CH632394A5 - 2-Aryl-1,3-cyclohexanedione pesticides and process for preparing them - Google Patents

Description

The present invention relates to novel 2-aryl-1,3-cyclohexanediones, their alkali metal salts, their ammonium salts and their enolic esters. The invention also relates to a two-variant process for the preparation of these new compounds. According to another of its aspects, the invention relates to acaricide, mite ovicide, post-emergence herbicides and pre-emergence herbicides, formed from an acceptable carrier containing a pesticidally active amount of a compound of the invention. tion, as well as a method of destroying mites and parasitic plants, which method comprises subjecting the mites, their eggs and the parasitic plants to a pesticidal amount of a compound of the invention.

The invention relates more particularly to compounds of formula:

a haloalkyl, polyhaloalkyl, halo, alkyl, alkoxy, cyano, nitro, alkylthio, alkanoyl, amido, amino, alkylsulfinyl or alkylsulfonyl radical;

O

II

Y is a hydrogen atom or a group —CR;

R is a hydrogen or halogen atom or an alkyl, alkenyl, alkynyl, bicycloalkyl, bicycloalkenyl, cycloalkyl, cy-cloalkenyl, phenyl, phenalkyl, naphthyl or naphthylalkyl group, all these radicals, except hydrogen and halogen , which may be substituted with one or more alkyl, cyano, nitro, alkoxy, halo, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl or dialkylamino radicals;

R1 is an alkyl, polyhaloalkyl or haloalkyl group or a halogen;

R-2 'Rîi Rji Rs and R7 represent, individually, hydrogen or an alkyl or phenyl group unsubstituted or substituted by one or more alkyl, cyano, halo, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino radicals; or two of the substituents R2, R3, R4, Rs, R6 or R, together form an alkylene or alkenyl chain having 2 to 20 carbon atoms and forming the complement of a 3,4,5,6 or 7-membered ring ;

provided that R1 (R2, R3, R4, Rs, R6, R7, Z, Z ', Z "and Z'" individually do not contain more than 10 aliphatic carbon atoms and that R does not contain more than 30 aliphatic atoms of carbon.

The following compounds endowed with acaricide, ovicide against mites or herbicide activity are examples of compounds corresponding to the general formula given above, which can be conveniently prepared by the process of the invention, by the simple choice of the reaction components to be used in the methods described below: 2- (2'-chlorophenyl) -3- (7-phenylheptanoyloxy) -5,5-dimethyl-2-cy-clohexenone,

2- (2'-chlorophenyl) -3- (2 ', 6'-dichlorohexanoyloxy) -2-cyclo-hexenone,

2- (2 ', 4'-dibromophenyl) -3- (hexanoyloxy) -2-cyclohexenone,

2- (2'-chlorophenyl) -3- (2-ethylhexanoyloxy) -2-cyclohexenone,

3- (2'-isopropylphenyl) -4-acetoxy-spiro [5,5] undéc-3-ene-2-one, 2- (2'-chlorophenyl) -3-benzoyloxy-5,5-dimethyl-2- cyclohexenone, 2- (2'-bromophenyl) -3- (4'-chlorobenzoyIoxy) -5,5-dimethyl-2-cy-

clohexenone,

2- (2'-chlorophenyl) -3- (5'-diethylaminophenylcarbonyloxy) -5,5-dimethyl-2-cyclohexenone,

2- (2'-chlorophenyl) -3- (4'-chlorophenylcarbonyloxy) -5,5-dimé-thyl-2-cyclohexenone,

2- (2'-chlorophenyl) -3- (4'-methylthiophenylcarbonyloxy) -5,5-di-methyl-2-cyclohexenone,

2- (2'-chloro-5'-nitrophenyl) -3- (4'-dimethylaminophenylcarbonyl-oxy) -5,5-dimethyl-2-cyclohexenone,

2- (2'-chlorophenyl) -3- (trifluoroacetoxy) -5,5-dimethyl-2-cyclo-hexenone,

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2- (2'-chlorophenyl) -3- (acetoxy) -5,5-dimethyl-2-cyclohexenone, 2- (2'-trifluoromethyl-4'-nitrophenyl) -3-chlorocarbonyloxy-5,6-dimethyl-2 -cyclohexenone,

2- (2'-methyl-4'-nitrophenyl) -3-chlorocarbonyloxy-5,6-dimethyl-5 2-cyclohexenone,

2- (2'-methyl-6'-nitrophenyl) -3-naphthylcarbonyloxy-4,4-diethyl-2-cyclohexenone,

2- (2 ', 4'-dimethylphenyl) -3-hexanoyloxy-5,5-dimethyl-2-cyclo-hexenone,

io 2- (2 ', 4'-dimethylphenyl) -3- (2-ethylhexanoyloxy) -5,5-dimethyl-2-cyclohexenone,

2- (2 ', 3'-dimethylphenyl) -3-stearoyloxy-5,5-dimethyl-2-cyclo-hexenone,

2- (2 ', 5'-dichlorophenyl) -3-acetoxy-5,5-dimethyl-2-cyclo-15 hexenone,

2- (2 ', 4'-dibromophenyl) -3-isobutyryloxy-5,5-dimethyl-2-cyclo-hexenone,

2- (2 ', 6'-dichlorophenyl) -3-hexanoyloxy-5,5-dimethyl-2-cyclo-hexenone,

2- (2 ', 6'-dichlorophenyl) -3- (2-ethylhexanoyloxy) -5,6-dimethyl-2-cyclohexenone,

2- (2 \ 5'-dichlorophenyl) -3-stearoyloxy-5,5-dimethyl-2-cyclo-hexenone,

2- (2 ', 3'-dimethylphenyl) -3-benzoyloxy-5,5-dimethyl-2-cyclo-25 hexenone,

2- (2 ', 4'-dimethylphenyl) -3-phenylcarbonyloxy-4,6-dimethyl-2-cyclohexenone,

2- (2 ', 4'-difluorophenyl) -3- (2', 4'-dichlorophenylcarbonyloxy) -5,5-dimethyl-2-cyclohexenone, 2- 2- (2 ', 4'-dimethylIphenyl) -3- ( 4'-dimethylamino-phenylcarbonyloxy) -5,5-dimethyl-2-cyclohexenone,

2- (2 ', 4'-dimethylphenyl) -3- (4'-chlorophenylcarbonyloxy) -5,6-di-methyl-2-cyclohexenone,

2- (2 ', 4'-dimethylphenyl) -3- (2'-ethylthiophenylcarbonyloxy) -5,5-35 dimethyl-2-cyclohexenone,

2- (2 ', 4'-dimethylphenyl) -3-trifluoroacetoxy-5,5-dimethyl-2-cyclo-hexenone,

2- (2 ', 4'-dimethylphenyl) -3-dimethylammoacetoxy-4,5-dimethyl-2-cyclohexenone, 40 2- (2', 4'-dimethylphenyl) -3-methylthioacetoxy-5,5-dimethyl-2 - "cyclohexenone,

2- (2 ', 4'-dimethylphenyl) -3-methylsulfonylacetoxy-5,5-dimethyl-2-cyclohexenone,

2- (2 ', 4'-dimethylphenyl) -3- (2-cyclohexenylcarbonyloxy) -5,5-di-45 methyl-2-cyclohexenone,

2- (2'-trichloromethyl-4'-nitrophény]) - 3- (2 ', 4-dicyanohexanoyl-oxy) -4- (2'-chlorethyl) -2-cyclohexenone,

2- (2'-chloro-4'-nitrophenyl) -3- (2'-nitroethanoyloxy) -4,5-diethyl-2-cyclohexenone,

so 2- (2'-chloro-6'-methoxy-4'-nitrophenyl) -3-pentanoyloxy-6- (2'-cyanoethyl) -2-cyclohexenone,

2- (2'-chlorophenyl) -3-acetoxy-5,5-dimethyl-2-cyclohexenone, 2- (2'-chlorophenyl) -3- (cyclopropylcarbonyloxy) -4,5-dimethyl-2-cyclohexenone,

55 2- (2'-bromophenyl) -3- (2-ethylhexanoyloxy) -5,6-dimethyl-2-cyclohexenone,

2- (2 ', 4', 6'-trimethylphenyl) -3- (4'-cyanobenzoyloxy) -4-methyl-2-cyclohexenone,

2- (2'-methylphenyl) -3-ethanoyloxy-5- (3'-ethylsulfinylphenyl) -2-60 cyclohexenone,

2- (2'-methylphenyl) -3- (4'-methoxyphenylcarbonyloxy-5,5-dimé-thyl-2-cyclohexenone,

2- (2 ', 6'-dimethylphenyl) -3- (2', 4'-dicyanophenylcarbonyloxy) -5,5-dimethyl-2-cyclohexenone, 65 2- (2 ', 4'-dimethylphenyl) -3- ( 3'-nitrophenylcarbonyloxy) -5,5-di-methyl-2-cyclohexenone,

2- (2'-methyl-4'-chlorophenyl) -3- (trifluoracetoxy) -5,5-dimethyl-2-cyclohexenone,

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2- (2 ', 4'-dimethylphenyl) -3- (3'-methylthiobenzoyIoxy) -5,5-dimé-thyl-2-cyclohexenone,

2- (2'-methylphenyl) -3- (2'-methylsulfinylbenzoyloxy) -5,5-dimê-thyl-2-cyclohexenone,

2- (2'-methylphenyl) -3- (4'-methylsulfonylphenylcarbonyloxy) -5,5-dimethyl-2-cyclohexenone,

2- (2 ', 4', 6'-trimethylphenyl) -3-cyclopropylcarbonyIoxy-5,5-dimé-thyl-2-cyclohexenone,

2- (2 ', 4', 6'-trimethylphenyl) -3- (2-cycIohexenylcarbonyloxy) -5,5-dimethyl-2-cyclohexenone,

2- (2'-methylphenyl) -3-propynoyloxy-5,5-dimethyl-2-cyclo-hexenone,

4-acetoxy-3- (2 ', 4'-dimethylphenyl) -bicyclo- [3.2.1] -oct-3-ene-2-one,

4- (2-ethylhexanoyloxy) -3- (2'-chlorophenyl) -spiro- [5.5] -undéc-3-ene-2-one,

2-hexanoyloxy-3- (2 ', 4'-dichlorophenyl) -bicyclo- [4.4.0] -dec-2-ene-4-one,

3-isobutyryloxy-4- (4'-chlorophenyl) -2- (2 ', 5'-dimethylphenyl) -2-cyclohexenone,

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-cyclohexane-dione,

2- (2'-trifluoromethyl-6'-methyl) -4-trichloromethyl-1,3-cyclohexanedione,

triethylammonium salt of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione pyrrolidinium salt,

piperidinium salt of 2- (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

1-adamantanammonium salt of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione,

2- (2'-methylphenyl) -5,5-dimethyl-1,3-cy-clohexanedione pyridinium salt,

morpholinium salt of 2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione,

benzyldimethylammonium salt of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

dicyclohexylammonium salt of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione,

N, N-diethylanilinium salt of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione 2-picolinium salt,

piperazinium salt of 2- (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

imidazolium salt of 2- (2'-chlorophenyl) -5,5-dimethyl-l, 3-cy-clohexanedione,

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-cyclo-hexanedione,

2- (2'-methyl-4'-chlorophenyl) -5-methyl-5-isopropyl-1, 3-cyclo-hexanedione,

2- (2'-ethyl-6'-ethoxyphenyl) -5,5-dimethyl-1,3-cyclohexanedione, 2- (2 ', 6'-diethylphenyl) -5,5-ditrifluoromethyl-1,3-cyclohexane- dione,

2- (2'-methyl-6 '- (methylsulfinyl) phenyl) -5,5-dimethyl-1,3-cyclo-hexanedione,

2- (2'-trichloromethyl-6'-cyanophenyl) -5,6-dimethyl-1, 3-cyclo-hexanedione,

2- (2 ', 6'-dimethyl-4'-tertiobutylphenyl) -5,5-dimethyl-l, 3-cyclo-hexanedione,

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-cyclohexanedione,

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-cyclohexane-dione,

2- (2'-nitro-4 ', 6'-dibromophenyl) -5,5-dimethyl-1, 3-cyclohexane-dione,

5- (4'-chlorophenyl) -2- (2 ', 4', 6'-trimethylphenyl) -1,3-cyclohexane-dione,

5- (3'-bromophenyl) -2- (2 ', 4', 6 ', trimethylphenyl) -1,3-cyclohexane-dione,

5- (2'-methylthiophenyl) -2- (2 ', 4', 6'-trichlorophenyl) -1,3-cyclo-hexanedione,

5- (4'-methoxyphenyl) -2- (2 ', 4', 6'-trimethylphenyl) -1,3-cyclo-hexanedione,

5- (3'-ß-möthoxyethylphenyl) -2- (2 ', 4', 6'-trimethylphenyl) -l, 3-cy-clohexanedione,

2- (2 ', 4', 6'-trimethylphenyl) -4- (4'-methylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

2- (2 ', 4', 6'-trimethylphenyl) -4-phenyl-5,5-dimethyl-1,3, cyclo-hexanedione,

2- (2 ', 4', 6'-trimethylphenyl) -4- (4'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione,

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-cyclohexanedione,

2- (2'-N-methylcarbamoyl-6'-methylphenyl) -4- (4'-methoxyphé-nyl) -5,6-dimethyl-1,3-cyclohexanedione,

2- (2 ', 6'-dimethylphenyl) -4- (4'-methylthiophenyl) -5,5-dimethyl-1,3-cyclohexanedione,

