of methylene chloride. The CH2CI2 solution was washed six times with water, dried over anhydrous MgSO4 and stripped to leave 8.87 g of a tacky, white solid. This material was recrystallized from ethyl acetate to give 5.85 g (63%) of 2 (2'-chlorophenyl)-1,3-cyclohexanedione as a white, crystalline solid, m.p.
148.5 -149 C.
Calculated for: Cr2H,'C102: C, 64.73; H,4.98 Found: C, 64.49; H, 4.89 EXAMPLE XIX.
Preparation of 6-(2',4'-Dimethylphenyl)5-ketohexanoic acid Utilizing the procedure of EXAMPLE XVII ethyl 6-(2',4'-dimethylphenyl)-6cyano-5-ketohexanoate was hydrolyzed in the presence of concentrated hydrochloric acid to prepare 6-(2',4'-dimethylphenyl)-5-ketohexanoic acid in 49% yield as a tan solid, m.p. 75.0-76.5 C. This solid was characterized by infrared and nuclear magnetic resonance spectrometry.
IR (CHCI3"u, principal absorptions): 2.9-4.2 (OH); 5.92 (C=O) NMR (CDCl3, 6): 1.7-3.3 (multiplet, 6H); 2.48 (singlet 3H); 3.71 (singlet, 2H); 7.31 (singlet, broad, 3H) EXAMPLE XX.
Preparation of Ethyl 6-(2 ',4 imethylphenyl)-5-ketohexanoate A 500 ml one-neck round bottom flask equipped with a Soxhlet extraction apparatus containing 100 g of molecular sieves having a pore size of 3A was charged with 12.74 g (0.0544 mol) of 6-(2',4'-dimethylphenyl)-5-ketohexanoic acid, 125 ml of absolute ethanol, 125 ml of dry benzene, and 2.0 ml of concentrated sulfuric acid. The mixture was refluxed for 12 hours, then 2/3 of the ethanolbenzene removed under reduced pressure. The residue was poured into 500 ml of ice water, and extracted into 300 ml of ether. The ether was washed three times with 10% K2CO3, then once with water, dried over anhydrous MgSO4, and removed to leave 13.34 g of a dark yellow oil. This was distilled to give 12.77 g (89%) of ethyl 6-(2',4'-Dimethylphenyl)-5-ketohexanoate as a clear, colorless oil, b.p.
133-145 C. (0.05 mm). This oil was further characterized by infrared and nuclear magnetic resonance spectrometry.
IR (neat, , principal absorptions): 5.85 (C=O), 8.60 (C=O) NMR (CDCl3, 8): 1.15 (triplet, 3H); 1.50--2.6 (multiplet, 6H); 2.10 (singlet, 3H); 2.20 (singlet, 3H; 3.52 (singlet, 2H); 3.95 (quartet, 2H); 6.80 (singlet, broad, 3H).
EXAMPLE XXI.
Preparation of 2-(2 '.4 '-Dimethylphenyl)-l ,3-cyclohexanedione A 500 ml 3-neck round bottom flask was equipped with a mechanical stirred addition funnel, and reflux condenser. The glassware was dried thoroughly and the flask charged with 4.62 g (0.096 g-atoms) of 50% sodium hydride in mineral oil. The oil was washed off the NaH using toluene, and then 100 ml of toluene added. The mixture was warmed to 65 C. and 12.62 g (0.0481 mol) of ethyl 6-(2',4' dimethylphenyl)-5-ketohexanoate added, dropwise, over a 2 hr. period. The mixture was maintained at 650C. for 12 hours., then carefully quenched with 25 ml of ice water. The reaction mixture was diluted with 250 ml of water and extracted twice with 150 ml of ether. The aqueous base solution was acidified to pH=3 with 6N HCI, and extracted twice with 150 ml of methylene chloride. The methylene chloride was washed with water, dried over anhydrous MgSO4, and stripped to give 5.88 g of a semi-solid. This was recrystallized from ethyl acetate to give 5.10 g (49%) of 2-(2',4'-Dimethylphenyl)-1,3-cyclohexanedione as a white, crystalline solid, m.p.
143--145"C.
Calculated for: C,4H,602: C, 77.75; H, 7.46 Found: C, 76.99; 11, 7A6 EXAMPLE XXII.
Preparation of Ethyl 6-(2',5'-Dimethylphenyl-6-cyano-5-keto-3,3-dimethylhexanoate Utilizing the procedure of EXAMPLE XVI, 29.04 g (0.200 mol) of 2,5dimethylbenzyl cyanide and 64.88 g (0.300 mol) of diethyl 3,3-dimethyl glutarate were reacted to yield 45.24 g (72%) of ethyl 6-(2',5'-dimethylphenyl)-6-cyano-5keto-3,3-dimethylhexanoate as a clear, colorless viscous oil. Structure was confirmed by infrared and nuclear magnetic resonance spectrometry.
IT (neat, , principal absorptions): 2.9-3.7 (OH, emol); 4.55 (C=N); 5.80, 5.98, 6.10 (C=O); 6.23 (C=C); 7.35; 7.60; 8.15; 9.70; 12.30.
NMR (CDCl3, 8): 1.18 (multiplet, 9H); 1.67-2.73 (multiplet, 10H); 4.12 (quartet, 2H); 4.88 (singlet 1H); 7.05 (broad, singlet, 3H).
EXAMPLE XXIII.
Preparation of 6-(2 '.5 '-Dimethylphenyl)-5-keto-3.3-dimethyl-hexanoic acid and 2-(2',5 '- D imethylphenyll-5,5-dimethyl-l ,3-cyclohexanedione A solution of 45.24 g (0.14 mol) of ethyl 6-(2',5'-Dimethylphenyl)-6-cyano-5keto-3,3-dimethylhexanoate, 250 ml of glacial acetic acid. 250 ml of concentrated HCI, and 70 ml of water was refluxed for 48 hours. After 24 hours, an additional 100 ml of concentrated HCI and 150 ml of glacial acetic acid were added.
After 48 hours of refluxing, the reaction mixture was cooled to room temperature and the solvent removed under reduced pressure. The residue was shaken vigorously with 250 ml of water and 250 ml of diisopropyl ether. A white, crystalline precipitate formed which was removed by suction filtration to give 7.90 g (23% yield) of 2-(2',5'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione m.p.
168-170 C.
Calculated for C,6H2002: C, 78.65; H, 8.25 Found: C, 78.16; H, 8.03 The ether layer was separated from the filtrate, washed once with water, dried over anhydrous MgSO4, and stripped to give 17.97 g of 6-(2',5'-Dimethylphenyl)-5keto-3,3-dimethylhexanoic acid as a yellow oil. This oil was not purified, but was characterized by infrared and nuclear magnetic resonance spectrometry.
IR (neat, principal absorptions): 2.9-3.8 (OH); 5.90 (C=O); 12.3 (aromatic) NMR (CDCl3, y): 1.08 (singlet, 6H); 2.03 (singlet, 2H); 2.13 (singlet, 2H): 2.27 (singlet, 3H); 2.33 (singlet, 3H); 7.0 (singlet, 3H) EXAMPLE XXIV.
Preparation of Ethyl 6-02',5'-dimethylphenyl)-5-keto-3,3-dimethylhexanoate Utilizing the procedure of EXAMPLE XX 6-(2',5'-dimethylphenyl)-5-keto- 3,3-dimethyl hexanoic acid was esterified with absolute ethanol in the presence of a catalytic amount of concentrated sulfuric acid to provide 15.52 g (78% yield) of ethyl 6-(2',5'-dimethylphenyl)-5-keto-3,3-dimethylhexanoate as a pale viscous oil.
EXAMPLE XXV.
Preparation of 2-(2 '.5 '-Dimethylphenyl)-5.5-dimethyl-1 .3-cyciohexanedione Utilizing the procedure of EXAMPLE XXI, 6-(2',5'-dimethylphenyl-5-keto3,3-dimethylhexanoate was treated with sodium hydride to yield 9.87 of crude product, which on recrystallization yielded 8.77 g (64%) of 2-(2',5' dimethylphenyl)-5,5-dimethyl- 1 3-cyclohexanedione as a white, crystalline solid m.p. 167--1680C.
EXAMPLE XXVI.
Preparation of 3-(2-Ethylhexanoyloxy)-2-(2 '-chlorophenyl)-5.5-dimethyl-2- cyclohexenone A solution of 1.009 (3.99 mmol) of 2-(2'-chlorophenyl)-5,5-dimethyl-1,3- cyclohexanedione and 0.03 g (8.0 mmol) of pyridine was cooled in an ice bath and stirred under N . The 2-ethylhexanoyl chloride (0.69 g, 4.25 mmol) was added, the mixture was then allowed to warm to room temperature, stirred at room temperature for one hour and refluxed for one hour. The solvent was removed under reduced pressure and the residue taken up in ether and water. The ether was washed three times with 0.25N NaOH, three times with 10% HCI and with water.
The ether was dried over anhydrous MgSO4 and decanted to give 1.23 g (82%) of 3 (2'-ethylhexanoyloxy)-2-(2'-chlorophenyl)-5,5-dimethyl-2-cycohexenon e as a clear colorless oil which was homogeneous by thin layer chromatography.
Calculated for C22H29CIO3: C, 70.10; H, 7.76 Found: C, 70.09; H, 7.86 EXAMPLE XXVII.
Preparation of 3-(2 '-Ethylhexanoyloxy)-2-(2 ',4 '-dichlorophenyl)-5,5-dimethyl-2 cyclohexenone A solution of 1.76 g (7.02 mmol) of 2-(2',4'-dichlorophenyl)-5,5-dimethyl-l,3- cyclohexanedione in 10 ml of chloroform was cooled in ice and 1.11 g (14.04 mmol) of pyridine added followed by 1.21 g (7.47 mmol) of 2-ethylhexanoyl chloride. The mixture was stirred for 2 hrs. at room temperature and then refluxed for 12 hrs.
The reaction mixture was worked up exactly as described for Example XXVI above to give 2.09 g of a yellow oil. This material was chromatographed using low pressure liquid chromatography on silica gel with a hexane-ethyl acetate gradient to give 1.15 g (41%) of 3-(2'-ethylhexanoyloxy)-2-(2' ,4'-dichlorophenyl)-5 ,5- dimethyl-2-cyclohexenone as a clear, colorless oil. The thin layer chromatogram (80:20 hexane-ethyl acetate) of this material showed one spot at Rf=0.46.
Calculated for C22H28C1203: C, 64.23; H,6.86 Found: C, 64.44; H, 6.80 EXAMPLE XXVIII.
Preparation of 3-hexanoyloxy-5 ,5-dimethyl-2-(2'.4 '-dimethylphenyl )-2-cyclohexenone A solution of 1.50 g (6.14 mmol) of 2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3- cyclohexanedione in 10 ml of chloroform was cooled in ice and 1.94 g (24.56 mmol) of pyridine added followed by 1.64 g (12.28 mmol) of hexanoyl chloride. The mixture was stired for 2 hrs. at room temperature, then refluxed for 5 hrs.
The reaction mixture was cooled to room temperature and taken up in 150 ml of ether. The ether was washed three times with 50 ml of 0.25N NaOH, twice with 50 ml portions of ice cold 6N HCI, and twice with water. The ether was dried over anhydrous (MgSO4) and removed under reduced pressure to leave 0.98 g (47so yield) 3-hexanoyloxy-5,5-dimethyl-2-(2',4'-dimethylphenyl)-2-cyclohexenone as a clear, colorless oil. This oil showed one spot on a thin layer chromatogram (70:30 hexane-ethyl acetate) at Rf=0.49.
Calculated for C22H3003: C, 77.1511,8.83 Found: C, 77.25; H, 8.92 EXAMPLE XXIX.
Preparation of 3-(2-Ethylhexanoyloxy)-5,5-dimethyl-2.(2 ',4 '-dimethylphenyl)-2 cyclohexenone A solution of 1.50 g (6.14 mmol) of 2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3- cyclohexanedione in 10 ml of chloroform was cooled in ice and 1.94 g (24.56 mmol) of pyridine added followed by 2.00 g (12.28 mmol) of 2-ethylhexanoyl chloride. The mixture was stirred for 2 hrs. at room temperature,then refluxed for 12 hrs. The mixture was worked up exactly as described in Example XXVI above to give 1.58 g of a slightly yellow, viscous oil. This material was chromatographed through 75 g of silica gel (0.0634.2 mm) using a gradient ranging from 98:2 to 90:10 hexane-ethyl acetate. The chromatography gave 1.15 g (51%) of 3-(2-ethylhexanoyloxy)-5,5dimethyl-2-(2',4'-dimethylphenyl)-2-cyclohexenone as a clear colorless oil which showed one spot on a thin layer chromatogram (70:30 hexane-ethyl acetate) at Rf=0.52.
Calculated for: C241134O3: C, 77.80; H, 9.25 Found: C, 77.34; H, 9.48 EXAMPLE XXX.
Preparation of 3-Hexanoyloxy-2-(2 '.4 '-dichlorophenyl)-5.5-dimethyl-2-cyclohexenone A solution of 2.00 g (8.00 mmol) of 2-(2',4'-dichlorophenyl)-5,5-dimethyl-1,3- cyclohexanedione in 10 ml of chloroform was cooled in ice and 1.26 g (16.00 mmol) of pyridine was added followed by 1.14 g (8.50 mmol) of hexanoyl chloride. The mixture was stirred for 2 hrs. at room temperature and refluxed for 12 hrs.
The reaction mixture was worked up exactly as described for Example XXVI above to give 1.94 g of a slightly yellow oil. This material was chromatographed using a low pressure liquid chromatography system and a hexane-ethyl acetate gradient. Work-up of the chromatography gave 1.55 g (51% yield) of 3 hexanoyloxy-2-(2' ,4'-dichlorophenyl)-5 ,5-dimethyl-2-cyclohexenone as a clear, colorless oil which on a thin layer chromatogram (80:20 hexane-ethyl acetate) showed one spot at Rf=0.27.
Calculated for: C20H24Cl2O3: C, 62.67; H, 6.31 Found: C, 62.83; H, 6.32 EXAMPLE XXXI.
Preparation of 3-(2-Ethylhexanoyloxy )-5.5-dimethyl-2-(2 '.5 '-dimethylphenyl)-2- cyclohexenone A suspension of 1.50 g (6.14 mmol) of 2-(2',5'-dimethylphenyl)-5,5-dimethyl- 1,3-cyclohexanedione in 15 ml of dry benzene was prepared and 0.49 g (7.37 mmol) of 85% powdered potassium hydroxide was added, followed by 1 drop of dicyclohexyl- 1 8-crown-6-ether. After stirring for 30 minutes, 1.20 g (7.37 mmol) of 2-ethylhexanoyl chloride was added, and the reaction mixture refluxed for 12 hrs.
The reaction mixture was cooled to room temperature, taken up in 150 ml ether and 50 ml of water, washed three times with 0.25N NaOH, two times with water, two times with 6N HCI, and once more with water. The ether solution was dried and stripped to leave 2.10 g (92% yield) of 3-(2-ethylhexanoyloxy)-5,5-dimethyl-2 (2',5'-dimethylphenyl)-2-cyclohexenone as a clear, colorless oil.
Calculated for: C241134O3: C, 77.80; H, 9.25 Found: C, 77.46; H, 8.98 EXAMPLE XXXII.
Preparation of 2-(2 '.4 '-Dimethylphenyl)-1 ,3-cyclohexanedione A 500 ml 3-neck round bottom flask was equipped with a mechanical stirred addition funnel, and reflux condenser. The glassware was dried thoroughly and the flask charged with 4.62 g (0.096 g-atom) of 50% sodium hydride in mineral oil. The oil was washed off the NaH using toluene, and then 100 ml of toluene added. The mixture was warmed to 65"C. and 12.62 g (0.0481 mol) ethyl 6-(2',4' dimethylphenyl)-5-ketohexanoate added, dropwise, over a 2 hr. period. The mixture was maintained at 650 C. for 12 hrs., then carefully quenched with 25 ml of ice water. The reaction mixture was diluted with 250 ml of water and extracted twice with 150 ml of ether. The aqueous base solution was acidified to pH=3 with 6N HCI, and extracted twice with 150 ml of methylene chloride. The methylene chloride was washed with water, dried over anhydrous MgSO4 and stripped to give 5.88 g of a semi-solid. This was recrystallized from ethyl acetate to give 5.10 g (49%) of 2-(2',4'-dimethylphenyl)-1,3-cyclohexanedione as a white, crystalline, solid, m.p. l43l450C.
Calculated for: Ct4H,602: C, 77.75; H, 7.46 Found: C, 76.99; H, 7.46 EXAMPLE XXXIII.
Preparation of 2-(2'-Chlorophenyl)-1,3-cyclohexanedione A 500 ml one-neck round bottom flask was charged with 10.0 g (0.0416 mol) of 6-(2'-chlorophenyl)-5-ketohexanoic acid and 100 ml of 72% sulfuric acid. The reaction mixture was stirred and heated to 1200C. for 5 1/2 hrs. (oil bath) then poured into 600 ml of ice water. A tacky, white solid formed, and this was extracted into 300 ml of methylene chloride. The CH2Cl2 solution was washed six times with water, dried over anhydrous MgSO4, and stripped to leave 8.87 g of a tacky, white solid. This material was recrystallized from ethyl acetate to give 5.85 g (63%) of 2 (2'-Chlorophenyl)-l,3-cyclohexanedione as a white, crystalline solid, m.p. l48.50-l490C.
Calculated for: C,2H,1C102: C, 64.73; H, 4.98 Found: C, 64.49; H, 4.89 EXAMPLE XXXIV.
Preparation of 2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione A solution containing 42.05 g (0.300 mol) of 5,5-dimethyl-1,3cyclohexanedione and 100 g (0.718 g-atom) of anhydrous potassium carbonate in 300 ml of dry dimethylformamide was heated to 750C under nitrogen and stirred for one hour. The 3,4-dichloronitrobenzene, 57.60 g (0.300 mol) was dissolved in 100 ml dimethylformamide and added dropwise to the reaction mixture while stirring and maintaining the temperature of the reaction mixture at 750C. A deep red-colored solution formed, and when the addition was complete the reaction temperature was raised to 100"C and held at this temperature for 3 hours. Most of the dimethylformamide was removed by vacuum distillation. The residue was poured into 2 1 of ice water and extracted three times with 500 ml of benzene.
Nitrogen was then passed through the aqueous solution while warming to remove dissolved benzene. The aqueous solution was cooled in an ice bath and acidified to give a tacky precipitate, which, upon warming solidified and was collected by suction filtration. The reaction product was recrystallized from acetone to give 31.7 g (36%) of 2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl- 1 ,3-cyclohexanedione as a white powder, m.p. 25--253"C.
Calculated for: Ct4H,4CINO4. 1/2H,O: C, 55.18; H, 4.96; N, 4.60 Found: C, 55.53; H, 4.73; N, 5.09 EXAMPLE XXXV.
Preparation of 2-(2 '-Chloro4 '-aminophenyl)-5 .5-dim ethyl-I .3-cyclohexanedione A solution of 20.0 g (0.067 mol) of 2-(2'-chloro-4'-nitrophenyl)-5,5-dimethyl- 1,3-cyclohexanedione in 150 ml of concentrated ammonium hydroxide and 150 ml of ethanol was stirred at room temperature while passing hydrogen sulfide gas through the solution at such a rate that all of the H2S was absorbed. When the solution was saturated with H2S, the temperature was raised to the reflux point and H2S continuously passed slowly through the refluxing solution for 24 hours. The reaction mixture was filtered to remove sulfur, and the filtrate evaporated under reduced pressure. To the residue was added 300 ml of 0.25N NaOH, and the solution filtered once more. The filtrate was cooled and carefully acidified to pH=4 with 6N HCI. A white solid formed which was collected by suction filtration to give 13.3 g (74%) of 2-(2'-Chloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione, m.p. 218--2190C.
Calculated for: C14H16ClNO2.H2O: C, 61.20; H, 6.24; N, 5.10 Found: C, 60.44; H, 5.83; N, 5.32 EXAMPLE XXXVI.
Preparation of 2 -(2 '-Chlorophenyl)-5 .5-dim ethyl-i 3-cyclohexanedione The 2-(2'-chloro-4'-aminophenyl)-5,5-dimethyl. 1 3-cyclohexanedione (9.66 g.
0.0364 mol) was added to 7.0 ml of concentrated HC1 in 150 ml of water, and the mixture stirred and heated almost to boiling. An additional 15.0 ml of HCI was added and the mixture cooled to 00--50C. A solution of 3.22 g (0.0467 mol) of sodium nitrite in 9.0 ml of water was added dropwise while the reaction mixture was stirred and maintained at 00 -50C. When addition of the sodium nitrite solution was complete, the reaction mixture was stirred at 00--50C. for one hour.