2- (2'-methyl-3 ', 6'-dicyanophenyl) -6- (methylthioethyl) -1,3-cycIo-hexanedione,

5- (4'-methylsulfinylphenyl) -4,6-dimethyl-2- (2 ', 6'-dimethylphenyl-1,3-cyclohexanedione,

N-methylpiperidinium salt of 5- (2'-methoxyphenyl) -2- (2 ', 4', 6'-trimethylphenyl) -1,3-cyclohexanedione,

trimethylammonium salt of 2- (2 ', 6'-dimethylphenyl) -4- (4'-methylthiophenyl) -5,6-dimethyl-1,3-cyclohexanedione,

2- (2'-chloro-4'-methoxyphenyl) -5,5-dimethyl-1,3-cyclohexane-dione,

2- (2'-methyl-4'-cyanophenyl) -5,5-dimethyl-1,3-cyclohexane-dione,

2- (2'-methyl-4'-trifluoromethylphenyl) -5,5-dimethyl-l, 3-cyclo-hexanedione,

2- (2'-trifluoromethyl-4'-methoxyplienyl) -5,5-dimethyl-1,3-cyclo-hexanedione,

2- (2'-trifluoromethyl-4'-chlorophenyl) -5,5-dimethyl-1,3-cyclo-hexanedione,

2- (2'-trifluoromethyl-4'-cyanophenyl) -5,5-dimethyl-l, 3-cyclo-hexanedione,

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-cyclohexane-dione ,

2- (2 ', 4'-dimethylphenyl) -4- (4'-trifluoromethylphenyl) -1,3-cyclo-hexanedione,

2- (2 ', 4'-simethylphenyl) -5- (2'-chlorophenyl) -1,3-cyclohexane-dione,

2- (2 ', 4'-dichlorophenyl) -6- (2'-methylthiophenyl) -1,3-cycIo-hexanedione,

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632394

2- (2 ', 4'-dichlorophenyl) -5- (4'-methylphenyl) -1,3-cyclohexanedione,

2- (2 ', 4'-dichlorophenyl) ~ 5- (4'-methoxyphenyl) -1,3-cyclohexane-dione,

3- (2'-methylphenyl) -spiro- [5.5] -undecane-2,4-dione, 3- (2 ', 4'-dimethylphenyl) -spiro-t5.5] -undecane-2,4-dione, 3- (2'-chlorophenyl) -spiro- [5.5] -undecane-2,4-dione, 3 (2 ', 4'-dichlorophenyl) spiro-t5.5] -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-cyclohexanedione,

2- (2 ', 4'-dichlorophenyl) -6- (4'-dimethylaminophenyl) -1,3-cyclo-hexanedione,

2- (2'-trifluoromethyl-5-cyanophenyl) -6-methylsulfinylethyl-1,3-cyclohexanedione,

2- (2'-chloro-4'-methoxyphenyl) -4,6-dimethyl-1,3-cyclohexane-dione,

pyridinium salt of 2- (2 ', 4'-dibromophényI) -6-methoxy-methyl-1,3-cyclohexanedione,

N-methylmorpholinium salt of 2- (2'-methylphenyl) -4,6-diethyl-1,3-cyclohexanedione,

5- (2 ', 4'-dimethylphenyl) -2- (2', 4 ', 6'-trichlorophenyl) -1,3-cyclo-hexanedione,

5- (2 ', 4'-dichlorobutyl) -2- (2'-ethoxy-3', 5'-6'-trifluorophenyl) -1,3-cyclohexanedione,

5- (methylthiomethyl) -2- (2'-chloro-6'-cyanophenyl) -1,3-cyclo-hexanedione,

5- (2'-dimethylaminophenyl) -2- (2 ', 6'-dimethylphenyl) -1,3-cyclo-hexanedione,

2- (2'-nitro-3'-methylthio-6'-trichloromethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione,

2- (2'-methyl-5'-cyano-6'-nitrophenyl) -4,6-dimethyl-l, 3-cyclo-hexanedione,

2- (2 ', 4'-dichloro-6'-trifluoromethylphenyl) -4- (2'-chloroethyl) -1,3-cyclohexanedione,

3- (2'-chloro-6'-fluorophenyl) -spiro- [5.5] -undecane-2,4-dione, 2- (2'-chloro-4'-nitro-6'-cyanophenyl) -5.5 -propyl-1,3-cyclo-

hexanedione,

2- (2 ', 6'-dichloro-4'-nitrophenyl) -5- (2'-cyanoethyl) -1,3-cyclo-hexanedione,

2- (2'-chloro-6'-methoxy ~ 4'-nitrophenyl) -5,5-dimethyl-l, 3-cycIo-hexanedione,

2- (2'-chloro-6'-cyano-4'-nitrophenyl) -5,5-dimethyl-l, 3-cyclo-hexanedione,

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-cyclo-hexanedione,

5- (4'-cyanophenyl) -2- (2'-chloro-6'-methoxy-4'-nitrophenyl) -1,3-cyclohexanedione,

5- (2 ', 4'-dichlorophenyl) -2- (2 /, 4'-dichloro-6'-nitrophenyl) -1,3-cyclohexanedione,

5- (3'-nitrophenyl) -2- (2'-chloro-4'-nitrophenyl) -1,3-cyclohexane-dione,

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-l, 3-cyclo-hexanedione,

2- (2 ', 4'-dichloro-6'-aminophenyl) -5,5-dimethyl-l, 3-cyclohexanedione,

2- (2 ', 6'-dichloro-4'-aminophenyl) -5,6-dimethyl-1, 3-cyclohexanedione,

2- (2'-chloro-6'-nitro-4'-aminophenyl) -5,5-dimethyl-l, 3-cyclo-hexanedione,

5- (4'-chlorophenyl) -2- (2'-chloro-6'-methoxy-4'-aminophenyl) -1,3-cyclohexanedione,

5- (4'-chloro-6'-nitrophenyl) -2- (2'-bromo-4'-methylsulfinyl-6'-cyanophenyl) -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-l, 3-cyclohexanedione,

2- (2'-methyl-3'-nitro-6'-methoxyphenyl) -4,5-dimethyl-1,3-cyclo-hexanedione,

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-l, 3-cyclo-hexanedione,

2- (2'-bromo-4'-aminophenyl) -5,5-dimethyl-1,3-cyclohexane-dione,

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-cyclohexane-dione,

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-cyclohexanedione,

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, 5- (2', 4'-dimethoxyphenyl) -2- (2 ', 6'-dimethylphenyl) -1.3 -cyclohexanedione,

5- (2'-cyanopropyl) -6-methyl-2- (2 ', 6'-dimethylphenyl) -1,3-cyclo-hexanedione,

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 the compounds which correspond to the general formula given above display, to a greater or lesser degree, acaricidal, ovicidal against mites, pre-emergent herbicide and post-emergent herbicide activity. Some of these compounds have very high levels of miticide, mite ovicide or herbicide activity at extremely low doses, while others must be used at higher doses to exert a pesticidal effect. In general, the compounds of the invention which display the highest degree of herbicidal activity also display the highest degree of acaricidal and ovicidal activity against mites. Miticide and ovicide activity against mites is greatest in compounds that carry

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a hydrogen atom or an alkyl, alkoxy, cyano, tri-halomethyl or halo substituent in one of the ortho positions of the 2-phenyl group and an alkyl or halo substituent in the other ortho position of the 2-phenyl group. Particularly active compounds include those in which the ortho substituents are relatively small groups such as methoxy, ethoxy, methyl, ethyl or halo.

It has also been found that some of the pesticidal compounds of the invention also have the property of being excellent fumigants. In addition, these compounds are relatively non-toxic to 10

mammals when used in sufficient quantities to destroy mites, their eggs or parasitic plants.

In addition to their acaricide, ovicide against mite and herbicide properties, the 2-aryl-1,3-cyclohexanediones of the invention can also be used as intermediate compounds in the preparation of other compounds endowed with pesticidal activity. For example, 2- (2'-chloro-6'-methoxy-4'-nitrophenyl) -5,5-dimethyl-1,3-cyclohexanedione can be reacted with 2-ethyl-hexanoyl chloride in the presence of pyridine as solvent and as acid acceptor to form 3- (2-ethylhexanoyloxy) -2- (2'- chloro-6'-methoxy-4'-nitrophenyl) -5,5-dimethyl-2-cyclohexenone, that is to say the enolic ester corresponding to pesticidal activity. The 2-aryl-1,3-cyclohexanediones of the invention can also be reacted with other chemical compounds exhibiting electron-deficient reaction sites, for example organic anhydrides such as acetic anhydride.

We prefer, for their higher degrees of acaricide activity,

ovicide against mites and herbicide and because of their ability to

be used as intermediate compounds in the preparation of other substances endowed with pesticidal activity, the compounds of the invention in the formula of which:

O

II

Y represents a group —CR;

Z, Z ', Z "and Z'" represent, individually, hydrogen or an alkyl, alkoxy, cyano, halo or trihalomethyl radical;

Ri is an alkyl radical or a halogen atom;

R2, R3, R4, Rs, Re and R7 represent, individually, hydrogen or an alkyl group.

The most active compounds which are particularly appreciated include those in which:

Z, Z ', Z "and Z'" represent, individually, hydrogen or a methyl, methoxy, cyano or halo radical;

R is a straight or branched chain alkyl radical having 1 to 30 carbon atoms or a hydrogen atom;

Rj is a methyl group or a halogen;

R2, R3, R4, R5, R6 and R7 represent, individually, hydrogen or a methyl or ethyl radical.

The enolic esters of 2-aryl-1,3-cyclohexanediones of the present invention can be conveniently prepared by various methods. Two preferred methods which use the basic 2-aryl-1,3-cyclohexanedione as precursor are illustrated by the general reaction schemes given below in which R, Rlt R2, R3j R4, R5, R6, R7, Z, Z ' , Z "and Z '" have the definitions given

O

above and X is a halogen or a hydroxyl group or - OCR, except in the cases indicated:

Diagram I

In the reaction illustrated in Scheme I, an equivalent of the 2- organic interesting to use as acid acceptors in the corresponding arylcyclohexane-1,3-dione is reacted with a conduct of these reactions include tertiary amines, armati -

acid, a suitable acid halide or anhydride or heterocyclic such as pyridine or N, N-dimethyl-substituted in the presence of at least one equivalent of an aniline acceptor 65, linear tertiary amines such as triethylamine , acid, preferably in an inert solvent. pyridine, trimethylamine or 1,4-diazobicyclo- [2.2.2] -octane; or

The acid acceptor used in the reactions of scheme I can alkali metal alcoholates such as, for example, methylate

be an organic base or a mineral base. Examples of sodium bases, sodium ethylate, etc. Bases such as carbonate

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sodium, sodium hydroxide or potassium hydroxide are examples of mineral bases which can advantageously be used as acid acceptors. Preferred organic acid acceptors are tertiary amines such as triethylamine, pyridine or trimethylamine.

In general, any organic solvent which is inert towards the reactants or under the reaction conditions used can be used in the reaction according to scheme I. Examples of organic solvents which are generally suitable for carrying out these reactions include saturated, unsaturated and aromatic hydrocarbons such as hexane, cyclohexane, octane, cyclo-hexene, dodecane, naphtha, decalin , kerosene, cyclo-heptane, benzene, toluene, xylene, naphthalene, etc. ; of

ethers such as dioxane, tetrahydrofuran, diethyl ether, tetrahydropyran, 1,2-dimethoxybenzene, 1,2-diethyl-benzene, dialkyl ethers of ethylene glycol, propylene glycol; or chlorinated aliphatic hydrocarbons such as, for example, chloroform, dichloromethane, dichloromethylene, 1,1-dichloroethane, carbon tetrachloride, etc.

The 2-aryl-1,3-cyclohexanediones of the present invention can be conveniently prepared by various methods. Two preferred processes for the preparation of the compounds of the invention are illustrated by the following reaction schemes in which Rj, R2, R3, R4, R5, Rö, R7, Z, Z ', Z "and Z'" have the definitions given above and Rs is an alkyl group, unless otherwise specified:

Diagram II

Z Ri

Diagram III

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Preferably, the reactions illustrated in Schemes II and III are carried out by contacting equivalent amounts of the reactants in a suitable solvent. In the conduct of the reaction according to scheme III, the nature and the quantity of the solvent used are not decisive. Examples of suitable inert solvents are ethanol, methanol, dimethylformamide, dimethylsulfoxide, methylene chloride, benzene, xylene, toluene, dioxane, dimethoxyethane, tetrahydrofuran, etc.

The reaction illustrated in Scheme II can be carried out in any solvent which is chemically inert to the reactants and the reaction conditions, and in which the acid catalyst is soluble. Examples of these solvents include water and carboxylic acids such as acetic acid, butanoic acid, etc. The preferred reaction solvents are water and acetic acid.

The cyclization reaction illustrated in Scheme II is carried out in the presence of a strong mineral acid used as a catalyst. Examples of mineral acids which can be used in carrying out this reaction are sulfuric acid, hydrochloric acid, perchloric acid, etc. The preferred acid catalyst is sulfuric acid. 20

The amount of acid catalyst which is used in carrying out the reaction according to scheme III is not decisive. In general, to obtain a suitable reaction rate, the reaction is carried out in the presence of about 1 to about 85% by weight of the acid catalyst based on the total weight of the reaction solvent. Preferred acid concentrations range from about 50 to about 85% by weight based on the weight of the reaction solvent.

The cyclization reaction illustrated in scheme III is carried out in the presence of at least one equivalent of a strong, organic or inorganic acid. Examples of bases which are advantageous to use in carrying out this reaction are the alkali metal alcoholates such as sodium methylate or ethylate or potassium tert-butoxide; alkali metal alkylides; or alkali metal hydrides such as sodium hydride, lithium hydride, etc. The basis of choice for carrying out this reaction is sodium hydride.

Other variants for the preparation of a more limited class of 2-aryl-1,3-cyclohexanediones are illustrated by the reaction schemes given below, in which Rx, R2, R3, R4, Rs, R6, R7, Z, Z ', Z "and Z'" have the definitions given above and X is a fluorine or chlorine atom, unless otherwise specified:

Scheme IV

, R2 0 R1 2 r2 ° R1 2

fr- ïQ-ft-

'r7 0 Z'M Z "R7 0 Z'" Z "

In Scheme IV, Rj is an alkyl group and Z, Z ', Z "and Z'" denote something other than a nitro group.

Scheme V

Fz 0 R1 z R2 0 R1? r3 _J / \ / R3 [f \ 1

—O-

R7 Z Z jl 0 21 "Z

In scheme V, Z 'is an alkylsulfonyl group or a low pressure group, lamps for germicidal use, nitro light sources; or Z 'can also be an alkyl or alkoxy group when black, etc.

R, or Z '"is a nitro group. Preferably, the reaction illustrated in scheme V is carried out

The procedure illustrated in diagram IV involves the ss by contact of equivalent quantities of the reactants in a photosensitized decomposition of a suitable 2-diazocycloalkane-1,3-dione solvent, in the presence of at least one equivalent of a base in an aromatic solvent, in the presence of a photosensitive organic or mineral agent. Examples of healthy reaction solvents, preferably benzophenone. In this process, a suitable 2- are dimethylformamide, dimethyl sulfoxide,

suitably substituted diazocycloalkane-1,3-dione is decompo- hexamethylphosphoramide, etc. Examples of bases which can be photochemically used to form the triplet carbene M to be used in carrying out this reaction include correspondents which, in turn, react with an aromatic solvent carbonates or bicarbonates of alkali metals such as bicarbo-

suitable for forming the desired 2-arylcycloalkane-1,3-dione. Sodium nate or potassium carbonate; hydrides of photolysis reaction is conducted under the action of ultraviolet rays of alkali metals such as lithium hydride, sodium hydride or having a wavelength of more than 290 nm. Ultraviolet rays potassium hydride or metal alcoholates or hydroxides can be produced using any conventional source of alkaline light such as sodium hydroxide, sodium methylate or ultraviolet of the type known to specialists in terms of photolysis. potassium tert-butylate. The base of choice is carbonate

Examples of suitable sources of anhydrous potassium light production.

ultraviolet lamps include high mercury arc lamps and Reactions according to schemes II to V are neither sensitive nor to

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temperature or pressure and can be conducted over a wide range of temperatures and pressures to form the desired product. In general, these reactions can be carried out at a temperature of from about -30 to about 200 ° C. For convenience, they are carried out under autogenous pressure or at atmospheric pressure.

The alkali metal and ammonium salts of the compounds of the invention can be conveniently prepared by conventional methods. For example, the alkali metal and ammonium salts can be prepared by treating the corresponding 2-aryl-1,3-cyclohexanedione with, respectively, an alkali metal alcoholate, ammonia or an amine.

The 6-aryl-5-ketopolyalkylhexanoic acids used as reactants in the reaction according to scheme II can be advantageously prepared by reaction of a suitably polysubstituted benzyl cyanide with a derivative of suitable polyalkylglutaric acid in the presence of a base to form the corresponding 6-aryl-6-cyano-5-ketopolyalkylhexanoic acid ester which, in turn, is hydrolyzed under acidic conditions to the desired reactant.

The esters of 6-aryl-5-ketopolyalkylhexanoic acids used as reactants in the reaction illustrated in scheme III can be conveniently prepared by esterification of the 6-aryl-5-ketopolyalkylhexanoic acid reaction in scheme II esterification.

The 2-diazo-1,3-cyclohexanediones used as reactants in the reaction according to scheme IV can be prepared by treatment of a cyclohexane-1,3-dione correctly substituted with a sulfonylazide in the presence of an acid acceptor , for example a trialkylamine, as described in detail by H. Stetter and K. Kiehr in "Chem. Ber. ", 98,1181 (1965), M. Regitz and P. Stodler," Liebigs Ann. Chem. ”, 687,214 (1967) and the bibliographic references described in these articles. Cyclohexane-1,3-dione can be prepared, for its part, by conventional operations, for example by condensation of a suitably substituted α, β-ketone with diethyl malonate in the presence of a basic catalyst such as described in detail by KW Rosenmund, H. Herzberg and H. Scutt in "Chem. Ber. ”, 87,1258 (1954), C.K. Shuang and Y.L. Yours in "Chem. Ber. ”, 69.27 (1936), and in the bibliographical references cited in these articles.

Substituted arylcyclohexanediones, acid halides, acids and anhydrides used as reactants in reactions according to Schemes II to V are known classes of compounds which are commercially available or which can be prepared in accordance with to conventional methods known to specialists in the field of synthesis.

The following practical examples illustrate more particularly the preparation of the new compounds of the invention.

Example 1:

Preparation of 2- (2'-chloro-4'-nitrophenyl) -5-5-dimethyl-

1,3-cyclohexanedione

The mixture is heated to 75 ° C. under a nitrogen atmosphere and a solution containing 42.05 g (0.300 mol) of 5,5-dimethyl-1,3-cyclohexanedione and 100 g (0.718 gram-atom) is stirred for 1 hour. anhydrous potassium carbonate in 300 ml of anhydrous dimethylformamide. The 3,4-dichloronitrobenzene (57.60 g; 0.300 mol) is dissolved in 100 ml of dimethylformamide and the solution is added dropwise to the reaction mixture, with stirring and keeping the temperature of the mixture at 75 ° C. It forms a solution of intense red color and, when the addition is complete, the reaction temperature is brought to 100 ° C. and maintained at this value for 3 h. Most of the dimethylformamide is removed by vacuum distillation. The residue is poured into 21 of ice water and extracted three times with 500 ml of benzene. Nitrogen is passed through the aqueous solution with heating to remove the dissolved benzene. The aqueous solution is cooled in an ice bath and acidified to give a tacky precipitate which, when heated, solidifies and is collected by vacuum filtration. The product recrystallized from acetone gives 31.7 g (36%) of 2- (2'-chloro-4'-nitrophenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of a white powder melting at 250-253 ° C.

Analysis for Ci4H14CIN04 ■ '/ zH20:

Calculated: C 55.18 H 4.96 N 4.60%

Found: C 55.53 H 4.73 N5.09%

Example 2:

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-dimethyl-1,3-cyclo-hexanedione in 150 ml of solution is stirred at room temperature concentrated ammonium hydroxide and 150 ml of ethanol by passing a stream of hydrogen sulfide gas through the solution at a chosen rate so that the hydrogen sulfide is completely absorbed. When the solution has been saturated with hydrogen sulfide, the temperature is raised to the reflux point and a slow flow of H 2 S in the solution at reflux is maintained for 24 h. The reaction mixture is filtered to remove the sulfur and the filtrate is evaporated under reduced pressure. 300 ml of 0.25N sodium hydroxide solution are added to the residue and the solution is filtered again. The filtrate is cooled and carefully acidified to a pH of 4 by the addition of 6N hydrochloric acid. 2- (2'-chloro-4'-aminophenyl) -5,5-dimethyl-1,3-cyclohexanedione is collected by suction filtration. Yield: 13.3 g (74%); melting point: 218-219 ° C.

Analysis for Ci4H16C1N02 ■ / 2H2O:

Calculated: C 61.20 H 6.24 N5.10%

Found: C 60.44 H 5.83 N 5.32%

Example 3:

Preparation of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione

9.66 g (0.0364 mol) of 2- (2'-chloro-4'-aminophenyl) -5.5-dimethyl-1,3-cyclohexanedione are added to 7.0 ml of water and the mixture is stirred. mixture by heating it almost to the boil. A further 15.0 ml of HCl is added and the mixture is cooled to 0-5 ° C. A solution of 3.22 g (0.0467 mol) of sodium nitrite in 9.0 ml of is added dropwise. water while stirring the reaction mixture and keeping it at 0-5 ° C. When the addition of the sodium nitrite solution is complete, the reaction mixture is stirred at 0-5 ° C for 1 h.

The diazonium salt solution prepared as indicated above is added in portions to 161 ml of 50% hypophosphorous acid at 0 ° C, with stirring and cooling. The reaction mixture is stirred for 12 h and filtered to obtain 8.55 g of a tan solid substance. This substance is chromatographed on 250 g of silica gel (particles from 0.063 to 0.2 mm) with an elution gradient ranging from pure benzene to a 70:30 mixture of benzene and ethyl acetate. A total of 7.12 g of reaction product is obtained by chromatography; by recrystallization of this product from a mixture of benzene and ethyl acetate, 6.85 g (75%) of 2- (2'-chlorophenyl) -5.5-dimethyl-1,3-cyclohexanedione are obtained under the form of white crystals melting at 191-192 ° C.

Analysis for C14Hj 5C102:

Calculated: C 67.07 H 6.03%

Found: C 67.04 H 6.00%

Example 4:

Preparation of 2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione

A cuprous chloride sample is prepared by slow addition of 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 of CuSO4 / 5H20 and 2.75 g of NaCl in 100 ml of hot water. Let cool

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cuprous chloride suspension at room temperature and washed several times with water, taking 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 is stirred in 75 ml of water containing 4, 0 ml of concentrated hydrochloric acid and it is almost heated to boiling for 10 min, then it is cooled to 10 ° C and another 7 ml of concentrated hydrochloric acid is added thereto; then the solution is cooled to 0-5 ° C. A solution of 2.00 g (0.0282 mol) of sodium nitrite in 6.0 ml of water is added dropwise to the hydrochloride solution. amine by maintaining the temperature at 0-5 ° C. When the sodium nitrite solution has been completely added, the diazonium salt solution is stirred for 30 min at 0C.

The diazonium salt solution is added in small portions to a solution of cuprous chloride in 40 ml of concentrated hydrochloric acid, at 0 ° C. When the diazonium salt solution has been fully added, the reaction mixture is stirred for about 16 h at room temperature and filtered to obtain 6.22 g of a tan solid substance melting at 175-178 ° C . This crude product is chromatographed on silica gel (0.063-0.2 mm) using a benzene / ethyl acetate gradient ranging from pure benzene to a 70:30 mixture of benzene and ethyl acetate, to obtain 3.51 g (65%) of 2- (2 ', 4'-dichlorophenyl-5,5-dimethyl-1,3-cyclohexanedione in the form of a white crystalline solid melting at 208.5-210 ° C.

Analysis for Ci4H14Cl202:

Calculated: C 58.97 H 4.95%

Found: C 59.06 H 4.82%

Example 5:

Preparation of 2- (2 ', 6'-dichloro-4'-nitrophenyl) -5,5-dimethyl-

1,3-cyclohexanedione

Heated to 75 ° C with stirring under a nitrogen atmosphere for 1 h 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. The 3,4,5-tri-chloronitrobenzene (50.0 g; 0.221 mol) is dissolved in 100 ml of dimethylformamide and the solution is added to the reaction mixture with stirring, maintaining the temperature at 75 ° C. It forms a solution of an intense red and, when the addition is complete, the temperature is raised to 100 ° C and the mixture is stirred for about 16 h at this temperature. Most of the dimethylformamide is removed by vacuum distillation and 21 of water are added to the residue. The aqueous solution is extracted three times with 500 ml portions of benzene, then a stream of nitrogen gas is introduced into the aqueous solution which is heated to remove the dissolved benzene. The solution is cooled in an ice bath and acidified with 6N hydrochloric acid, which gives 63.8 g (87%) of 2- (2 ', 6'-dichloro-4'-nitrophenyl) -5.5 -dimethyl-1,3-cyclohexanedione in the form of a tan-colored powder melting at 288-290 ° C.

Analysis for Ci4H13Cl2N04:

Calculated: C 50.93 H 3.97 N 4.24%

Found: C 50.09 H 3.79 N 4.26%

Example 6:

Preparation of 2- (2 ', 6'-dichloro-4'-aminophenyl) -5,5-dimethyl-

1,3-cyclohexanedione

A solution of 20.0 g (0.0606 mol) of 2- (2 ', 6'-dichloro-4'-nitrophenyl) -5.5-dimethyl-1,3-cyclohexanedione in 150 is stirred at room temperature ml of concentrated ammonia and 150 ml of ethanol, while passing a stream of hydrogen sulphide through the solution at a chosen rate so that the hydrogen sulphide is completely absorbed. When the solution has been saturated with hydrogen sulfide, it is refluxed for 24 h while maintaining the passage of a slow stream of H2S in the solution. The reaction mixture is cooled to room temperature, the precipitated sulfur is removed by filtration and the filtrate is evaporated to dryness under reduced pressure. 300 ml of 0.25N sodium hydroxide is added to the residue and the solution is filtered once more. The filtrate is cooled and acidified to a pH of 4 by addition of 6N hydrochloric acid. A solid, tan-colored substance is formed which is collected by filtration, which gives 11.2 g of dry product. This product is washed with methylene chloride and gives, after washing, 8.2 g (45%) of 2- (2 ', 6'-dichloro-4'-aminophenyl) -5,5-dimethyl-1,3-cyclohexanedione under the form of a white powder melting at 243 ° C as it decomposes.