The diazonium salt solution prepared above was added in portions to 161ml of 50% hypophosphorous acid at OOC, with stirring and cooling. The reaction mixture was stirred for 12 hours and filtered to give 8.55 g of a tan solid. This material was chromatographed through 250 g of Woelm silica gel (0.063-0.2 mm) eluting with a gradient from pure benzene to 70:30 benzene-ethyl acetate. A total of 7.12 g of product was obtained from the chromatography and recrystallized from benzeneethyl acetate to give 6.85 g (75%) of 2-(2'-Chlorophenyl)-5,5-dimethyl-l 1,3- cyclohexanedione as white crystals, m.p. 191--192"C.
Calculated for: C,4H,5C,O2: C, 67.07; H, 6.03 Found: C, 67.04; H,6.00 EXAMPLE XXXVII.
Preparation of 2C2 '.4 '.6 '-Trimethylphenyl)-cyclohexane-1 .3-dione A solution of 5.00 g (0.036 mol) of 2-diazocyclohexane-l,3-dione in 500 ml of mesitylene (dry, distilled) containing 32.8 g (0.18 mol) benzophenone was degassed with nitrogen for one hour, and irradiated with a 200 watt Hanovia (Registered Trade Mark) immersion lamp through a borosilicate glass filter, until the complete disappearance of the diazo band (4.68 u) in the infrared was observed. The reaction was also monitored by thin layer chromatography (90:10 ethyl acetate-benzene) and irradiation continued until no diazoketone at Rf=0.31 could be seen. The irradiation required 11 hours. The mesitylene was extracted with 0.25N sodium hydroxide until a small aliquot showed no cloudiness upon acidification. The combined base extracts were washed twice with 200 ml of ether, and acidified (pH=5) with IN HCI. The aqueous solution was extracted three times with 75 ml portions of chloroform, dried over anhydrous MgSO4, and the solvent stripped to give 5.06 g of a tan solid.
This solid was chromatographed through 250 g of silica gel (0.065-1.2 mm) eluting with a gradient from pure benzene to 80:20 benzene-ethyl acetate. A total of 2.60 g (31%) of a white solid (homogeneous by thin layer chromatography) was obtained and recrystallized from diisopropyl ether to give 1.96 g of 2-(2',4',6'trimethylphenyl-1,3-cyclohexanedione as white crystals, mp 196--198"C.
Calculated for: C,5H,802: C, 78.23; H, 7.88 Found: C, 77.94; H, 8.20 Selected 2-aryl-l ,3-cyclohexanedione compounds and certain of their alkali metal salts, ammonium salts and enol ester derivatives representative of those useful in accordance with this invention were tested with respect to their miticidal, mite ovicidal and pre-emergent and post-emergent herbicidal activity.
Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxyethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 160 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. The thus prepared stock suspension contained 0.5 percent by weight of compound. The test concentrations employed in the tests described hereinbelow were obtained by diluting the stock suspension with water.
The test procedures were as follows: MITE FOLIAGE SPRAY TEST Adults and nymphal stages of the two-spotted mite (tetranychus urticae: (Koch)), reared on Tendergreen bean plants at 80 + 50F. and 50 + 5 percent relative humidity, were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a-half inch clay pot. 150--200 Mites, a sufficient number for testing, transferred from the excised leaves to the fresh plants in a period of twentyfour hours. Following the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to provide suspensions containing the desired amount of test compound per million parts of final formulation. The potted plants (one pot per compound) were placed on a revolving turntable and sprayed with 10W110 milliliters of test compound formulation by use of a DeVilbis spray gun set at 40 psi. air pressure. This application, which lasted 30 seconds, was sufficient to wet the plants to run-off. As a control, 100110 milliliters of a water solution containing acetone and emulsifier in the same concentrations as the test compound formulation, but containing no test compound, were also sprayed on infested planets. The sprayed plants were held at 80+ 5"F. and 50 + 5 percent relative humidity for four days, after which, a mortality count for motile forms was made.
Microscopic examination for motile forms was made on the leaves of the test plants. Any individual which was capable of locomotion upon prodding was considered living.
Mite Ovicide Test The test organism was the egg of the two-spotted mite (Tetranychus urticae (Koch)), as obtained from adults reared on Tendergreen bean plants under controlled conditions of 80 + 50F. and 50 + 5 percent relative humidity. Heavily infested leaves from a stock culture were placed on the primary leaves of two bean Plants six to eight inches in height, growing in a two-and-a-half inch clay pot.
Females were allowed to oviposit for a period of 48 hours and then the leaves of the invested plants were dipped in a solution containing 800 parts of tetraethyl pyrophosphate per million parts of water in order to destroy the reproductory forms and thus prevent further egg laying. This solution of tetraethyl pyrophosphate does not affect the viability of the eggs. The plants were allowed to dry thoroughly. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing varying amounts of test compound per million parts of final formulation. The potted plants (one pot per compound) were placed on a revolving turntable and sprayed with 100110 10 milliliters of test compound formulation by use of a DeVilbis spray gun set at 40 psig. air pressure. This application, which lasted 30 seconds, was sufficient to wet the plants to run-off. As a control, 10W110 milliliters of a water solution containing acetone and emulsifier in the same concentrations as the test compound formulation, but containing no test compound, were also sprayed on plants infested with eggs. The sprayed plants were held at 80 + 50F. and 50 l 5 percent relative humidity for four days, after which a microscopic examination was made of unhatched (dead) and hatched (living) eggs.
In these tests the pesticidal activity of the compounds against mites and mite eggs was rated as follows: A=Excellent Control B=Partial Control C=No Control Preliminary Herbicide Seed Germination Test The following seeds were used in this test: Perennial rye grass - Soliumperenne Crabgrass - Digitaria sanguinalis Red root pigweed - Amaranthus retroflexus Mustard - Brassicapincea var. foliosa (Florida broadleaf) Two seed-soil mixtures were prepared as follows: Mixture I 196 cc. Rye grass seed 75 cc. Mustard seed 18,000 cc. Sifted, fairly dry soil Mixture II 99 cc. Crabgrass seed 33 cc. Amaranthus 18,000 cc. Sifted, fairly dry soil Each of above mixtures was rolled separately in 5 gallon containers for approximately one-half hour on a ball mill to insure uniform mixing of seeds and soil. For each compound four 3-inch pots were filled with and 4 indicate intermediate degrees of injury based upon the number and extent to which leaves were injured.
The results of these experiments are summarized and set forth in Table I and II below. Table I contains the test results for 2-aryl- 1,3-cyclohexanedione compounds and their alkali metal salts and Table II contains the test results for 2-aryl-1,3cyclohexanedione enol ester derivatives.
TABLE I PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1, 3-CYCLOHEXANEDIONE COMPOUNDS AND THEIR ALKALI METAL SALTS