Analysis for C14Hj s C12N02:

Calculated: C 56.02 H 5.04 N 4.67%

Found: C 56.34 H 4.95 N 4.67%

Example 7:

Preparation of 2- (2 ', 6'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione

2- (2 ', 6'-dichloro-4'-aminophenyl) -5.5-dimethyl-1,3-cyclohexanedione (5.00 g; 0.0167 mol) is added to 3.5 ml of acid concentrated hydrochloric acid in 75 ml of water and the mixture is stirred while heating it almost to the boil. The suspension is cooled to 10 ° C and another 7.5 ml of concentrated hydrochloric acid is added thereto. The mixture is cooled to 0-5 ° C and a solution of 1.44 g (0.0209 mol) of sodium nitrite in 3.5 ml of water is added dropwise, while the mixture is stirred. reaction mixture while maintaining it at 0-5 ° C. When the addition of the sodium nitrite solution is finished, the reaction mixture is stirred at 0 ° C for 1 h.

The solution of the diazonium salt prepared above is added in portions to 75 ml of 50% hypophosphorous acid, with stirring and cooling to 0 ° C. The reaction mixture is stirred for 2 h and filtered to give 5.03 g of a brown powder. This substance is recrystallized from a mixture of benzene and chloroform, giving 2.69 g of a light brown solid substance melting at 227-229 ° C. The residue of the mother liquor (1.70 g) is chromatographed on silica gel (0.063-0.2 mm) giving 0.84 g of a white solid melting at 228-232 ° C. The total yield of 2- (2 ', 6'-dichlorophenyl) -5, 5-dimethyl-1,3-cyclohexane-1,3-dione is 3.53 g (74%).

Analysis for C14H14C1202:

Calculated: C 58.97 H 4.95%

Found: C 58.64 H 4.86%

Example 8:

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 (anhydrous, distilled) containing 32.8 g (0, 3) is degassed with a stream of nitrogen for 1 h. 18 mol) of benzo-phenone and irradiated using a 200 W mercury arc lamp equipped with a borosilicate glass filter until the band corresponding to the diazo function (4.68 (j.) in the infrared spectrum has completely disappeared The reaction is also monitored by thin layer chromatography (ethyl acetate / benzene 90/10) and the irradiation is continued until no more is observed of diazoketone at an Rf equal to 0.31. The irradiation lasts 11 h. The mesitylene is extracted with 0.25N sodium hydroxide until a small sample has no cloudiness when it is After collecting the basic extracts, they are washed twice with 200 ml portions of ether and acidified (pH 3-5)

with normal hydrochloric acid. The aqueous solution is extracted three times with 75 ml portions of chloroform, dehydrated over anhydrous magnesium sulfate and the solvent is removed, leaving 5.06 g of a brown solid.

This solid substance is chromatographed on 250 g of silica gel (0.063-0.2 mm) eluted with a gradient ranging from pure benzene to a

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80:20 mixture of benzene and ethyl acetate. A total of 2.60 g (31%) of a white solid is obtained (homogeneous according to thin layer chromatography) which is recrystallized from diisopropyl ether to give 1.96 g of 2- ( 2 ', 4', 6'-trimethyl-phenyl) cyclohexane-1,3-dione in the form of white crystals, melting at 196-198 ° C.

Analysis for C, 5Hi802:

Calculated: C 78.23 H 7.88%

Found: C 77.94 H 8.20%

Examples 9 and 10:

Preparation of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethylcyclo-hexane-1,3-dione and of 2- (2', 6'-dimethylphenyl) -5,5-dimethyl-cyclohexane -1,3-dione

A solution of 5.00 g (0.0301 mol) of 2-diazo-5,5-dimethylcyclohexane-1,3-dione in 500 ml of m-xylene containing 27.4 g is degassed with nitrogen for 1 h. (0.15 mol) of benzophenone and it is irradiated for approximately 16 h with a 200 W mercury arc lamp equipped with a borosilicate glass filter. The mixture treated by photolysis is extracted with 0.25N sodium hydroxide, the combined basic extracts are washed with ether and acidified with chloroform, then they are dried over anhydrous magnesium sulfate and the solvent is removed, leaving 3.61 g of a tan solid substance. The irradiation is repeated using 7.00 g (0.042 mol) of 2-diazo-5,5-dimethylcyclohexane-1,3-dione and 38.38 g (0.21 mol) of benzophenone in 500 ml of m- xylene. The treatment gives 5.48 g of a solid substance of tan color.

The combined crude products (9.09 g) are chromatographed on silica gel (0.063-0.2 mm), the eluent consisting of a mixture of benzene and ethyl acetate. The column is eluted with: 1) 500 ml of benzene, 2) 500 ml of 95: 5 mixture of benzene and ethyl acetate, 3) 1000 ml of 90:10 mixture of benzene and acetate d 'ethyl, and 4) 1000 ml of 80:20 mixture of benzene and ethyl acetate. After collecting 21 of solvent, the column is connected to an automatic fraction collector and 15 ml fractions are collected. Tubes 1 to 94 contain small amounts of a yellow oil. Tubes 95 to 150 contain a light yellow solid which contains a single component (Rf 0.55 in a mixture of hexane and ethyl acetate at 50:50) according to thin layer chromatography and which weighs 2.18 g. This substance gives, by recrystallization from benzene, 1.17 g of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of a white powder melting at 167- 169 ° C.

Analysis for C, 6H20O2:

Calculated: C 78.65 H 8.25%

Found: C 78.68 H 8.12%

This compound is found to be 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione.

The tubes 151 to 230 are assembled; they give 2.0 g of a white solid which contains a single component (Rf = 0.57 in a mixture of hexane and ethyl acetate at 50:50 according to thin layer chromatography). This substance is recrystallized from benzene giving 1.90 g of 2- (2 ', 6'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of white crystals, melting at 177-186 ° C .

Analysis for C, 6H20O2:

Calculated: C 78.65 H 8.25%

Found: C 78.28 H 8.21%

This compound is found to be 2- (2 ', 6'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione.

Example 11:

Preparation of 2-diazo-5-phenylcyclohexane-1,3-dione A solution of 20.0 g (0.106 mol) of 5- is cooled to -10 ° C.

phenylcyclohexane-1,3-dione in 75 ml of ethanol and stirred under a nitrogen atmosphere using a magnetic stirrer. 10.75 g (0.106 mol) of triethylamine are added to the mixture. The tosylazide (20.95 g; 0.106 mol) is added slowly at once and the mixture is stirred for 1 h at 0-5 ° C. The solvent is removed in vacuo at a temperature below 40 ° C. to the residue 200 ml of ether and the mixture is extracted with a solution containing 3.1 g of potassium hydroxide in 200 ml of water. The ether solution is dried over anhydrous magnesium sulphate, filtered, and the solvent is removed, leaving a yellow solid which, by recrystallization from a mixture of ethanol and hexane, gives 8.38 g (32 %) of 2-diazo-5-phenylcyclohexane-1,3-dione in the form of yellow crystals, melting at 122-124 ° C.

Example 12:

Preparation of 2- (2 ', 4', 6'- trimethylphenyl) -5-phenylcyclo-hexane-1,3-dione

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 are degassed with nitrogen for 1 h and it is irradiated with a 200 W mercury arc lamp equipped with a borosilicate glass filter, for approximately 16 h. The mixture treated by photolysis is extracted with 0.25N sodium hydroxide, the combined basic extracts are washed with ether, acidified with IN hydrochloric acid, then extracted with chloroform. The chloroform solution is dried over anhydrous magnesium sulfate and the solvent is removed, leaving 5.7 g of a tan solid substance. This material is purified by column chromatography on silica gel (0.063-0.2 mm) using a mixture of benzene and ethyl acetate to give 5.7 g (57%). 'a white solid. By recrystallization of this substance from a mixture of benzene and ethyl acetate, 4.08 g (41%) of 2- (2 ', 4', 6'-trimethylphenyl) -5-phenylcyclohexane-1 are obtained, 3-dione in the form of a white crystalline solid substance melting at 215-216 ° C.

Analysis for C2iH2202:

Calculated: C 82.32 H 7.24%

Found: C 82.38 H 7.14%

Example 13:

Preparation of 2- (2 ', 6'-dimethyl-4'-tertiobutylphenyl) -5,5-dimethyl-1,3-cyclohexanedione

Irradiated for approximately 16 h, with a 200 W mercury arc lamp equipped with a borosilicate glass filter, a solution of 7.00 g (0.042 mol) of 2-diazo-5,5-dimethylcyclohexane-l , 3-dione in 300 ml of 5-tert-butyl-m-xylene and 250 ml of chlorobenzene containing 38.38 g (0.21 mol) of benzophenone, after degassing for 1 h under nitrogen atmosphere. The mixture treated by photolysis is extracted with 0.25N sodium hydroxide, washed with ether, acidified with a solution of IN hydrochloric acid and extracted with chloroform. The chloroform is dried over anhydrous magnesium sulfate and removed leaving a crude yellow solid. The photolysis is repeated and the crude products of these reactions, after having been combined, are chromatographed on silica gel (0.063-0.2 mm) using a mixture of benzene and ethyl acetate. The solid obtained by chromatography is recrystallized from benzene to give 2.76 g (11%) of 2- (2 ', 6'-dimethyl-4'-tertiobutylphenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of white crystals melting at 244-249 ° C.

Analysis for C20H28O2:

Calculated: C 79.95 H 9.39%

Found: C 79.76 H 9.45%

Example 14:

Preparation of 2-diazodecaline-l, 3-dione

A solution of 10.0 g (0.0768 mol) of decaline-1,3-dione in 50 ml of ethanol is stirred using a magnetic stirrer under

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nitrogen atmosphere and cooled to -10 ° C. To the solution is added 7.77 g (0.0768 mol) of triethylamine and then 15.14 g (0.0768 mol) of p-toluenesulfonylazide, added all at once. The mixture is stirred for 1 h at 0 ° C and the solvent is removed at a temperature below 40 ° C under reduced pressure. 200 ml of ether are added to the residue and the ether is removed to obtain a yellow solid. By recrystallization of this substance from ethanol, 5.23 g of yellow crystals are obtained, melting at 81-83 ° C.

Example 15:

Preparation of 2-f2'-methylphenyl) -decaline-1, 3-dione

A solution of 7.0 g (0.0364 mol) of 2-diazodecaline-1,3-dione and 33.18 g (0.182 mol) of benzophenone in 500 ml of toluene is degassed for 1 h under nitrogen atmosphere and it is irradiated with a 200 W mercury arc lamp fitted with a borosilicate glass filter, for approximately 16 h. The mixture treated by photolysis is extracted with 0.25N sodium hydroxide, the basic extracts are combined, washed with water, acidified with 1M hydrochloric acid and extracted with chloroform. The chloroform extracts are dried over anhydrous magnesium sulfate and the solvent is removed, giving 4.56 g of a crude product, yellow in color. This product is purified by column chromatography on silica gel (0.063-0.2 mm) using a mixture of benzene and ethyl acetate. The solid obtained is recrystallized from benzene, giving 1.85 g (20%) of 2- (2'-methylphenyl) decaline-1,3-dione in the form of white crystals, melting at 165-167 ° C.

Analysis for Q 7H20O2:

Calculated: C 79.65 H 7.86%

Found: C 79.82 H 7.43%

Example 16:

Preparation of 6- (2 ', 4'-dimethylphenyl) -6-cyano-5-keto-

Ethyl 3,3-dimethylhexanoate

A dry and clean 500 ml capacity three-tube flask is equipped with a reflux condenser, a mechanical stirrer, a dropping funnel and a nitrogen inlet tube. 70 ml of absolute ethanol and then 6.00 g (0.26 gram-atom) of sodium are loaded into this flask and the reaction mixture is stirred and heated until all the sodium has dissolved. The temperature of the reaction mixture is 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 3.3 -diethyl dimethylglutarate is added dropwise over 2 hours using the dropping funnel. When the addition is complete, the reaction mixture is maintained at reflux for 12 h. At the end of this period, about two-thirds of the ethanol was distilled off and the reaction mixture was heated at reflux for another 2 h, then cooled to room temperature and poured into 600 ml of an ice mixture and water.

The basic aqueous solution is extracted twice with 300 ml of ether, then acidified (pH 3) with 6N hydrochloric acid. An oil is formed and the aqueous acid solution is extracted twice with 250 ml portions of ether. The ether phase coming from the extraction of the aqueous acid is washed twice with water, dried over anhydrous magnesium sulfate and evaporated, leaving 52.83 g (84%) of 6- (2 ', Ethyl 4'-dimethylphenyl) -6-cyano-5-keto-3,3-dimethylhexanoate in the form of a very viscous clear colorless oil. This oil is not purified, but characterized by infrared spectrometry and by the nuclear magnetic resonance spectrum.

Infrared spectrum (without dilution, dd, main absorptions): 2.8-3.2 (OH, enol); 4.55 (C = N); 5.85, 6.02.6.19 (C = 0); 6.3 (C = C); 7,45,8,25,9,85,12,25.

NMR (CDClj, S): 1.20 (multiplet, 9H); 2.33 (multiplet, 8H), 2.68 (multiplet, 2H); 4.17 (quadruplet, 2H); 4.90 and 12.0 (singlet, 1H); 7.05 (multiplet, 3H).

Example 17:

Preparation of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione and 6- (2', 4'-dimethylphenyl) -5-keto-3.3 acid -dimethylhexanoic

52.50 g (0.17 mol) of 6- (2 ', 4'-dimethylphenyl) -6-cyano-3,3-dimethyl-hexanoate ethyl are loaded into a round bottom flask with a single tube, 250 ml of concentrated hydrochloric acid, 250 ml of glacial acetic acid and 100 ml of water. The reaction mixture is stirred and refluxed for 48 h. After 12 and 24 h of reflux, a further 100 ml of concentrated hydrochloric acid and 100 ml of glacial acetic acid are added. After 48 h, the mixture is evaporated to dryness under reduced pressure. 150 ml of water and 150 ml of ethyl ether are added to the residue and the mixture is stirred with vigorous shaking. A white crystalline precipitate is formed which is separated by suction filtration, which gives 13.20 g (32%) of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethyl-1, 3-cyclohexanedione in the form of a white crystalline substance melting at 167-168.5 ° C.

Analysis for Cl6H20O2:

Calculated: C 78.65 H 8.25%

Found: C 78.68 H 8.12%

The ether phase is separated from the filtrate, washed once with water, dried over anhydrous magnesium sulfate and evaporated, leaving 29.04 g (65%) of 6- (2 ', 4'-dimethylphenyl) acid. ) -5-keto-3,3-dimethylhexanoic in the form of a viscous yellow oil. This oil is not purified, but characterized by the infrared spectrum and the nuclear magnetic resonance spectrum.

Infrared spectrum (CHC13, p., Main absorptions): 2.9-4.3 (OH); 5.90 (C = 0).

NMR (CDCl3, S): 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, large, 3H).

Example 18:

Preparation of 2- (2'-chlorophenyl) -1,3-cyclohexanedione Loaded into a 500 ml round-bottomed flask 10.0 g (0.0416 mol) of 6- (2'-chlorophenyl) acid 5-ketohexanoic and 100 ml of 72% sulfuric acid. The reaction mixture is stirred and heated at 120 ° C for 5.5 h (oil bath), then poured into 600 ml of a mixture of ice and water. A tacky white solid is formed which is extracted into 300 ml of methylene chloride. The chloromethylenic solution is washed six times with water, dried over anhydrous magnesium sulfate and evaporated, leaving 8.87 g of white sticky solid substance. This substance is recrystallized from ethyl acetate giving 5.85 g (63%) of 2- (2'-chlorophenyl) -1,3-cyclohexanedione in the form of a white crystalline solid melting at 148 , 5-149 ° C.

Analysis for C ^ HuClOj:

Calculated: C 64.73 H 4.98%

Found: C 64.49 H 4.89%

Example 19:

Preparation of 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoic acid

Following the procedure of Example 17, ethyl 6- (2 ', 4'-dimethylphenyl) -6-cyano-5-ketohexanoate is hydrolyzed in the presence of concentrated hydrochloric acid to prepare the acid 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoic in a yield of 49%, in the form of a solid substance of tan color melting at 75.0-76.5 ° C. This solid substance was characterized by the infrared spectrum and the nuclear magnetic resonance spectrum.

Infrared spectrum (CHC13, | x, main absorptions): 2.9-4.2 (OH); 5.92 (C = 0).

NMR (CDCl3, S): 1.7-3.3 (multiplet, 6H); 2.48 (singlet, 3H); 3.71 (singlet, 2H); 7.31 (singlet, large, 3H).

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Example 20:

Preparation of ethyl 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoate

A 500 ml round-bottomed flask with a single tubing equipped with a Soxhlet extraction apparatus and 100 g of molecular sieves with a pore diameter of 3 Å, 12.74 g (0.0544 mol) are loaded 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoic acid, 125 ml of absolute ethanol, 125 ml of anhydrous benzene and 2.0 ml of concentrated sulfuric acid. The mixture is refluxed for 12 h, then two thirds of the mixture of ethanol and benzene is removed under reduced pressure. The residue is poured into 500 ml of ice water and extracted into 300 ml of ether. The ether is washed three times with 10% potassium carbonate, then once with water, it is dried over anhydrous magnesium sulfate and evaporated, to obtain 13.34 g of an oil dark yellow in color. By distillation of this oil, 12.77 g (89%) of ethyl 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoate are obtained in the form of a clear colorless oil boiling at 134-145 °. C (0.05 mm). This oil has also been characterized by the infrared spectrum and the nuclear magnetic resonance spectrum.

Infrared spectrum (without dilution, | x, main absorptions): 5.85 (C = 0), 8.60 (C = 0).

Nuclear magnetic resonance (CDC13, S): 1.15 (triplet, 3H); 1.50-2.6 (multiplet, 6H); 2.10 (singlet, 3H); 2.20 (singlet, 3H); 3.52 (singlet, 2H); 3.95 (quadruplet, 2H); 6.80 (singlet, large, 3H).

Example 21:

Preparation of 2- (2 ', 4'-dimethylphenyl) -1,3-cyclohexanedione

A round bottom flask with three tubes of 500 ml capacity is equipped with a mechanical stirrer, a dropping funnel and a reflux condenser. The glassware is properly dried and the flask is loaded with 4.62 g (0.096 gram atom) of 50% sodium hydride in mineral oil. The oil is removed from the sodium hydride by washing with toluene, then 100 ml of toluene are added. The mixture is heated to 65 ° C., then added dropwise over 2 h to 12.62 g (0.0481 mol) of ethyl 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoate. The mixture is maintained at 65 ° C for 12 h, then carefully cooled with 25 ml of ice water. The reaction mixture is diluted with 250 ml of water and extracted twice with 150 ml of ether. The basic aqueous solution is acidified to a pH equal to 3 by addition of 6N hydrochloric acid and extracted twice with 150 ml of methylene chloride. The methylene chloride is washed with water, dried over anhydrous magnesium sulfate and evaporated, leaving 5.88 g of a semi-solid substance. This substance is recrystallized from ethyl acetate giving 5.10 g (49%) of 2- (2 ', 4'-dimethylphenyl) -1,3-cyclohexanedione in the form of a white crystalline solid melting at 143-145 ° C.

Analysis for Cj ^ Hj 602:

Calculated: C 77.75 H 7.46%

Found: C 76.99 H 7.46%

Example 22:

Preparation of 6- (2 ', 5'-dimethylphenyl) -6-cyano-5-keto-

Ethyl 3,3-dimethylhexanoate

Following the procedure of Example 16, 29.04 g (0.200 mol) of 2,5-dimethylbenzyl cyanide and 64.88 g (0.300 mol) of 3,3-dimethylglutarate diethyl are reacted to obtain 45, 24 g (72%) of 6- (2 ', 5'-dimethylphenyl) -6-cyano-5-keto-3,3-dimethylhexanoate in the form of a clear colorless viscous oil. The structure is confirmed by the infrared spectrum and the nuclear magnetic resonance spectrum.

Infrared spectrum (without dilution, [i, main absorptions): 2.9-3.7 (OH, enol); 4.55 (C = N); 5.80, 5.98.6.10 (C = 0); 6.23 (C = C); 7,35,7,60,8,15,9,70, 12,30.

NMR (CDClj, 8): 1.18 (multiplet, 9H); 1.67-2.73 (multiplet, 10H); 4.12 (quadruplet, 2H); 4.88 (singlet, 1H); 7.05 (wide,

singlet, 3H).

Example 23:

Preparation of 6- (2 ', 5'-dimethylphenyl) -5-keto-3,3-dimethylhexanoic acid and of 2- (2', 5'-dimethylphenyl) -5,5-dimethyl-1,3 -cyclohexanedione

A solution of 45.24 g (0.14 mol) of ethyl 6- (2 ', 5'-dimethylphenyl) -6-cyano-5-keto-3,3-dimethylhexanoate, 250 ml of glacial acetic acid, 250 ml of concentrated hydrochloric acid and 70 ml of water. After 24 hours, another 100 ml of concentrated hydrochloric acid and 150 ml of glacial acetic acid are added.

After reflux for 48 h, the reaction mixture is allowed to cool to room temperature and the solvent is removed under reduced pressure. The residue is vigorously shaken with 250 ml of water and 250 ml of diisopropyl ether. A white crystalline precipitate is formed which is removed by suction filtration, which gives 7.90 g (23% yield) of 2- (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1, 3-cyclohexanedione melting at 168-170 ° C.

Analysis for Ci 6H20O2:

Calculated: C 78.65 H 8.25%

Found: C 78.16 H 8.03%

The ether phase is separated from the filtrate, washed once with water, dried over anhydrous magnesium sulfate and evaporated, leaving 17.97 g of 6- (2 ', 5'-dimethylphenyl) -5- acid. keto-3,3-dimethyl-hexanoic in the form of a yellow oil. This oil is not purified, but it is characterized by the infrared spectrum and the nuclear magnetic resonance spectrum.

Infrared spectrum (without dilution, dd, main absorptions): 2.9-3.8 (OH); 5.90 (C = 0); 12.3 (aromatic).

NMR (CDCl3, S): 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 24:

Preparation of ethyl 6- (2 ', 5'-dimethylphenyl) -5-keto-3,3-dimethyl hexanoate

Following the procedure of Example 20, the 6- (2 ', 5'-dimethylphenyl) -5-keto-3,3-dimethylhexanoic acid is esterified with absolute ethanol in the presence of a catalytic amount. concentrated sulfuric acid to obtain 15.52 g (78% yield) of ethyl 6- (2 ', 5'-dimethylphenyl) -5-keto-3,3-dimethylhexanoate in the form of a pale viscous oil .

Example 25:

Preparation of 2- (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione

Following the procedure of Example 21, the ethyl 6- (2 ', 5'-dimethylphenyl) -5-keto-3,3-dimethylhexanoate is treated with sodium hydride to obtain 9.87 g of crude product which, by recrystallization, gives 8.77 g (64%) of 2- (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of a solid substance white crystalline melting at 167-168 ° C.

Example 26:

Preparation of 3- (2-ethylhexanoyloxy) -2- (2'-chlorophenyl) -5,5-dimethyl-2-cyclohexenone

Cooled in an ice bath and stirred under a nitrogen atmosphere a solution of 1.009 g (3.99 mmol) of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione and 0, 03 g (8.0 mmol) of pyridine. 2-Ethylhexanoyl chloride (0.69 g, 4.25 mmol) is added, then the mixture is allowed to warm to room temperature, stirred at this temperature for 1 h and refluxed for another 1 h. The solvent is removed under reduced pressure and the residue is taken up in ether and water. The ether is washed three times with 0.25N sodium hydroxide, three times with 10% hydrochloric acid, then with water. Dehydrate ether on sulfate

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anhydrous with magnesium and poured out by settling, which gives 1.23 g (82%) of 3- (2'-ethylhexanoyloxy) -2- (2'-chlorophenyl) -5,5-dimethyl-2-cyclohexenone under the form of a clear colorless oil which is homogeneous according to thin layer chromatography.

Analysis for C22H29CIO3:

Calculated: C 70.10 H 7.76%

Found: C 70.09 H 7.86%

Example 27:

Preparation of 3- (2'-ethylhexanoyloxy) -2- (2 ', 4'-dichloro-phenyl) -5,5-dimethyl-2-cyclohexenone

A solution of 1.76 g (7.02 mmol) of 2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione in 10 ml of chloroform is cooled with ice. add 1.11 g (14.04 mmol) of pyridine, then 1.21 g (7.47 mmol) of 2-ethylhexanoyl chloride. The mixture is stirred for 2 h at room temperature, then it is refluxed for 12 h.

The reaction mixture is treated exactly as described in Example 1 above to give 2.09 g of a yellow oil. This oil is chromatographed by low pressure liquid chromatography on silica gel using a gradient of hexane and ethyl acetate; 1.15 g (41%) of 3- (2'-ethylhexanoyl-oxy) -2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-2-cyclohexenones are obtained in the form of a clear oil colorless. The thin layer chromatogram (hexane / ethyl acetate 80/20) of this material has a single spot of Rf equal to 0.46.

Analysis for C22H28CI2O3:

Calculated: C 64.23 H 6.86%

Found: C 64.44 H 6.80%

Example 28:

Preparation of 3-hexanoyloxy-5,5-dimethyl-2- (2 ', 4'-dimethyl-phenyl) -2-cyclohexênone

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 is cooled with ice. 1.94 g (24.56 mmol) of pyridine, then 1.64 g (12.28 mmol) of hexanoyl chloride. The mixture is stirred for 2 h at room temperature, then it is refluxed for 5 h.

The reaction mixture is cooled to room temperature and taken up in 150 ml of ether. The ether is washed three times with 50 ml of 0.25N sodium hydroxide, twice with 50 ml portions of ice-cold 6N HCl and twice with water. The ether is dried over anhydrous magnesium sulfate and removed under reduced pressure; 0.98 g (47% yield) of 3-hexanoyloxy-5,5-dimethyl-2- (2 ', 4'-dimethylphenyl) -2-cyclohexenone remains in the form of a clear colorless oil. This oil has a single spot in the thin layer chromatogram (hexane / ethyl acetate 70/30) at an Rf equal to 0.49.

Analysis for C22H30O3:

Calculated: C 77.15 H 8.83%

Found: C 77.25 H 8.92%

Example 29:

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 is cooled with ice. 1.94 g (24.56 mmol) of pyridine, then 2.00 g (12.28 mmol) of 2-ethylhexanoyl chloride. The mixture is stirred for 2 h at room temperature, then it is refluxed for 12 h. It is treated exactly as described in Example 1 above to obtain 1.58 g of a slightly yellow viscous oil. This material is chromatographed on 75 g of silica gel (0.063-0.2 mm) using an elution gradient ranging from 98: 2 to 90:10 (hexane / ethyl acetate). Chromatography gives 1.15 g (51%) of 3- (2-ethylhexanoyloxy) -5,5-dimethyl-2- (2 ', 4'-dimethylphenyl) -2-cyclohexenone as a colorless oil 5 clear which has a single spot in the thin layer chromatogram (hexane / ethyl acetate 70/30), at an Rf equal to 0.52.