Post-Emergent Herbicidal Pre-Emergent Herbicidal Miticidal Tom- Cot- Soy- Crab- Amar- Mus R1 Z"' R5 R6 Z' Z" Y MP C. Adult Egg Bean Corn ato ton bean Rye grass anthus tard Cl H H H H H H 148.5-149 A A 2 4 1 2 2 5 5 1 2 Cl H H H Cl H H 163-165 A A 2 3 2 2 1 5 5 3 3 -CH3 H H H H H H 146-147 B C 2 4 1 2 2 5 4 2 3 -CH3 H H H -CH3 H H 143.5-145 A A 2 3 2 2 2 5 5 1 2 -CH3 H -CH3 -CH3 H H H 178-179.5 A A 1 1 1 1 1 5 5 1 2 -CH3 H -CH3 -CH3 -CH3 H H 167-168.5 A A 2 1 2 2 1 5 5 4 4 -CH3 H -CH3 -CH3 H -CH3 H 168-169 A A 2 1 2 2 1 5 5 3 3 Cl H -CH3 -CH3 -CH3 Cl H 238-240 C B 1 1 2 1 1 5 1 1 1 Cl H -CH3 CH3 H H Na+ > 250 A A 2 4 1 2 1 5 5 4 4 Cl H H H H H Na+ > 250 A B 3 4 1 2 2 5 5 3 3 -CH3 H -CH3 CH3 -CH3 H Na+ > 250 A A 2 5 1 2 2 5 5 3 5 Cl H -CH3 CH3 Cl H Na+ > 250 A A 2 4 2 2 2 5 5 5 5 TABLE I (continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1, 3-CYCLOHEXANEDIONE COMPOUNDS AND THEIR ALKALI METAL SALTS
Post-Emergent Herbicidal Pre-Emergent Herbicidal Miticidal Tom- Cot- Soy- Crab- Amar- Mus R1 Z"' R5 R6 Z' Z" Y MP C. Adult Egg Bean Corn ato ton bean Rye grass anthus tard -CF3 H -CH3 CH3 NO2 H H 235-237 C C 1 1 1 1 1 1 1 1 1 -CF3 H -CH3 CH3 H H H 209-211.5 B C 1 1 1 1 1 4 3 3 2 -CF3 H -CH3 CH3 Cl H H 209.5-211 A B 1 1 1 1 1 5 4 3 2 -CH3 H -CH3 CH3 NO2 H H 240-245 C C 1 1 1 1 1 1 1 1 2 -CH3 -NO2 -CH3 -CH3 NO2 H H 233-235 C C 1 1 1 3 2 1 1 1 1 -CH3 -NO2 -CH3 -CH3 H H H 226-229 A B 1 1 1 2 1 4 3 3 2 -CN H -CH3 -CH3 -NO2 H H 234d C C 1 1 1 1 1 1 1 1 1 Cl -NO2 -CH3 -CH3 -NO2 H H 238d C C 1 1 1 1 1 1 1 1 1 Cl H -CH3 -CH3 -NO2 H H 248-251 C C 2 2 2 2 3 1 1 1 1 Cl H -CH3 -CH3 -CH3 H H 141-142 A A 1 2 1 1 1 5 5 3 3 Cl H -CH3 -CH3 Cl H H 207-209 A A 1 1 1 1 1 5 5 3 3 Cl Cl -CH3 -CH3 -NO2 H H 288-290 C C 1 1 1 1 1 1 1 1 1 Cl Cl -CH3 -CH3 H H H 227-229 A A 1 3 2 2 1 5 5 1 3 TABLE I (continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1, 3-CYCLOHEXANEDIONE COMPOUNDS AND THEIR ALKALI METAL SALTS
alNm m mmmm c vl PI) F Ce ç S (ds u Uao b C Q X ~ a9 Post-Emergent Herbi ci dal Pre-Emergent Herbi cidal 6 0 bO E- CS N RE Z"' R5 Re Z' Z'- Y MP0 C. Adult Egg Bean Corn ato ton bean Rye grass anthus tard E -CE3 -CE3 H t > H H < A A 3 C) N a 8 m -CE2 -CE3 -CE3 -CE3 H H H 177-186 A A 1 1 2 1 2 S 5 1 2 bboo H -CE3 -CE3 H H H 118-121 C m 2 5 2 2 2 . S 1 1 o I a -CE3 -CE3 H H 196-202 v U v 5 5 3 -CE3 H -CE3 -CE3 -Cl H H 190-192 A B 1 1 1 1 1 S 4 3 3 . G O 0\ H t sD F V H Cl -CE3 -CE3 H H H 188-191 ~I > 1 5 4 3 3 a\0 I I 1 11111 11 X > F 00 O 00 m t H > H F H o Ch CO t D F -CE3 -CE3 H > 000rn-F1 > -C113 -CE3 -CE3 C(CH3)3 H H 244-249 x = 1 1 1 1 1 1 1 1 1 -CE(CH2)2 H -CE3 -CE2 H H H 161-164 C C 1 3 2 2 2 5 5 1 3 N OCH3 -CE3 CE3 H H H 172-174 A B 1 2 1 1 1 5 5 1 3 v y I : X y q = I V ~s = y V U Vl Y y y y v Y = q q q q q SC zI q q f7 rw N 9 9 V X 5 = V 5 CIJ dC o vr v 3 x, = V z V = I y I D V y y D TABLE I (continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1, 3-CYCLOHEXANEDIONE COMPOUNDS AND THEIR ALKALI METAL SALTS
(d rr Cr) 6, ZC P C D 3: " hl rl Y V: D tS E P u 9 Herbici dal Pre-Emergent Herbi cidal Ticidal Tom- 0 < c R, Z"' Ra Re Z' Z" Y MP0 C. Adult Egg Bean Corn ato ton bean Rye grass anthus tard -CE3 -OCH3 -CH3 CE3 -CE3 H H 155- A A 1 5 1 2 2 1 1 1 1 159 m ~ -CH3 -CE3 -CE3 me -OCE3 H H 155- A A V 5 1 2 2 1 1 1 1 159 111 ~ * H H H as 143- A A 1 1 1 1 2 5 5 2 3 145 -CE3 H -CE3 -CE3 -CN m m m * t eo 191 -CE3 -CN -CE3 -CE3 H H H 193- A C 2 2 2 2 1 1 1 1 1 195 N 8 W CC V = 04 VX vC O f f n f f f f N N Yl = NC 8 Y &verbar; Vl y y a) a mixture of two isomers TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
cc, QT: o ra o A? m m Pre-emergent m Mi ti cidal MP 0C Soy- Crab- Amar 0 or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 0 D S (ester 0 (H Amax (t): uU 6.05 (keto C,,',0) Amax c zo = t a X C=0); A t t ~ ~ (keto H3C C=0) o Amax (t): - 5.75 (ester Cl 6{?o6c05o A A 1 4 1 1 1 5 5 1 3 2 o x t É cS 1I É V ^ X Q Q H S 0O :D o= > 0to TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-ct 1 rc ccr 1 1 ,E Herbi cidal Pre- emergent Herbi cidal o :t t MP 0C Soy- Crab Amar I 6 > rd ~ ~ II H3C- (H2c) 16 Amax D V o O 113 C0); 6.05 (keto E N É EZ Cl Qoz 76.5-78 A A 1 5 2 v, cc, m ~ w" 91-93 A A 1 3 1 1 1 5 5 3 3 cl :E m5; Sg X V} o O O m TABLE I (Continued) PHSYSICAL PROPERTIES AND BILOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOIL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
N c (d E cl É Ú m rl Herbi cidal Pre- emergent Herbicidal X ticidal MP 0C Soy- Crab Amar | or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 0 U C > r X eS D U c E r l H3C 5.70 (ester (keto C=0) U Oii L0 S Amax (: H3C 5.70 (ester O e 6.0, 6.05 ~ ~ bO vo b O .W &verbar; H3C0C1 Y h Y V A A 2 2 2 93 1, Ct: x o Ô vD E rl cJ i o=tV Cot TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
1 N m 7 E E .~ rwl r I < a: Y E Voo s X vo > m Pre-emergent Herbicidal Mi ticidal MP 0C Soy- Crab Amar c SB N 'O O ..
* D A A 2 2 2 2 1 5 5 1 2 S o c O 8 E N N O 99.5-101 A A . 3 . 1 1 2 2 . 1 W H3C a u }i3c rwl (d 4 ;io O . ~~ . ~ . . . ~.~~ . = ~ 6.0, 6.05 h (keto CO) Wf $ TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
J m m Z = . D ' O Herbicidal Pre-emergent Herbi cidal MP 0C Soy- Crab Amar a 02 = "m Amax r -o 5.70 (ester A A 2 5 1 1 1 2 2 1 D U r es ~ - 6.0 (keto =.
9 C 2 5.68 (ester H3 CO); V Y, v, 5.95, 6.0 m es rz rZ ~ 00 -acil o W 2 H3C CO); A A 1 5 1 1 1 5 5 3 3 6.0, 6.0 H3- (keto CO) E z V V z V ur m V D ~ D r TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a c1 1 m Post-emergent J r n Ticidal b a rc, v, a c CL Amax (tL); II 5.75 (ester 0 A A 1 4 1 1 1 4 5 1 2 6.0, 6.05 == O 6 E ~ r I rl e c E . d eo < < 'Ei I' :2 = t; Cl sQ ,i9 a i F o = 8 ~ 2 o > > , > > TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
71 r t e 3 " E9 m M cdd u" b In v, In E r O m ro ur Pre-emergent Herbicidal Miticidal MP 0C Soy- Crab Amar 8 or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 0 II (d Cl 'o~ A A 2 5 2 2 3 5 5 3 4 Q s Q E Ei ev S H3CcO C\l C=0); A A 2 4 2 2 3 5 5 3 3 t . CO) ~ eo n:l Amax .
' 5.73 ~ E CO); A A 1 4 2 2 3 5 5 4 ~ ç ö C) o s ^. rn sJ ,, rn o r ) sO J O X ~ ez a: co, I Yx: m É íl 2 O xD < mUçV t:VeCJ rQ 9 r4 Ç rXJX U F tv t ~ rtl U O rn F) t ( V) S xFS n :C X TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
m (ri m 2 8 (d v) V, O &verbar; rn E V eo ur Uocr m m o ~ MP 0C Soy- Crab Amar a or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard op, N rn D > r ~ ~ w0 77-78 A A 2 3 2 2 2 C\1 D Qo oo E N (H3C)3C(1'o CL 86-87 A A 2 2 2 2 1 5 5 1 3 m Q cr, hl VI 0 m cq es l s e i H3CC 0 6.05, 6.10 H3C (keto CO) H3C V o o I &verbar; E > c5 U X X = = TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a . 8 Pre-emergent å < d MP 0C Soy- Crab Amar X or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 0 n ç N 3c D 238-240 A A 2 5 2 2 3 5 5 4 5 C\1 E N H3C 42-44 C C 1 1 1 1 1 1 1 1 1 n Ú < 8 ~ ~ ~ "9.5-81 A A V < : R3C E s V Ug N t o S g fb r,;46 4 N i Ov OW/ 0 v F ~ S ~ n C,7 Q TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 5; N C I 1 E D a MP 0C gPOStCCt Soy- Crab- Amar IE N n > D ~ ii a 3CC 0 C3 H3 H3 NO7 101.5-103 A A 1 1 1 1 1 5 5 2 2 T E ~ c rz C "Cl Amax (tt); H3CC 5.70 (ester 9 CO); V A 2 to Cd - (keto CO) ~s < N O ~ 2 CO; 6.00 A V 6.05 (keto m o E cS 0 2 E CO) Q \; Qp 4 43 u o = v o = 8 t O-a, C H xx ~ TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a G É D - r X I vl o Miticidal ~ ac ccr or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 58 0 I ii ~ a D U o :n: S 6.10 (keto - CO) L m E gLo V m Cl Amax (u); a u C=0; 6.00, 6.1 (keto d , D a 0 2 Amax Q u CO), 5.98, 6.08 V Cl (keto 3 "9 O ag, xn ,oz -~ 1I E > i X n o < oUqx :vxDu t:oVo U w4 p 4~91 r4 ~ H W *0 ag a rn TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
71 1 1 z m c Z .n 8 (d8 r, oE Herbi ..
Mi ticidal MP 0C Soy- Crab Amar a vi v, 0 ~ o CC1CH3 5.73 (ester D D 6.12 (keto CO) 0 0 CO 3 Amax (t); n E CO), 6.00 6.08 (keto = . . ~ ~ d ~ ea m v cs 106-107 C C I 1 1 1 1 1 1 1 113C ,0f Og s U rn O ç n O &commat; O D E > 3 ^ D E > 11 r4 6 G t o=rr TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-ct 1 cu 1 C V UD ro H Pre-ernergent < Miticidal MP 0C Soy- Crab Amar C mo II li3CCO cF3 S s b~ C C 2 3 2 2 2 5 S 1 2 o E F II a 93-96 A A 1 1 1 1 1 1 1 1 NO2 m > < < ~ ta u 24a V Q II 2 U CH3 ~ o L- 1. 1 Od 9 q\ 7 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
P (df3 E9 8 a M d P 2 O MP 0C Soy- Crab Amar X or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 0 D ~ es ' C H > D D c E ~ ~ ~ 0 II m cri 103-106 A A 1 1 1 1 1 1 1 1 1 o e .0 111-112 G < V II :E V l y, cu OUn F I I 2 4 ~ H ;4 t; + r t - 4 & i U =F O a 0 < TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1, 3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
1 'o" ra M O C V w < H U ao E a Mi ti ci dal MP 0C Soy- Crab Amar e 8 II =. c E 102 65-68 A A 2 1 2 1 2 1 1 1 0 II m c4 ~ s m 113C < TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
X d Z a c V r4 t vo F E X > rr Pre-emergent Herbicidal Mi ticidal MP É C\1 h N 3 II ( 3c)2scco Amax (); c 5.75 (ester A A 2 S 2 2 2 c4 c4 C=O) - 6.03, 6.12 b (keto a UO v, v, o 0 Amax ~ ~ X CO 5.70 A A 2 S 2 2 2 S S 1 z L 6 CO) fizz a ~ o stoSo ua D B TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 Xo a Herbi cidal Pre-emergent Herbicidal Mi ticidal MP 0C Soy- Crab- Amar X c S ~ ~ D U )3-CII-CO c E Amax ~ Cl 5.70 A A 2 3 1 1 2 1 1 1 E F 5.98, 6.08 Xo (keto V n O U ^1 ' Am 7 P v 34.0-34.5 A ts v elr 2 x- F r 0s O 4 Q t G o=8 bf = t on Q"1 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 I E a a In Pre-emergent Herbicidal Miticidal MP 0C Soy- Crab Amar I 6 SX N D;, E II S "max (u); 5.75 A A 1 5 1 1 2 5 3 C CO) É ss H < 't c o o trr e 24 113C-(H2C)16-CO 5.75 A A 1 3 1 1 1 5 5 a (ester CO) 6.00, 6.15 CM (keto CO) V ^ d Ho Ô a d m Q, tM X lT ~ oX w eXs rx) w Ô q s < T \ o sO 4 Jc2 d ,8AP OO cr gg 2rt e TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 Y ~ ct o > m Dex Pre-emergent v, C\1 8 MP 0C Soy- Crab Amar STRUCTURE or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard n Q ~ c4 D Ú 113C- (M2(:)-HC-CO CM3 Amax O M3 5.78 A A 1 5 1 1 1 5 É FE < ~ - 6.05, 6.15 ra V r > ~ a S lo ro4 H i. I' 5.78 A A 1 1 2 1 2 W4 CL .0 CO) V du0 CM3 H0 o , F w9 É a (3 O O we SY t &verbar; = a eU X TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-ct 1 ~ . .
E P g a Herbi ci dal Pre-emergent Herbi cidal 9 MP 0C Soy- Crab Amar S8 N a c -o 9 N < E c M3C(M S.7S A A 2 4 2 2 2 5 4 1 H C (ester CO) 3 CM3 6.0, 6.05 (keto CO) E m c4 X Pw r; CM3 Ainax (t); MC 3 5.75 A A 1 2 1 1 2 1 1 1 (ester CO) H3C\0 6.05, 6.10 CM3 (keto 8 = å zzE ~ = CO) sQ Ev TABLE I (Continued) PHYSICAL PROPEERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
ca vl D D e a o" m PC Herbicidal Pre-emergent. Herbi cidal Miticidal MP 0C Soy- Crab Amar e m D cl o C CR Amax (tt); A A 2 5 H 2 2 S 5 3 3 H3C 5.70 ç o (keto rn eCi 8 0 :5 ~ 2 H3C V , V No V oo o x O o O o TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
- 1 1 r s D eJ &commat; o E c ~ fs -O caS " 9 N E b O CL o N Pre-emergent rs n I C MP 0C Soy- Crab Amar mOB m rl Ld C 9 1 C s 0 (d C1 es (v); M 5.78 A A 2 5 2 1 3 2 1 1 " CO) Xa C (keto et E m C 24 O ~ . . ~ ~~ ~~~~ -- (ester " 6.00, 6.10 (keto CO) . ~ ~ Q > S V so V t V o V Cz X oo o oP o X O oF o :S E o X E > o o D : Cot F O e :S rn TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3 CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-ct 1 c3 a a Dz > % m u I F1 Herbi cidal Pre-emergent Herbi cidal Mi ti cidal MP 0C Soy- Crab Amar " hl CJ 0 X o tb err E es HC S.7S A A 2 3 2 2 2 5 3 a C II Q 6.05, 6.10 g: m es es ~ wO ;:i m ~ H3C (ester CO) e 0 (keto CO) o sg CXS Ur CXS o o o C; K > CD O O Y oO ca H O v ç o Y o . 4 2 o o < m o < o Sen ; t1 SO ~1 U 0 X < 0 S X n: TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a m v, m E v Z m m 0 Du o m Mi ti cidal MP 0C Soy- Crab Amar 8 c c 'R H ~ es 113C CH 110-111 A A 1 1 1 1 2 5 5 4 3 c É CR3 E o a E X V H H3C 29-30 A A 1 1 1 1 1 5 S 2 \CR3 ~ ~ a o Amax ~ 2 CR 5.78 A A 2 2 2 2 5 S 4 5 Ô 3 (ester CO) H3C CR3 (keto CO) V 6.05,6.15 ~ ~ el E r- O o o = Sn H s O=U,t 0~20 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 T- 1 1 a E a Y, cc, Herbi cidal Pre-emergent Herbi cidal Mi ti ci dal ,c oX 1 r 02 es H ~ ;E V , 79-84 o ~ .~~ R3C P, II rn = Q rl =s m es H ,~ 3 X, CR3 111-113 v s w 2 V V ~ R3C cf o ct: so fI I D D D 04 ú a t0=o-d TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONE ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-cr 1 1, 2 m -C rv t0 e m t S a" h Herbi ci dal Pre-emergent Herbicidal Ck ur I > or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard e C V H H H C O, 0 9, E rn 71-73 B B 1 t ~ 3 1 au" LP 3 u " 61-62 A m m 4 R3C CR3 V O es o .,1 1 91o 2 o F No i &num; o = TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
1 7 ~ 1 a 2 L j: I I I CL Herbi m d MP 0C. Soy- Crab Amar Oe, cl mP rn D 71 c: cu C X2 (6 I I I m u es t cNN33 (cm3): 1760 (ester A A - 4 - 2 2 5 - - 4 ecru 1645 m l l l I 'O ;i a 2 ~ ~ V 1750 (ester A O O el' 1678, 1645 (Keto CO) a" N X TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
rd ~ D É ~ m m ve 1 5 Z CLf W So ~ t Miticidal n > 8 D ~ t rd C . ~ D U C Amax (cm: A A 1 2 cHcH c3 E E H t CO); n C f 6 eCJ H m Cl r m art CR3 CH3 r :E u O < F s f X z fvf TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
71 2;j 5: a N m 1 a" E l;R Herbi cidal Pre-emergent Herbi cidal Miticidal MP 0C. Soy- Crab Amar I hB rvq D CR3 w H H D U c CR2CR3 II o - C - CUCli2CH3 E CR3 1750 (ester n 1678 A Y, N CH3 U e es m esM o (keto CO) m CcH2) I m I CR3 Amax (cm1): . ~ ~ ~ e Xi F 3~u ~ II 0-C (CM2) 14CH3 V \C/H3\ iE n b - 2 - il 5 n Xo 3 CR3 - Zo 1 -z I X U, > g 3; B R iD ; Q 2 U C; rJ TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 n 1 1 r: I vl 8 1 it is cidal n d MP 0C. Soy- Crab Amar B 8 e C o Q rS rs XS 1750 (ester A A - S - 2 2 S - - S CR3 CM3 CO); 1678, c (keto C CO) E 8CH3 n U m Amax v, V) 1758 (ester A A - 1 - 2 2 5 - - 3 E CM3 1640 (keto =:i CO) w oCo Amax ): a 3 CO); fioo"TS CR3 Cll3 o E n o O ~ rn O(keto 2 o EV sD V E F V sD V E rJ H U 41 Ê Q 4 iPs Sf08t0 00 V iD rm TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a m m 8 P.' F m I lvl DO 0 , a Herbi cidal Pre-emergent H erbi cidal X MP 0C. Soy- Crab- Amar 6 CH2CH3 D U ~ Cel CH3 Amax (cm-1): c 1755 (ester A A 2 3 1 1 1 2 2 1 CO); 1660 c E - c cs rs CH3 \0C3 143-145 A A 2 3 1 3 1 5 5 3 3 r PiX - A A 3 Cg, V ;~ O O i iM XtO > o O I O Y oX n0 < X,0 Ms g ç = co TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
71 1 .~ 1 ~ cd ..
C V 00 oE ~ P Q I I I m H O Pre-emergent vr v, a MP 0C Soy- Crab Amar oo m o o < rt D cd oC '" Amax (cm1): 'D 1758 (ester A XS 5 - 2 3 5 - - 4 v c o CR3CH2 E (keto or cho vc CH3 1750 (ester A A m S - 1 1 1 - (53 1 I con - 71 - /H3 1758 (ester A 32 fm^Q 1678, oE 1650 (keto v - Omy) O iM m Xd m cXd O ô E os zE > Ú Ç ) E > ti XD V z tV sD V lll 8 tro=R8 2 C e t 6 = x e 5 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 D XE C 8 ad I I I 9 V: F I I I Post-emergent Herbi cidal Pre-emergen u Herbi cidal Miticidal I 2: ~ or D Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard " F1 nl '6 Amax (cm1): CH3 1760 (ester A A - S - 2 2 5 - - S c E o (keto CO) o CH3 Amax v ur 1760 (ester A A - S - 2 3 5 - - S 1 I I m (keto l l l ~ Amax (cm1): H3 In (ester A A d S - 2 2 S - - S hF( 1642 (keto V E , F E CO) E E Q x o O O x o 3t fs O U 9 yc Cc 8 > to in TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
p 1 d E h TO I O e cidal Pre-emergen t H a" MP 0C. Soy- Crab Amar 8 cu hl 0 II w v CH3 )1113\Cu3 {{{16: E B 2 (d 0 E o-C-C}L(CM2)CM3 5.75 (ester A A 1 3 1 1 1 1 1 1 CH3 CO); 6.00, X C ~ CM3 b 6.08 (keto CM3 CM3 167-169 S m v V rn sS O XS 5E o n En3XDV s s Xn P D o=y-DD o U CJ V c5'q TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
rd N c 1 a E C X a o o X Herbi cidal Pre-emergent Herbi cidal Mi ti cidal I E: U) or H Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard O o D 3CU3 Amax (tj): A A 1 3 5 C (d 6.10 (keto CR3 CO) rå rC c; Amax (ij): v e rc, m H H EP " " " X CO) zo 2 43CR3 184-18S.S d A V 1 1 1 5 3 1 2 - w o - w o 1 ra v O 2 rn 2 o Vo V ~ o b A: ~ o XD u oo 2 r x rb O O Ô x w{} Ô O Ô U o = y v o st p ov TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
ct 1 N a 1 z C V u0 I m to I 1 X Herbici dal Pre-emergent Herbi m \n Mi tici dal - lc hb C\1 o CR2CH3 II I o 3CR3 CH3 Amax (cm1): A A es > CH3 1750 (ester $c ~ -- 1648 (keto CR3 CO) a n C Dz (CR2)6 5 m I H > C)(3 6.05 (keto fo U} p c CR3 CH3 V 00^9E D X 2 : > O ~ E F V \ V xo V 3 B 3 O N 3 f X u jo Oat N TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
Post-emergent Herbi cidal Pre-emergen t Herbicidal C O) MP 0C Soy- Crab Amar a or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass antlius Mustard oC0 CEL3 Cl CR3 \Cl 91-92.5 A A - 3 - 2 2 S - - 3 0 II 0-C (CR2)6CR3 O Cl Amax (cm'): 1760 (ester A A - 4 - 1 2 5 - - 4 a CO); 1670 II (keto CO) 0-c tCR2) 8CR3 C113 Cll3 Amax 4t): 5.75 (ester A A 1 4 1 1 2 S 3 CR CR3 CO); 6.05, 6.15 (keto o CO) II -C (CR2)6CR3 A;nax (tt): CR3 5.75 ";3 A A 1 3 1 \dO CR3 CO); 6.02, CR CR3 6.13 (keto tR3 r;g\dO zzCO) TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-cl (r, ccr m 1 E a | Herbi cidal Pre-emergen t Herbicidal Mi ticidal MP 0C Soy- Crab Amar Cr: CX D ~ s CR3 122-23 A A - 1 - 1 1 4 - e c TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
ti Y lw D a1 = o (dg I I I ] Ea Ld b 4" m Cr) Pre-emergent Herbicidal . . C MP 0C. Soy- Crab Amar O or N Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard Mo C5H11 . r a D V - 119-120 B C - 2 - 1 1 1 - (:5H11 8 CH3 OCOCH3 Amax > 113 1760 (ester A A - S - 2 2 3 - c I I I I I a ~ z1 V < 6 ~ CM3 -C5U11 Amax (cm1): .. ..