Analysis for C24H34O3:

Calculated: C 77.80 H 9.25%

10 Found: C 77.34 H 9.48%

Example 30:

Preparation of 3-hexanoyloxy-2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-2-cyclohexenone 15 A solution of 2.00 g (8.00 mmol) of 2- is cooled with ice. (2 ', 4'-dichlorophényI) -5,5-dimethyl-1,3-cyclohexanedione in 10 ml of chloroform and 1.26 g (16.00 mmol) of pyridine are added, then 1.14 g (8, 50 mmol) of hexanoyl chloride. The mixture is stirred for 2 h at room temperature and refluxed for 12 h. The reaction mixture is treated exactly as described in Example 1 above to obtain 1.94 g of a slightly yellow oil. This material is analyzed by low pressure liquid chromatography using a gradient of hexane and ethyl acetate. By treating the chromatographic fraction, 1.55 g (51% yield) of 3-hexanoyloxy-2- (2'-4'-dichlorophenyl) -5.5-dimethyl-2-cyclohexenone are obtained in the form of a Clear colorless oil which gives in the thin layer chromatogram (hexane / ethyl acetate 80/20) a single spot at an Rf equal to 0.27.

3 °

Analysis for C20H24Cl2O3:

Calculated: C 62.67 H 6.31%

Found: C 62.83 H 6.32%

35 Example 31:

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- is prepared. (2 ', 5'-40 dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione in 15 ml of anhydrous benzene and 0.49 g (7.37 mmol) of potassium hydroxide powder is added to 85 %, then a drop of dicyclohexyl-18-corona-6-ether. After stirring for 30 min, 1.20 g (7.37 mmol) of 2-ethylhexanoyl chloride is added and the reaction mixture is refluxed for 12 h. It is allowed to cool to room temperature, it is taken up in 150 ml of ether and 50 ml of water, it is washed three times with 0.25N sodium hydroxide,

twice with water, twice with 6N hydrochloric acid and once more with water. The ether solution is dried and evaporated, leaving 2.10 g (92% yield) of 3- (2-

ethylhexanoyloxy) -5,5-dimethyl-2- (2 ', 5'-dimethylphenyl) -2-cyclo-hexenone in the form of a clear colorless oil.

Analysis for C24H34O3:

55 Calculated: C 77.80 H 9.25%

Found: C 77.46 H 8.98%

Example 32:

Preparation of 2- (2 ', 4'-dimethylphenyl) -1,3-cyclohexanedione

60 A round bottom flask with three tubes of 500 ml capacity is equipped with a mechanical stirrer, a dropping funnel and a reflux condenser. The glassware is dried properly and the flask is loaded with 4.62 g (0.096 gram atom) of 50% sodium hydride in mineral oil. The oil is removed from the 65 sodium hydride by washing with toluene, then 100 ml of toluene are added. The mixture is heated to 65 ° C. and 12.62 g (0.0481 mol) of ethyl 6- (2 ', 4'-dimethylphenyl) -5-ketohexanoate are added dropwise over 2 hours. The mixture is maintained at 65 ° C. for 12 h, then it is

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cooled by carefully adding 25 ml of ice water. The reaction mixture is diluted with 250 ml of water and extracted twice with 150 ml of ether. The aqueous basic solution is acidified to a pH equal to 3 by addition of 6N hydrochloric acid and extracted twice with 150 ml of methylene chloride. The methylene chloride is washed with water, dried over anhydrous magnesium sulfate and evaporated, leaving 5.88 g of a semi-solid substance. By recrystallization of this substance from ethyl acetate, 5.10 g (49%) of 2- (2 ', 4'-dimethylphenyl) -1,3-cyclohexanedione is obtained in the form of a crystalline solid substance. white melting at 143-145 ° C.

Analysis for C14.H] 602:

Calculated: C 77.75 H 7.46%

Found: C 76.99 H 7.46%

Example 33:

Preparation of 2- (2'-chlorophenyl) -1,3-cyclohexanedione Loaded into a round bottom flask, with three tubes of 500 ml capacity, 10.0 g (0.0416 mol) of acid 6- (2'-chlorophenyl) -5-ketohexanoic and 100 ml of 72% sulfuric acid. The reaction mixture is stirred and heated at 120 ° C for 5.5 h (oil bath), then poured into 600 ml of ice water. A tacky white substance is formed which is extracted into 300 ml of methylene chloride. The chloromethylenic solution is washed six times with water, dried over anhydrous magnesium sulfate and evaporated, leaving 8.87 g of a white sticky substance. This substance is recrystallized from ethyl acetate yielding 5.85 g (63%) of 2- (2'-chlorophenyl) -1,3-cyclohexanedione in the form of a white crystalline solid substance melting at 148, 5-149 ° C.

Analysis for C12Hj iC102:

Calculated: C 64.73 H 4.98%

Found: C 64.49 H 4.89%

Example 34:

Preparation of 2- (2'-chloro-4'-nitrophenyl) -5,5-dimethyl-1,3-cyclohexanedione

The solution is heated to 75 ° C. under a nitrogen atmosphere, with stirring for 1 hour, a solution containing 42.05 g (0.300 mol) of 5,5-dimethyl-1,3-cyclohexanedione and 100 g (0.718 gram-atom) of carbonate. anhydrous potassium in 300 ml of anhydrous dimethylformamide. A solution of 57.60 g (0.300 mol) of 3,4-dichloronitrobenzene in 100 ml of dimethylformamide is added dropwise to the reaction mixture, with stirring and keeping the temperature at 75 ° C. An intense red solution is obtained and, when the addition is complete, the temperature of the reaction mixture is raised to 100 ° C. and the temperature is maintained at this value for 3 h. Most of the dimethylformamide is removed by vacuum distillation. The residue is poured into 21 of ice water and the mixture is extracted three times with 500 ml of benzene. Nitrogen is then passed through the aqueous solution with heating to remove the dissolved benzene. The aqueous solution is cooled in an ice bath and acidified to give a tacky precipitate which, when heated, solidifies and is collected by vacuum filtration. The reaction product is recrystallized from acetone, giving 31.7 g (36%) of 2- (2'-ch! Oro-4'-nitrophenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of a white powder melting at 250-253 ° C.

Analysis for C14H14C1N04 • 'AHjO:

Calculated: C 55.18 H 4.96 N 4.60%

Found: C 55.53 H 4.73 N 5.09%

Example 35:

Preparation of la2- (2'-chloro-4'-aminopkényl) -5,5-dimethyl-1,3-cyclohexanedione

A solution of 20.0 g (0.067 mol) of 2- (2'-chloro-4'-nitrophenyl) -5.5-dimethyl-1,3- is stirred at room temperature

cyclohexanedione in 150 ml of concentrated ammonium hydroxide and 150 ml of ethanol while passing a stream of hydrogen sulfide through the solution at a chosen rate so that the hydrogen sulfide is completely absorbed. When the solution has been saturated with hydrogen sulfide, the temperature is raised to the point of reflux and the passage of hydrogen sulfide is continued for 24 h at a slow rate in the solution maintained at reflux. The reaction mixture is filtered to remove the sulfur and the filtrate is evaporated under reduced pressure. 300 ml of 0.25N sodium hydroxide is added to the residue and the solution is filtered again. The filtrate is cooled and carefully acidified to a pH of 4 by addition of 6N hydrochloric acid. A white solid substance is formed which is collected by vacuum filtration, and 13.3 g (74%) of 2- (2'-chloro-4'-aminophenyl) -5.5-dimethyl- are thus obtained. 1,3-cyclohexanedione melting at 218-219 ° C.

Analysis for CI4Hi6C1N02 '' / 2H2O:

Calculated: C 61.20 H 6.24 N5.10%

Found: C 60.44 H 5.83 N 5.32%

Example 36:

Preparation of 2- (2'-chlorophenyl) -5,5-dimethyl-

1,3-cyclohexanedione

9.66 g (0.0364 mol) of 2- (2'-chloro-4'-aminophenyl) -5.5-dimethyl-1,3-cyclohexanedione are added to 7.0 ml of concentrated hydrochloric acid in 150 ml of water and the mixture is stirred, practically heating it to the boil. A further 15.0 ml of hydrochloric acid is added and the mixture is cooled to 0-5 ° C. A solution of 3.22 g (0.0467 mol) of sodium nitrite in 9.0 ml of water is added dropwise while stirring the reaction mixture and keeping it at 0-5 ° C. When the addition of sodium nitrite solution is complete, the reaction mixture is stirred at 0-5 ° C for 1 h.

The diazonium salt solution prepared above is added in portions to 161 ml of 50% hypophosphorous acid at 0 ° C with stirring and cooling. The reaction mixture is stirred for 12 h and filtered giving 8.55 g of a tan solid substance. This substance is chromatographed on 250 g of Woelm silica gel (0.063-0.2 mm), eluting with a gradient ranging from pure benzene to a mixture of benzene and ethyl acetate at 70:30. A total of 7.12 g of product is obtained by chromatography; this product is recrystallized from a mixture of benzene and ethyl acetate, which gives 6.85 g (75%) of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of white crystals melting at 191-192 ° C.

Analysis for C14H [5C102:

Calculated: C 67.07 H 6.03%

Found: C 67.04 H 6.00%

Example 37:

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 (anhydrous, distilled) containing 32.8 g (0.18 mol) is degassed with nitrogen for 1 h. ) of benzophenone and it is irradiated with a Hanovia 200 W immersion lamp, through a borosilicate glass filter until the diazo band (4.68 y.) has completely disappeared from the infrared spectrum. The reaction is also followed by thin layer chromatography (ethyl acetate / benzene 90/10) and the irradiation is continued until the diazoketone can no longer be observed at an Rf equal to 0.31. The irradiation requires a period of 11 h. The mesitylene is extracted with 0.25N sodium hydroxide until a small sample becomes cloudy when acidified. The combined basic extracts are washed twice with 200 ml of ether and acidified (pH 5) with IN hydrochloric acid. The solution

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632394

16

aqueous solution is extracted three times with 75 ml portions of chloroform, dehydrated over anhydrous magnesium sulfate, then the solvent is removed, leaving 5.06 g of a tan solid substance.

This solid substance is chromatographed on 250 g of silica gel (0.065-1.2 mm), the elution being carried out with a gradient ranging from pure benzene to an 80:20 mixture of benzene and ethyl acetate. A total of 2.60 g (31%) of a white solid is obtained (homogeneous according to thin layer chromatography), which is recrystallized from diisopropyl ether, which gives 1.96 g of 2- (2 ', 4', 6'-trimethylphenyl) -1,3-cyclohexanedione in the form of white crystals melting at 196-198 ° C.

Analysis for Ci 5H1802:

Calculated: C 78.23 H 7.88%

Found: C 77.94 H 8.20%

2-Aryl-1,3-cyclohexanediones and certain of their alkali metal salts, their ammonium salts and their enolic esters were chosen as representative examples of compounds according to the invention and they were used in tests to test their acaricide, ovicide against mites and herbicide pre-emergence and post-emergence activities.

Suspensions of the test compounds were prepared by dissolving 1 g of each compound in 50 ml of acetone containing in solution 0.1 g (10% of the weight of the compound) of a surfactant alkylphenoxyethanol, used as an emulsifying agent or dispersant. The resulting solution was poured with stirring into 160 ml of water to form approximately 200 ml of a suspension containing the compound in a finely divided form. The mother suspension thus prepared contained 0.5% by weight of compound. The test concentrations used in the experiments described below were obtained by diluting the mother suspension with water. The test methods were as follows:

Foliar spray test against mites

Adults and nymphs of the spider mite [Tetranychus urticae (Koch)] raised on bean plants of the Tendergreen variety at 27.8 ± 2.7 ° C and at a relative humidity of 50 + 5% constitute the organisms of test. Infested leaves from a mother crop are placed on the primary leaves of two 15.2 to 20.3 cm tall bean plants grown in a 6.35 cm soil pot. 150 to 200 mites, representing a sufficient number for the test, pass from excised leaves to fresh plants in a 24 h period. After the 24 h transfer period, the excised leaves are removed from the infested plants. Test compounds are formulated by diluting the mother suspension with water to form suspensions containing the desired amount of test compound per million parts of final formulation. Plants grown in pots (1 pot per compound) are placed on a turntable and treated by spraying with 100 to 110 ml of test compound formulation, using a DeVilbis spray gun set at an air pressure of 2, 8 bar. This application, which lasts 30 s, is sufficient to wet the plants until drops come off. As a control test, 100 to 110 ml of an aqueous solution containing acetone and an emulsifier are also sprayed on the infested plants at the same concentrations as the formulation of the test compound, but not containing the compound d 'test. Plants treated by spraying are kept at 27.8 + 2.7 ° C and a relative humidity of 50 ± 5% for 4 d, after which a count of motile forms mortality is carried out. Motile forms are examined under the microscope on the leaves of the test plants. Anyone capable of locomotion when stimulated with a tip is considered to be alive.