- CO); 1678, C3\ 1645 (keto Od I s i E CO) U X t0 o o o TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
c cr 1 8 f I I I I 6 Ed L a 8 Mi ticidal MP 0C. Soy- Crab Amar np ~ :.. OP) CCI C MP ~ t C5N11 CO); 1678, D U ~, ~ ~ < X CO) s:: E ss E = -C5U 1 CU3 CO); 1678, il = (keto CO) ~ Amax m l l ~ izi 1760 (ester A m m CU CO); 1670 (keto CO) : ~ II 2 Amax (cm1); 1755 (ester B B - S - 1 3 5 - - 2 Cll2CU3 CO); 1675 g ,Eo CO) :E o < ~ V ~ V 4 > V V E > ( ~ E > V > se s ? S st 9 Ç ìt X 0fO TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 t; N m 1 a il o a Herbi cidal Pre-emerent Herbi cidal Miticidal MP 0C Soy- Crab Arnar 8 hi N II Amax (cm1): Iss 1760 (ester A A - S - 1 2 S - - 2 D V ~ < n = (keto CO) U2CU3 II E I Amax (cm '): E CM3 CO) 1678, no o" m es H m E o CU3 is I I H n bo o isl 6 6 w w % & II ~ ~ ~ ~ C}l 5.73 sso m ~ o ^ o, m CI{3 00 6.01, Cfl3 cs E (keto sW CO) m oo 0 < 0 im TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a, Z w n H > ~ wo E P ES cl U (d g: 3 am m E Herbi cidal Pre-emergent H erbi cidal io o MP 0C. Soy- Crab Amara V1 v, l 68 N ce . (CR2) 8CR3 -o oC CR3 CR3 ~ zz S 1 2 2 5 5 4 3 8 n E ~ ç CR3 CO) II I b) (CU2) o I Amax (u): CH3 CR3 5.80 (ester A A 1 1 1 1 1 1 1 1 8 CO); 6.03, 6.10 (keto mo H ~ tzo CR3 I 2 61-62 A A 1 6 6 II crE 4- e w V botx s ç= ot t a" O"qR t0h0" "i ------ ----- V CJ D St TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
E ca a v, m 1 X < : U s , 3 f, dC.
$ E m I $~ r $~ m I Vl E v bo 50 9 m m Herbi cidal Pre- v, ss: > % e N m m ~ ro C t t s 0 5 1 N É i,o, zo 1760 In iNo Vv t m v) = im H I to ~ ~ m ' ~ 1 2 6 6 6 H3 Amax (cm1): 1758 (ester oo oo o I o o C, U 3CR2CR2 5; w =0); 1678, CH3 I 164S (keto o i, ^ É CO) v7 e e M x = -J 9 9 N &commat; O q.9 O 0 ~i' iSJ ~ es Q e V i Q % iM U Q t.
TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 t a P EE: cr a Herbicidal Pre-emergent Herbi cidal E MP N tot (sl r c D U > ~ ~ :: ~ Q CR3 å ~ ~ 3 V m a" uO Y, v, m CR3 m H ~~ ~ ro (keto CO) 71 cH3cR2 S o ~ CR3 oo v t g < V < < } iM ç E > 3 X 4 F.X. So WoX TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
Z;i vl m Ea ~ ~ E V"o < Ei B X it < m H Pre-emergent Herbicidal Mi ti cidal , a ~ ~ c c a S 1 cl D U o1 N o1 Cl o Amax (cm1): 1760 (ester E N N 2 2 2 1 1 1 - CO); 1675 oE E o o v, V) a \O\,H3 123-124 A A 1 5 2 2 1 S S 4 3 ClI3 cp Cl{2CH3 5 :s 6 < 1: Amax (cm-'): CR3 C17=6(; (ester A A 2 5 2 2 2 1 1 1 -" 1670 (keto Li ,." E + o :E É rv 3 X > E > v V m 4 aD 51\Q TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-ct 1 In C1~L 8 cdS hl I I EE C a X Herbi cidal Y I E: o o n t op, N m E D Q N X .
C113 78-80 E > 2 WIZ E oE F Dz V m t m CR3 138-139 A A - 4 - 3 3 5 - - 4 m OCOCH3 0 -~ 6 1678, &verbar; o )s 1760 Erclro o o q: o 1650 ft .
> Y a ro i e e = = 5 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a v, c 1 D É I I cs k s 9 I I hl X :^ m Herbi cidal Pre-emergent Herbi cidal a lr, v, cc, MP 0C Soy- Crab Amar N c o W H N H D ç : .
CR3 CO); 1678, 1643 (keto CO) E oCo ~ m ~~ 1745 (ester A I v 1642 (keto 0 CO) CR2CM3 2 " " 1760 A A 2 S 5 C2; CR3CU3 CO); 1670 U Vv 0"4 (keto CO) TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
9 vl m C\1 1 I cbC I E' i N o ~ Pz o v) n n d Miticidal MP 0C. Soy- Crab Amar Viz or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard = 164.5-166 A A 2 3 1 2 1 S S 4 3 0 Ei oE c CL Amax v, 1760 (ester A A 1 1 1 1 1 2 2 1 m CO); 1670 ~ oa 6 bO 4 II o-C Cl ~ \0 ooo S 00^ D 1730 (ester e w 1 5 o w O OOh V U o m Y, II o: ~ E CO) SsXsSuS ND t0 < o < o V e ce TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANDIONES AND THEIR ESTER COMPOUNDS BIOLOGICAL ACTIVITY
71 1 hl 1 Z a a Herbi ci dal Pre-emergent Herbicidal Miticidal ooS H H > N C6H5 O ' O E E I I O E D V a ~ ~ ~ I I us O u 2 6 V V < : V e sg I oo ow oo I x > o oo ^ u TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
f a D a m t g m N X &commat; m m Herbi m Mi ti cidal MP 0C. - - Soy- Crab Amar STRUCTURE or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 7 E v0 V C6H5 5.65 (ester A A 1 S 1 4 3 S 5 3 4 / \ ~~ CO); 5.97, CH3 6.05 (keto E CO) X Amax ve A A 1 4 1 1 1 5 E < < ~ ~ 5.98, (keto CLO) 0 CR3CR V ?o''CH3 147-149 A A 1 1 1 t 1 S 4 2 2 o < 4 m 3 ç v E o. 3 0 , t s 8 30 Q 3 X TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
cj o b 1 a a L Herbi cidal Pre-emergent Herbi cidal ~ ~ z = 8 or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard o vg m H D Amax (cm'): / \ 1758 (ester A A - S - 3 3 5 - - 5 E I I 0 1645 (keto C=O) a c a u X V m . Amax (cm1): 1 1750 (ester A l l CO); 1678, CIS lì Wt ~ .. ..
CR3 1758 (ester A A o S o 3 3 5 ^ o CO); 1678, C16%5) (keto :E E > v o 3 E > 3 to V E > 3 v 3 D W0 k itigo TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-ct 1 I I a o cbj I I u p b m 0 (d a Herbicidal Pre-emergent I I Miticidal MP 0C. Soy- Crab Amar I I r Hg H D U C' ~ CO); 1678, Cii E 1650 (keto 3 0 CO) a a n" 3 c I I s:: CU3 7 ns m u a P C&num;4/'CH3 79-81 C C - - - - - - - - E m\o o V o o E 3 sD V I l e 6 SS m; 4S TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
o m m I a3 9 (dg rJ ci I o > n v) m Herbi Mi ti ci dal MP 0C. Soy- Crab Amar hm 8 c, C6H5 D Q ~ ~ = 0CH3 147-147.S C A 1 3 1 4 1 5 5 2 3 a I E Ez ~ C6H5 C3 u) CU CR 5.65 (ester A A 2 5 1 4 3 5 5 1 3 33 > 5.95 . ~ ~ M = E 6 V 6 6 CR3 5d%9 (ester A A - S - 3 3 S - - 3 CU3 ); 598, t E 6.05 m g 0 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
X P "9 I I I - = L a" cdV1 I I "Eu" I a o i eo X Ug E V ua b X o m m t MP 0C. Soy- Crab Amar 1 9 N Ld C a 9 D VV n: w O S c (d I I 1 s .f s: X viz 1760 t = I 1 I o CO) be a a 'S = E 6 c1i3 fCOOg 1 1678, Ems A A - 3 - 1 1 4 - i, tn (keto VV vV n I?fO ^,2 &commat; 010Q > 9 o H [+o A o TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
o t 1 m a 9 El I I I Bs a I I I h5 E 'B .6 b" U Amax s 9, (esfer A A - 5 - 2 3 S - - 4 = É oE F L a o" m v) V, a Arnax (cm1): R3 1750 (ester A A - S - 1 1 1 - CO); 1678, 1645(keto - CO) -8 a -s i6 6 6 6 c 06 o t Amax o E (cm1): V aO-. E,re O&commat;Y É 3 VV v S < 3 1678, 1645 (keto '0 CO) 1 E 4 V X e TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a I 1 t z L mS d E I At v, Pre-emergent vi Mi ticidal MP 0C Soy- Crab Amar V: or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard d g .0, = co X Amax O c CII 5.73 (ester A A 1 5 1 3 2 5 1 1 CR3 3 CO); 6.00 0 (keto CO) e)- c e 1 v m m C3 m ~ ~ ~ d (keto ~ ~ G s OCO (Cu2 ~ c A (ester A A 1 5 1 3 2 5 4 1 C6N5 \,iI3 5m7a0x (: CO); 6.00 CH30- 3 (keto du 2 t < m U ~ ,Ex ,r, U y tE m V V 4' t X 4'J TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 t ccl v, v, 3 efi D 6J 'o" vl I m I X emergent Herbi cidal Pre-emergent Herbicidal Mi ticidal ~ t9 or IR > N ~ " ' w < efx n D C) E I ~ e X viz e 3 1 I < sX 6, s 1762 (ester A A - S - 3 3 S - - S AS 1678, CR3 1645 (keto 0 C-O) < = Xs o V vo o H y D > cE X N o m ô i Q c \t TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
-za 1 a 2 0 "1 f3 N a dh r( I Herbi m Miticidal MP 0C Soy- Crab Amar 8 N N o CR2CH3 II I - (CM2) 3CM Cl Amax ( ): E (ester S B 2 2 1 n, CR3 CO); 5.98, Moo 6.05 (keto ~ aO Q N I ~ m > CH3 )0C,1 122-123 m m m 6 i m m L,m A A 1 1 1 1 1 S S 2 2 S=O > 4 m ~ -e oN%S oVo i TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
a 1 m I N Z 71. m C; Herbicidal Pre-emergent Herbi cidal Miticidal MP 0C Soy- Crab- Amar V) or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard 0 II '6 D CH3 = D W O d -I = Xo V H t H t CR3 CN3 'm 120-22 A A 1 1 I 1 1 4 4 2 2 CH3 ~ oo 6 6 2 6 6 6 6 I A A 1 4 1 3 1 5 5 3 4 CH3 C3c H3 vl 8 TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
J m v, I T o > P mS D É ~ = DA É Vv vioo ~ " ~ ~ .. X o a or IR Adult Egg Bean Corn Tomato Cotton bean Rye grass anthus Mustard I C II C < :(CR3)3 :d C r O D 124-26 A ~ oS d ~ :: f c E ~ < * ~ 0 <SE TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
1 N I "m 2 p w Post-emergent Herbi cidal Pre- emergent Herbi cidal Mi ti cidal MP 0C. Soy- Crab Amar u o CR (CR3)2 II I ~ .g: R3 Amax ( ): CR3 \cu3 D (ester B 1 > CO); 6.00, CR3 OC H D U :: II I bio Amax É I og H CR3 CR3 CO); 6.00, e 3 CO) CU3 0 0 I I Cl 1760 (ester A A - 4 - 2 3 S - - 4 CR3 CO); 1680 1: (keto 0 U Amax (cm1): oC(CR2)5CU3 1760 (ester A A - S - 2 2 S - - 4 CO); 0 0 0 0 0 0 CR3c1 Vac,',oo, O p: E i4 o 0 U4 0 Q ~tt D > &verbar;0 i uo jwo H TABLE I (Continued) PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1,3-CYCLOHEXANEDIONES AND THEIR ENOL ESTER COMPOUNDS BIOLOGICAL ACTIVITY
1 m 1 v Herbi cidal Pre-emergent H erbicidal I MP 0C. Soy- Crab Amar a pX v, Ct D " 76-78 A A - 4 - 2 2 5 - - 3 CU3 o c tested was E mixture of two É enol d of the mixture is the structure shown. m Y uo V cY oo o c4 E &commat; = c H g It will be understood that the plant species employed in the above tests are merely representative of a wide variety of plant pest that can be controlled by the use of the compounds of this invention. The compounds contemplated in this invention may be applied as mite ovicides, miticides and pre-emergent herbicides according to methods known to those skilled in the art. Pesticidal compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dissolving the toxicants in water with thje aid of suitable surface active emulsifying and dispersing agents.
The choice of dispersing and emulsifying agents and the amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not re-emulsify the toxicant after it is applied to the plant and wash it off the plant. Nonionic, anionic, amphoteric or cationic dispersing and emulsifying agents may be employed; for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, or quaternary ammonium compounds.
In the preparation of wettable powder or dust or granulated compositions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth or fullers earth. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included.
The required amount of the toxicants contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent and in from 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concentrate will usually vary from 10 to 95 per cent by weight and in the solid formulations from 0.5 to 90 per cent by weight. Satisfactory sprays, dusts, or granules for general use contain from 1/4 to 15 pounds of active toxicant per acre.
The pesticides contemplated herein prevent attack by insects and mites upon plants or other material to which the pesticides are applied, and they have relatively high residual toxicity. With respect to plants, they have a high margin of safety in that when used in sufficient amount to kill or repel the insects, they do not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture or, at least such decomposition, oxidation, and hydrolysis as would materially decrease the desirable pesticidal characteristic of the toxicants or impart undesirable characteristic for instance, phytotoxicity, to the toxicants. The toxicants are so chemically inert that they are compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants.
They may also be used in combination with other pesticidally active compounds.
When used as miticides they will normally be applied to the foliage of the plants to be treated. When used as herbicides they may be used in the soil or directly upon the seeds to be treated. It will be appreciated that the compounds of this invention can also be used in combination with other biologically active compounds.

Claims (25)

WHAT WE CLAIM IS:
1. A compound of the general formula:
wherein: Z, Z', Z" and Z"' are each individually a hydrogen atom or a haloalkyl, halogen, alkyl, polyhaloalkyl, alkoxy, cyano, nitro, alkylthio, alkanoyl, amido, amino, alkylsulfonyl or alkylsulfinyl substituent; Y is a hydrogen atom or
wherein: R is a hydrogen or halogen atom or an alkyl, alkenyl, alkynyl, bicycloalkyl, bicyloalkenyl, cycloalkyl, cycloalkenyl, phenyl, phenylalkyl, naphthyl or naphthylalkyl group, all of which except the hydrogen and halogen atom may be substituted with one or more alkyl, cyano, nitro, alkoxy, halogen, haloalkyl, alkoxyalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylthioalkyl or dialkylamino substitutents; R, is an alkyl, halogen, haloalkyl or polyhaloalkyl substituent; and RRR4, R5, Rss Re and R, are each individually a hydrogen atom or either a substituted or unsubstituted alkyl or phenyl group wherein the permissible substituents are one or more alkyl, cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino substituents; or any two R2, R3, R4, R5, Re, or R7 substituents together may form an alkylene or alkenylene chain containing from 2 to 20 carbon atoms completing a 3, 4, 5, 6 or 7 membered ring structure; with the proviso that the R1, R2, R3, R4, R R", R,, Z, Z', Z", Z"' substituents individually do not contain more than ten aliphatic carbon atoms and R does not contain more than thirty aliphatic carbon atoms; or an alkali metal salt or ammonium salt thereof.
2. A compound as claimed in Claim 1 wherein R is linear or branched chain alkyl group containing from I to 30 carbon atoms.
3. A compound as claimed in Claim 1 wherein R is a hydrogen atom.
4. A compound as claimed in Claim 1 or claim 2 wherein R1 is a methyl group or a halogen atom.
5. A compound as claimed in any one of the preceding claims wherein R2, R3, R4, Re, Re and R, are each individually a hydrogen atom or an alkyl group.
6. A compound as claimed in claim 5 wherein R2, R3, R4, R5, Re and R, are each individually a methyl or ethyl group.
7. A compound as claimed in any one of the preceding claims wherein Z, Z', Z" and Z"' are each individually a hydrogen atom or an alkyl, cyano, alkoxy, halogen or trihalomethyl group.
8. A compound as claimed in Claim 7 wherein Z, Z', Z" and Z"' are each individually a methyl or a methoxy group.
9. 3 - (2 - Ethylhexanoyloxy) - 5,5 - dimethyl - 2 - (2',4' - dimethylphenyl) - 2cyclohexenone.
10. 3 - (2 - Ethylhexanoyloxy) - 5,5 - dimethyl - 2 - (2' - methylphenyl) - 2cyclohexenone.
II. (2',4' - dimethylphenyl)- 5,5 - dimethyl - 2 - cyclohexane-l,3-dione.
12. (2' - methylphenyl) - 5,5 - dimethyl - 2 - cyclohexane - 1,3 - dione.
13. A compound as claimed in claim I substantially as hereinbefore described.
14. A method of preparing a compound of the general formula:
wherein Rt, R2, R3, R4, Re, R6, R7, Z, Z', Z" and Z"' are as defined herebelow which comprises reacting a compound of the formula:
wherein R2, R3, R4, R5, Re and R, are as defined herebelow, with a compound of the formula:
wherein R1, Z, Z', Z" and Z"' are as defined herebelow, in the presence of ultraviolet radiation having a wavelength of greater than 290 nanometers; wherein: Z, Z', Z" and Z"' are each individually a hydrogen atom or a polyhaloalkyl, halogen, cyan, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkanoyl, amino, or haloalkyl group; R1 is an alkyl group and R2, R3, R4, R5, R6 and R, and each individually a hydrogen atom or either a substituted or unsubstituted alkyl or phenyl group wherein the permissible substituents are one or more alkyl, cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino substituents; or any two R3, R4, Re, Re, R7 or R8 substituents together may form an alkylene or alkenylene chain containing from 2 to 20 carbon atoms completing a 3, 4, 5, 6 or 7 membered ring structure; with the proviso that the R1, Rv R3, R4, R5, Re, R7, Z, Z', Z" and Z"' substitutents individually do not contain more than ten aliphatic carbon atoms.