Ovicide test against mites

The test organism consists of eggs of the spider mite [Tetranychus urticae (Koch)], obtained from adults reared on bean plants of the Tendergreen variety under controlled conditions involving a temperature of 27.8 ± 2.7 ° C and a relative humidity of 50 ± 5%. Heavily infested leaves taken from a mother crop are placed on the primary leaves of two bean plants 15.2 to 20.3 cm high, grown in a 6.35 cm diameter earthen pot. The females are allowed to lay their eggs for a period of 48 h, then the leaves of the infested plants are immersed in a solution containing 800 parts of tetraethyl pyrophosphate per million parts of water so as to destroy the forms capable of reproducing and thus preventing any oviposition. This tetraethyl pyrophosphate solution does not affect the viability of the eggs. The plants are allowed to dry properly. The test compounds are formulated by diluting the mother suspension with water to obtain a suspension containing varying amounts of the test compound per million parts of final formulation. Potted plants (one pot per compound) are placed on a turntable and spray treated with 100 to 110 ml of the test compound formulation, using a DeVilbis spray gun set to a gauge air pressure of 2 , 8 bar. This application, which lasts 30 s, is sufficient to wet the plants until drops come off. As a control test, sprayed on plants infested with eggs 100 to 110 ml of an aqueous solution containing acetone and an emulsifier at the same concentrations as the formulation of the test compound, but not containing of test compound. Plants treated by spraying are kept at a temperature of 27.8 ± 2.7 ° C and a relative humidity of 50 ± 5% for 4 d, after which a microscopic examination is carried out to detect unhatched (dead) eggs and hatched (live) eggs.

In these tests, the pesticidal activity of the compounds against the mites and their eggs is evaluated according to the following rating scale:

A = excellent inhibition;

B = partial inhibition;

C = no inhibition.

Preliminary herbicide test on seed germination

The following seeds are used in this test:

Perennial tares Lolium perenne

Blood pan Digitarla sanguinalis

Amaranth reflected Amaranthus retroflexus

Brassica pincea var.foliosa mustard (Florida broadleaf herb)

Two seed-soil mixtures are prepared as indicated below:

Mixture I 196 cm3 of perennial rye seeds 75 cm3 of mustard seeds 18 000 cm3 of very dry sieved soil.

Mixture II 99 cm3 of blood pan seeds 33 cm3 of amaranth seeds 18000 cm3 of very dry sieved soil.

Each of the above mixtures is separately agitated by rotation in 18.91 containers for about 1 hour on a ball mill so as to ensure uniform mixing of the seeds and the soil. For each compound, three 7.6 cm pots are filled with soil, up to 3.8 cm from the edge. 70 cm3 of mixture I are added to two of these pots. 70 cm3 of mixture II are added to the two remaining pots. The mixture of seeds and soil is packed properly and the pots are placed in a greenhouse and lightly watered. 2 h after this operation, 25 ml of the test formulation are added to each of the two pots for each mixture of seeds and soil; there is therefore a replica of each mixture of seeds for each concentration. An equal volume of an aqueous solution containing acetone and an emulsifier at the same concentration as the herbicide mixture, but not containing the herbicide tested, is also added to each of the soil and seed mixtures . These pots are used as control pots or control pots. Test compounds are formulated by the conventional method, i.e. dissolving in

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632394

acetone, addition of the emulsifier and dilution with water. The tests are carried out on all compositions at low concentration (100 parts per million). Certain compositions are also tested at high concentration (1000 parts per million). The pots are kept in the greenhouse and lightly watered until the results are read. 10 to 12 d after the application of the chemical, the deterioration of each species is noted by comparison of the treated pots with the untreated pots. Assessments are made at high and low concentrations (1000 and 100 ppm) according to the following rating scale:

5 = no seedling emergence;

4 = some seedlings raised and / or very marked stunting;

3 = moderate population reduction and / or stunting; moderate;

2 = very slight reduction in population and / or slight stunting

I = no alteration; seedlings did not appear to differ from untreated controls in population or growth.

Post-emergence herbicide trial

Tests have also been carried out to determine the phytotoxicity of representative compositions, compared to fresh and healthy plants. Solutions of the compounds were prepared as described above to obtain a test compound concentration of 2500 parts per million. Test plants are spray treated in accordance with the method described above with respect to the foliar spray test against mites, to deliver about 100 ml of test solution to the leaves of each plant tested . The plants and the controls treated by spraying are left to stand for approximately 1 h to allow the solutions to dry, then they are installed in a greenhouse. After 10 d, visual inspection of the plants is carried out to determine the degree of deterioration of the foliage. Note 1 means that there is no noticeable alteration; 5 means that the plant is dead and notes 2,3 and 4 indicate intermediate degrees of deterioration based on the number of altered leaves and the extent of the deterioration.

The results of these tests are summarized in Tables I and II. Table I gives the results of tests relating to 2-aryl-1,3-cyclohexanediones and their alkali metal salts and Table II indicates results of tests corresponding to enolic esters, 2-aryl-1, 3-cyclohexanediones.

(Tables on the following pages)

It should be noted that the plant species used in the above tests are only representative examples of a wide variety of parasitic plants which can be destroyed using the compounds of the invention. The compounds of the present invention can be applied as ovicides against house dust mites, acaricides and herbicides according to methods known to those skilled in the art. Pesticide compositions containing the compounds of the invention as active substance usually contain a support and / or a diluent, liquid or solid.

Suitable diluents or liquid carriers include water, petroleum distillates or other liquid carriers with or without surface active agents. Liquid concentrates can be prepared by dissolving one of these compounds in a non-phytotoxic solvent such as acetone, xylene or nitrobenzene and by dispersing the active substances in water using emulsifying agents and suitable surfactant dispersants.

The choice of dispersants and emulsifiers and the amount used is dictated by the nature of the composition and by the ability of the agent in question to facilitate the dispersion of the active substance. Generally, it is desirable to use this agent in amounts as small as the desired dispersion of the active ingredient in the spray formulation allows, so that rain does not re-emulsify the active ingredient after it is applied to the plant and it does not remove it by washing the plant. Non-ionogenic, anionogenic, amphoteric or cationogenic dispersing and emulsifying agents can be used; for example, the condensation products of alkylene oxides with phenol and organic acids, alkylarylsulfonates, complex ether alcohols, quaternary ammonium compounds, etc. can be used.

In the preparation of a wettable powder or a powder for dusting or of granular compositions, the active ingredient is dispersed in and on the suitably divided solid support such as clay, talc, bentonite, diatomaceous earth, fuller's earth, etc. In the formulation of wettable powders, the above-mentioned dispersing agents, as well as lignosulfonates, can be included.

The desired quantity of active substances which it is intended to use in accordance with the invention can be applied, per hectare treated, in a volume of approximately 9.5 to 1900 or more than 19001 of vehicle and / or liquid diluent or in about 5.5 to 550 kg of inert solid support and / or diluent. The concentration in the liquid concentrate usually ranges from about 10 to 95% by weight and, in solid formulations, from about 0.5 to about 90% by weight. Satisfactory forms of sprayable compositions, powders for dusting or granules, for general applications, contain from about 275 g to about 16.5 kg of active substance per hectare.

The pesticides which are the subject of the present invention protect plants or another material to which pesticides are applied from attack by insects and mites, and their residual toxicity is relatively high. As far as plants are concerned, they have a large margin of safety since, when they are used in sufficient quantity to destroy or repel insects, they do not burn the plant or alter it in any way. other way and they resist atmospheric factors which involve a risk of elimination by washing under the effect of rain, of decomposition by ultraviolet light, of oxidation or of hydrolysis in the presence of humidity, or else they resist all at least to a degree of decomposition, oxidation and hydrolysis which would significantly reduce the desired pesticidal characteristics of active substances or which would give them an undesired characteristic, for example phytotoxicity. The active substances have such chemical inertness that they are compatible with practically all the other constituents involved in the spraying operation, and they can be used in the soil, on the seeds or on the roots of plants without any alteration of seeds or plant roots. They can also be used in combination with other compounds endowed with pesticidal activity. When used as acaricides, they are normally applied to the foliage of plants to be treated. When used as herbicides, they can be incorporated into the soil or applied directly to the seeds to be treated. It should be noted that the compounds of the invention can also be used in combination with other compounds with biological activity.

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Table I

N>

Physical properties and biological activity of 2-aryl-1,3-cyclohexanediones and their alkali metal salts ^

4 *.

h oy

* 5> H-

i °

Ri

Z "'

Rs

Re

Z '

Z "

Y

P.F.

(° C)

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

Cl

H

H

H

H

H

H

148.5-149

AT

AT

2

4

1

2

2

5

5

1

2

Cl

H

H

H

Cl

H

H

163-165

AT

AT

2

3

2

2

1

5

5

3

3

-ch3

h h

h h

H

H

146-147

B

vs

2

4

1

2

2

5

4

2

3

-ch3

h h

H

-ch3

H

H

143.5-145

AT

AT

2

3

2

2

2

5

5

1

2

-ch3

H

-ch3

-ch3

H

h h

178-179.5

AT

AT

1

1

1

1

1

5

5

1

3

-ch3

H

-ch3

-ch3

-ch3

H

H

167-168.5

AT

AT

2

1

2

2

1

5

5

4

4

-ch3

H

-ch3

-ch3

h

-ch3

h

168-169

AT

AT

2

1

2

2

1

5

5

3

3

Cl

H

-ch3

-ch3

-ch3

Cl

H

238-240

vs

B

1

1

2

1

1

5

1

1

1

Cl h

-ch3

ch3

H

h

Na +

> 250

AT

AT

2

4

1

2

1

5

5

4

4

Cl

H

H

h

H

H

Na +

> 250

AT

B

3

4

1

2

2

5

5

3

3

-ch3

h

-ch3

ch3

-ch3

H

Na +

> 250

AT

' AT

2

5

1

2

2

5

5

3

5

Cl h

-ch3

ch3

Cl

H

Na +

> 250

AT

AT

2

4

2

2

5

5

5

5

-Cp3

h

-ch3

ch3

no2

h h

235-237

CC

1

1

1

1

1

1

1

1

1

-cf3

h

-ch3

ch3

h

H

H

209-211.5

B

vs

1

1

1

1

1

4

3

3

2

-cf3

H

-ch3

ch3

Cl

H

h

209.5-211

AT

B

1

1

1

1

1

5

4

3

2

-ch3

H

-ch3

ch3

no2

H

H

240-245

CC

1

1

1

1

1

1

1

1

2

-ch3

-no2

-ch3

-ch3

no2

H

H

233-235

CC

1

1

1

3

1

1

1

1

-ch3

-no2

-ch3

-ch3

H

H

H

226-229

AT

B

1

1

1

2

1

4

3

3

2

-CN

H

-ch3

-ch3

-no2

H

H

234 Dec

CC

1

1

1

1

1

1

1,

1

1

Cl

-no2

-ch3

-ch3

-no2

H

H

238 Dec

vs

VS

1

1

1

1

1

1

1

1

1

Cl

H

-ch3

-ch3

-no2

H

H

248-251

CC

2

2

1

1

1

1

Cl

H

-ch3

-ch3

-ch3

H

H

141-142

AT

AT

1

2

1

1

1

5

5

3

3

Cl

H

-ch3

-ch3

Cl

H

H

207-209

AT

AT

1

1

1

1

1

5

5

3

3

Cl

Cl

-ch3

-ch3

-no2

H

H

288-290

CC

1

1

1

1

1

1

1

1

1

Table I (continued)

Physical properties and biological activity of 2-aryl-1,3-cyclohexanediones and their alkali metal salts r,

z '"

rs r6

z '

z "

y

P.F.

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity cc)

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

Cl

Cl

-ch3

-ch3

h h

h

227-229

a a

1

3

2

2

1

5

5

1

3

-ch3

-ch3

h h

-ch3

h h

196-198

AT

at

3

4

2

1

1

5

5

2

2

-ch3

-ch3

-ch3

-ch3

-ch3

h h

212-216

a a

1

2

1

2

1

5

5

1

3

-ch3

-ch3

-ch3

-ch3

h h

h

177-186

a a

1

1

2

1

2

5

5

1

2

-ch2ch3

h

-ch3

-ch3

h h

h

118-121

CC

2

5

2

2

2

5

5

1

1

-ch3

-ch3

((

)

-ch3

h h

196-202

CC

1

1

1

1

1

5

5

1

3

-ch3

h

\

-ch3

/

-ch3

-Cl h

h

190-192

a b

1

1

1

1

1

5

4

3

3

-ch3

Cl

-ch3

-ch3

h h

h

188-191

a a

1

1

1

1

1

5

4

3

3

-ch3

-ch3

h

-c6h5

-ch3

h h

215-216

CC

1

1

1

2

1

5

5

4

3

-ch3

-ch3

-ch3

-ch3

c (ch3) 3

h h

244-249

CC

1

1

1

1

1

1

1

1

1

—Ch (ch3) 2

h

-ch3

ch3

h h

h

161-164

CC

1

3

2

2

2

5

5

1

3

-och3

h

-ch3

ch3

-ch3

h h

115-119

CC

2

3

2

1

2

5

5

2

2

-ch3

och3

-ch3

ch3

h h

h

172-174

a b

1

2

1

1

1

5

5

1

3

-ch3

-och3

-ch3

ch3

-ch3

h h

155-159]

go to

at

1

5

1

2

2

1

1

1

1

-ch3

-ch3

-ch3

ch3

-och3

h h

155-159 days

at

1

5

1

2

2

1

1

1

1

-ch3

h

((

)

h h

h

143-145

a a

1

1

1

1

2

5

5

2

3

-ch3

h n

-ch3

/

-ch3

-cn h

h

188-191 -

a c

2

1

1

2

1

1

1

1

1

-ch3

-cn

-ch3

-ch3

h h

h

193-195

a c

2

2

2

2

1

1

1

1

1

a Mixture of the two isomers.