15. A method of preparing a compound of the general formula:
wherein R1, R2, R3, R4, Re, Re, R7, Z, Z', Z" and Z"' are as defined herebelow, which comprises reacting a compound of the formula:
wherein R2, R3, R4, R5, R6 and R7 are as defined herebelow, with a compound of the formula:
wherein R1, Z, Z', Z" and Z"' are as defined herebelow, and X is a fluorine or chlorine atom, in the presence of base, wherein Z, Z" and Z' are each individually a hydrogen atom or a poly-haloalkyl, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, amido, amine or haloalkyl group; Z' is a nitro or alkylsulfonyl group or Z' is an alkyl or alkoxy group when either Z"' or R, is a nitro group; R, is an alkyl, haloalkyl, halogen, or polyhaloalkyl group and R2, R3, R4, R5, R6, R7 are each individually a hydrogen atom or either a substituted or unsubstituted alkyl or phenyl group wherein the permissible substituents are one or more alkyl, cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino substitutents; or any two R2, R3, R4, R5, Razor R7 substituents together may form an alkylene or alkenylene chain containing from 2 to 20 carbon atoms completing a 3, 4, 5, 6 or 7 membered ring structure; with the proviso that the R1, R?, R3, R4, R5, Re, R7, Z, Z', Z" and Z"' substituents individually do not contain more than ten aliphatic carbon atoms.
16. A method of preparing a compound of the general formula:
wherein R1, R2, R3, R4, R5, R6, R7, Z, Z', Z" and Z"' are as defined in claim 1, which comprises treating a compound of the formula:
wherein R1, R2, R3, R4, R5, Re, R7, Z, Z', Z" and Z"' are as defined in claim 1 with acid.
17. A method of preparing a compound of the general formula:
wherein R1, R2, R3, R6, R5, Re, R7, Z, Z', Z" and Z"' are as defined in claim 1, which comprises treating a compound of the formula:
wherein R1, R2, R3, R4, Re,. Re, R7, Z, Z', Z" and Z"' are as defined in claim I and R8 is an alkyl group containing not more than ten aliphatic carbons with base.
18. A method of preparing a compound of the general formula:
wherein R1, R2, R3, R4, R5, Re, R7, Z, Z', Z" and Z"' are as defined in claim 1, which comprises reacting a compound of the formula:
wherein1, R2, R3,R4,R5, Re, R7, Z, Z', Z" and Z"' are as defined in claim 1 with a compound of the formula
wherein R is as defined in claim 1 and X is a chlorine or fluorine atom or a hydroxyl group or the group
wherein R is as defined in claim 1, in the presence of an acid acceptor.
19. A method as claimed in any one of claims 14 to 18 substantially as hereinbefore described.
20. A method as claimed in any one of claims 14 to 18 substantially as hereinbefore described in any one of the specific Examples.
21. A compound as claimed in claim 1 when prepared by a method as claimed in any one of claims 14 to 20.
22. A miticidal, mite ovicidal or herbicidal composition comprising an acceptable carrier and as the active toxicant a miticidally, mite ovicidally or herbicidally effective amount of a compound as claimed in any one of claims 1 to 13 or claim 21.
23. A composition as claimed in claim 22 substantially as hereinbefore described.
24. A method of controlling mites and plant pests which comprises subjecting the mites, the eggs of the mites and the plant pests or their environment to a miticidally, mite ovicidally or herbicidally effective amount of a compound as claimed in any one of claims 1 to 13 or claim 21, or of a composition as claimed in claim 22 or claim 23.
25. A method as claimed in claim 24 substantially as hereinbefore described.
GB12103/78A 1977-03-28 1978-03-28 Synthesis of biocidal 2-aryl-1,3-cycloalkane-diones and their enol esters Expired GB1567300A (en)

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US05/781,985 US4209532A (en) 1977-03-28 1977-03-28 Biocidal 2-aryl-1,3-cyclohexane dione compounds and alkali metal and ammonium salts thereof
US05/781,781 US4422870A (en) 1977-03-28 1977-03-28 Biocidal 2-aryl-1, 3-cyclohexanedione enol ester compounds

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088098A1 (en) * 2001-04-12 2002-11-07 Bayer Cropscience Ag Thiazolyl-substituted carbocyclic 1,3-diones as pesticidal agents
WO2010081688A3 (en) * 2009-01-19 2011-05-05 Bayer Cropscience Ag 4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones and their use as insecticides, acaricides and/or fungicides
US12319640B2 (en) 2019-07-31 2025-06-03 Syngenta Crop Protection Ag Cyclic diones as herbicidal compounds

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH649981A5 (en) * 1981-05-12 1985-06-28 Lonza Ag METHOD FOR PRODUCING 3,3-DIMETHYLGLUTARIC ACID.
LV5452A3 (en) * 1983-05-18 1994-03-10 Ciba Geigy Ag Catching down the legacy of Cyclohexandioncarbonate derivatives
US4780569A (en) * 1986-06-09 1988-10-25 Stauffer Chemical Company Certain 1,3-diphenyl-1,3-propanediones
US4918236A (en) * 1986-06-09 1990-04-17 Ici Americas Inc. Certain substituted 3-(substituted oxy)-2-benzoyl-cyclohex-2-enones
KR890003680A (en) * 1986-10-16 1989-04-17 죤 알.페넬 2- (2-substituted benzoyl) -4- (substituted) -1,3-cyclohexanedione and methods for preparing the same and methods for inhibiting compositions and plants using the same
US4808214A (en) * 1986-10-16 1989-02-28 Stauffer Chemical Company Certain 2-(2-substituted benzoyl)-4-(substituted oxy or substituted thio)-1,3-cyclohexanediones
EP0319075B1 (en) * 1987-11-28 1994-07-20 Nippon Soda Co., Ltd. Cyclohexenone derivatives
DE10016544A1 (en) * 2000-04-03 2001-10-11 Bayer Ag New phenyl-substituted cyclic keto-enol compounds useful e.g. as insecticides, acaricides, nematocides, acaricides, herbicides, ectoparasiticides, antifouling agents or intermediates
DE102005059469A1 (en) 2005-12-13 2007-06-14 Bayer Cropscience Ag Insecticidal compositions having improved activity
DE102006007882A1 (en) 2006-02-21 2007-08-30 Bayer Cropscience Ag New cyclic keto enol derivatives useful for controlling animal pests and/or unwanted plant growth
SA07280691B1 (en) 2006-12-14 2010-11-02 سينجنتا بارتسبيشنز ايه جي Novel 4-Biphenyl-Pyran-3,5-Diones and Their Use as Herbicides
GB0710223D0 (en) 2007-05-29 2007-07-11 Syngenta Ltd Novel Herbicides
GB0712653D0 (en) 2007-06-28 2007-08-08 Syngenta Ltd Novel herbicides
GB0715454D0 (en) 2007-08-08 2007-09-19 Syngenta Ltd Novel herbicides
GB0715576D0 (en) 2007-08-09 2007-09-19 Syngenta Ltd Novel herbicides
PL2222657T3 (en) 2007-12-13 2013-03-29 Syngenta Ltd Pyrandiones, thiopyrandiones and cyclohexantriones having herbicidal properties
GB0812310D0 (en) 2008-07-03 2008-08-13 Syngenta Ltd Novel herbicides
GB0819205D0 (en) 2008-10-20 2008-11-26 Syngenta Ltd Novel herbicides
GB0900641D0 (en) 2009-01-15 2009-02-25 Syngenta Ltd Novel herbicides
GB0901834D0 (en) 2009-02-04 2009-03-11 Syngenta Ltd Novel herbicides
GB0901835D0 (en) 2009-02-04 2009-03-11 Syngenta Ltd Novel herbicides
AU2010223535B2 (en) 2009-03-11 2015-09-10 Bayer Intellectual Property Gmbh Halogenalkylmethylenoxy-phenyl-substituted ketoenols
DE102010008644A1 (en) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft, 13353 Cyclic ketoenols for therapy
UA113753C2 (en) 2012-01-26 2017-03-10 PHENYL-SUBSTITUTED KETOENOLS FOR FISH PARASITIS

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3273992A (en) * 1962-02-06 1966-09-20 Fmc Corp Herbicidal use of substituted methylcyclohexenones
US4052446A (en) * 1973-08-06 1977-10-04 Hoffmann-La Roche Inc. 11,16-substituted prostaglandins

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088098A1 (en) * 2001-04-12 2002-11-07 Bayer Cropscience Ag Thiazolyl-substituted carbocyclic 1,3-diones as pesticidal agents
RU2306310C2 (en) * 2001-04-12 2007-09-20 Байер Кропсайенс Аг Thiazolyl-substituted carbocyclic 1,3-diones as agent for pest controlling
KR100862892B1 (en) 2001-04-12 2008-10-13 바이엘 크롭사이언스 아게 Thiazolyl-substituted carbocyclic 1,3-diones as pesticides
WO2010081688A3 (en) * 2009-01-19 2011-05-05 Bayer Cropscience Ag 4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones and their use as insecticides, acaricides and/or fungicides
US12319640B2 (en) 2019-07-31 2025-06-03 Syngenta Crop Protection Ag Cyclic diones as herbicidal compounds
AU2020320003B2 (en) * 2019-07-31 2026-02-05 Syngenta Crop Protection Ag Cyclic diones as herbicidal compounds

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PT67818A (en) 1978-04-01
CH635061A5 (en) 1983-03-15
DE2813341A1 (en) 1978-10-05
NL184777C (en) 1989-11-01
CH632394A5 (en) 1982-10-15
NL7803296A (en) 1978-10-02
CH635561A5 (en) 1983-04-15
AU525258B2 (en) 1982-10-28
FR2385674B1 (en) 1981-10-30
IL54350A0 (en) 1978-06-15
AR226150A1 (en) 1982-06-15
DE2857480C2 (en) 1987-02-12
EG13409A (en) 1982-12-31
JPS53149958A (en) 1978-12-27
FR2385674A1 (en) 1978-10-27
JPH0152375B2 (en) 1989-11-08
DE2813341C2 (en) 1983-04-28
GR72815B (en) 1983-12-06
NL184777B (en) 1989-06-01

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PS Patent sealed [section 19, patents act 1949]
732 Registration of transactions, instruments or events in the register (sect. 32/1977)
PCNP Patent ceased through non-payment of renewal fee