Table II S

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

II

t> - (h2c) 6-c0 ç1

I50-0- "

Vax. (f *) •

5.75 (C = 0 ester); 6.05 (C = O ketone)

AT

AT

1

5

2

2

2

5

5

4

4

<h3c) 2nd (h £) 6-Jo cl

C1

H3C / V_ / W

w.W:

5.70 (C = 0 ester); 5.75, 6.0 (C = 0 ketone)

AT

AT

1

4

1

1

1

5

5

3

3

0

f (h2c) 6-é0 cl

2o b- "

Y

Vax. (e);

5.75 (C = 0 ester); 6.0, 6.05 (C = 0 ketone)

AT

AT

1

4

1

1

1

5

5

1

3

0

II

h3c- (h2c) 16-co cl

5Q-0-

3 \

Vax. 0X) ■

5.75 (C = 0 ester); 6.05 (C = 0 ketone)

AT

AT

1-

1

1

1

1

4

5

2

3

to o

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

^ 0

76.5-78

AT

AT

1

5

2

2

3

5

5

4

4

0

II

(h3c) 3cc0 ci%

91-93

AT

AT

1

3

1

1

1

5

5

3

3

0

! 1 ci h3c- (h2c) .- Òp V

Vax. (t *) •

5.70 (C = O ester); 6,0,6,05 (C = 0 ketone)

AT

AT

2

4

1

2

3

5

5

3

4

ch-ch, 0

F H

h ^ - (h xi-hc-co cl

Vax. W •

5.70 (C = 0 ester); 6.0,6.05 (C = 0 ketone)

AT

AT

1

4

1

1

1

1

1

1

1

Table II (continued) 2

N>

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

H3CÜO Cl

H3Vx-_K

41-42.5

AT

AT

2

2

2

2

3

5

5

2

2

"3 ° ^^ - y

0 Cl

0

y

(H.C) „CCO Cl ao-b

84-85

AT

AT

2

2

2

2

1

5

5

1

2

0 II

H3CCO Cl

■ xfr-

^ Cl

99.5-101

AT

AT

1

3

1

1

1

2

2

1

1

0

II

H ^ - <H2C) a> - CO Cl

5Q-0

3 \

Vax. (t ^) •

5.72 (C = 0 ester); 6,0,6,05 (C = 0 ketone)

AT

AT

2

5

2

2

2

5

5

4

3

N> K)

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cycIohexanediones

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

CH3CH2 0

H3C- (H2C) j HC-Cp Cl \

Vax. (t1) •

5.70 (C = 0 ester); 5.95, 6.0 (C = O ketone)

AT

AT

2

5

1

1

1

2

2

1

1

0

II

0- (H2C) 6-CO Cl

: x> b

Vax. O-1) •

5.68 (C = 0 ester); 5.95, 6.0 (C = 0 ketone)

AT

AT

1

3

2

2

2

5

5

4

3

0

(H3C ^ HC (H2C) 6-0) Cl

: x £ b

^ 0

Vax. (t1) *

5.75 (C = 0 ester); 6.0, 6.05 (C = 0 ketone)

AT

AT

1

5

1

1

1

5

5

3

3

0

(f ^ CfcCO Cl

Vax. (t *):

5.75 (C = 0 ester); 6,0,6,05 (C = O ketone)

AT

AT

1

4

1

1

1

4

5

1

2

H3C \ / \ - /

0

Table II (continued)

K> W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyelohexanediones g

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard hi> (h2ö16io C1 m r— () —v

\

47-49

AT

AT

1

1

1

1

1

3

4

2

2

h3cc D cl

:; x worm

\

92.5-94

AT

AT

1

3

1

1

1

5

5

3

3

0

II

(h3c) 2hccp ci

SQ - & -

0

65.5-66.5

AT

AT

2

5

2

2

3

5

5

3

4

0

H3CCO Cl i: xi-b

M3

Vax. ((*) •

5.70 (c = 0 ester); 6.05 (c = 0 ketone)

AT

AT

2

4

2

2

3

5

5

3

3

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

ir

(H3C) 2HCC0 C1

schj

\

Vax. (t1) •

5.73 (C = 0 ester); 6.5 (C = O ketone)

AT

AT

1

4

2

2

3

5

5

4

4

r, s

O-C0 Cl

77-78

AT

AT

2

3

2

2

2

5

5

5

3

0

(h3c) 3cHo cl

;; x3-b

\

86-87

AT

AT

2

2

2

2

1

5

5

1

3

0

11

h3cc o ch3

Vax. (H *) •

5.75 (C = 0 ester); 6.5, 6.10 (C = 0 ketone)

AT

AT

2

5

2

2

3

5

5

5

3

i-o a \

u »

K "

W £

Table II (continued) S

ts>

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. CO or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

(h3c) 2hccd ra3

i :: x> b -

x0

238-240

a a

2

5

2

2

3

5

5

4

5

0

h3c (h2c) 16-io ch3

5Q-0—

o m2

42-44

CC

1

1

1

1

1

1

1

1

1

0

he h3cco ch3

% 4

79.5-81

AT

AT

1

3

2

2

2

4

4

4

3

0

II

(H3c) 3cc ° ch3

SQ-p x) no2

101.5-103

AT

AT

1

1

1

1

1

5

5

2

2

NJ 0 \

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

II

HoCCD Cl

Vax. (f *) •

5.70 (C = O ester); 6.00, 6.08 (C = O ketone)

VS

AT

2

5

2

1

2

5

4

1

3

0

'I

H3C- (HoC), - CO C1

Vax. (t1) •

5.70 (C = 0 ester); 6.00, 6.05 (C = O ketone)

AT

AT

3

5

2

2

2

5

5

1

1

HoCHoC 0

3 1 H

H ^ C- ^ HtCH-C - co Cl c ^ b

Vax. (m-):

5.72 (C = 0 ester); 6.00, 6.10 (C = O ketone)

AT

AT

2

5

1

1

2

3

4

1

1

0

II

Hf- (H2C) i6 "CO Cl

Vax. (H -) -

5.72 (C = 0 ester); 6.00, 6.10 (C = O ketone)

VS

AT

2

3

1

1

1

4

4

1

1

Table II (continuation J W

NOT

w

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones S

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

HjC- (H2C) 4-Cp Cl

Q-Ò- "

^ max. (i *) •

5.70 (C = O ester); 5.98, 6.08 (C = 0 ketone)

AT

AT

2

3

1

2

3

5

5

1

1

0

II

(H302HCCP CH3

Q ^>

0

W. W:

5.73 (C = 0 ester); 6,03,6,12 (C = 0 ketone)

AT

AT

2

5

2

2

2

5

5

1

1

0

RjCHH ^ CO CH3

0 ~ Ò

W. (f *):

5.70 (C = 0 ester); 6.00, 6.08 (C = 0 ketone)

AT

B

2

5

2

2

2

5

5

1

1

H w

0

<H3C) 3CCO ™ 3

;; X3 b- * \

106-107,

VS

VS

1

1

1

1

1

1

1

1

1

to

00

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyciohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

II

h3cco cf3

92.0-92.5

VS

VS

2

3

2

2

2

5

5

1

2

0

00 <% cïo ",

H3X3 Ö- "02

93-96

AT

AT

1

1

1

1

1

1

1

1

1

0

II

043C) 3CCO CH3

120-121

VS

VS

1

1

1

1

1

1

1

1

1

0

II

BjC- <H £> 6-co ai 3

z $ h

^ ir

62-63

AT

AT

1

1

1

1

1

1

1

\

1

1

K>

vo

© \

w

S)

(Ji

VO

-u

Table II (continued) S

N »U>

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

II

(H3c) 3cco ch3 0

103-106

AT

AT

1

1

1

1

1

1

1

1

1

0

II

(H, C)> CCO Cl D N02

111-112

VS

VS

1

1

1

2

2

1

1

1

1

0

II

(H3C) 3CCO Cl yS-th-

\

65-68

AT

AT

2

1

2

1

2

1

1

1

1

0

II

H3C- (H2C) 16-C0 Cl d a

44-45

b

VS

1

1

1

1

1

1

1

1

1

U)

o

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. ("C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 n

(H3C) 2HCCO CM,

0-ô

0

Vax. (ï1) •

5.75 (C = 0 ester); 6.03, 6.12 (C = 0 ketone)

AT

AT

2

5

2

2

2

5

5

1

1

0

H3C (H2C) 4-CO CH3

O

0

Vax. G *):

5.70 (C = 0 ester); 6.00,6.08 (C = O ketone)

AT

AT

2

5

2

2

2

5

5

1

1

HtCHOC 0

^ 1 II H, C- (CH0)., - CH-CO 3 23. Cl

0 — t> cl

0

Vax. (m-);

5.70 (C = 0 ester); 5.98.6.08 (C = 0 ketone)

AT

AT

2

3

1

1

2

1

1

1

1

0

II

H3C- (H2C) 16-CO Cl

0 — i> ci

0

34.0-34.5

AT

AT

1

3

1

1

1

5

2

1

1

Table II (continued) 25

In »W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

CiLjGUjû

h3c- (h2c) 4-hc-co ch

Vax. (f1) *

5.75 (C = 0 ester); 6.00,6.10 (C = 0 ketone)

AT

AT

1

5

1

1

2

5

3

1

1

0 n

H3C- (H2C) 16-CO CH3

C ^> ".

Vax. (f1) •

5.75 (C = 0 ester); 6,00,6,15 (C = 0 ketone)

AT

AT

1

3

1

1

1

5

5

1

1

CH3Clj2.9

413C- (H2C) 3-HC-CO CH-i 0

Vax. W:

5.78 (C = 0 ester); 6.05,6.15 (C = 0 ketone)

AT

AT

1

5

1

1

1

5

1

1

1

CH.CH., 0

J J. Il

H3C- (H2C) 3-HC-CO CL

Vax. (f *) •

5.78 (C = O ester); 6.05,6.10 (C = 0 ketone)

AT

AT

1

1

2

1

2

1

1

1

u »

tsJ

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

Q

H3C (H2C) a-C! O ch3 J 0 CH

3

Vax. (t4) *

5.75 (C = 0 ester); 6,0,6,05 (C = 0 ketone)

AT

AT

2

4

2

2

2

5

4

1

1

CH3CHj, j HoC-tHjOn-HC-CO CH »

30-0

D 0 CH3

Vax. (i *):

5.75 (C = 0 ester); 6.05,6.10 (C = O ketone)

AT

AT

1

2

1

1

2

1

1

1

1

0

not

HnCdo CH,

") CH3

h3c \

Vax. W •

5.70 (C = O ester); 6.00.6.05 (C = 0 ketone)

AT

AT

2

5

1

2

2

5

5

3

3

0

(h3c) 2hcIo ch

3ct — 1>

0

77-78

AT

AT

2

5

1

2

2

5

5

3

3

L> J

0 \ W N> W SO J *.

Table II (continued) S

K "U"

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones ^

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

CHctt o

^ 1 H

h3c- (h2c) 3-hc-cq ch3

cK>

Vax. 0):

5.78 (C = 0 ester); 6.00,6.10 (C = O ketone)

AT

AT

2

5

2

1

3

2

1

1

1

0

h3c- (h2c) 4-co ch3

0—

Vax. (f) •

5.73 (C = 0 ester); 6.00,6.10 (C = 0 ketone)

AT

AT

2

4

2

2

2

5

5

2

2

0

II

h3c- (h2c) 16-co ch3

Vax. (i1):

5.75 (C = 0 ester); 6.05, 6.10 (C = 0 ketone)

AT

AT

2

3

2

2

2

5

3

1

1

0

II

(h3c) 2hcco ch

VA <,

Vax. (H *) •

5.80 (C = 0 ester); 6.10, 6.15 (C = 0 ketone)

AT

b

2

4

1

2

3

5

5

1

2

u)

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

WE

Table II (continued) ^

W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones jS

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

1

CZXvZ ^ 0

132-133

VS

AT

1

1

1

1

1

3

3

1

1

0

II

(h3c) 3ccy ch3

yirp-

111-113

VS

VS

1

1

1

1

1

5

5

1

1

0

u h3c- (h2c)] 6-co ch3

O-ö

0

38-40

AT

AT

1

2

2

1

1

5

3

1

1

0

ii

(h3c) 3ccq cvh3

$ -9--

(j 3

71-73

b b

1

4

3

1

2

5

5

1

1

u>

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

II

(H3C) 3CCO CH3

61-62

AT

AT

1

1

1

1

2

5

4

1

1

0 c »3

dcH>

152-156

AT

AT

-

2

-

1

1

5

-

-

5

- OCOCHo r-, r-i iL

DQ-Ö

0

wc "11" 1):

1760 (C = 0 ester); 1670.1645 (C = 0 ketone)

AT

AT

-

4

-

2

2

5

-

-

4

ÇH2CH3. ocochch2ch3

cdr ^ b

^ 0

^ max. (cm-1):

1750 (C = 0 ester);

1678.1645 (C = 0 ketone)

AT

AT

-

3

-

1

1

4

-

-

1

OJ -j o \

W

W v © 4 *.

Table II (continued) 2d

W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones ^

Biological activity

Formula

P.F. ("C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

CH, CH,

1

OCOCH (CH2) CH3

"YwS

^ max. (cm) •

1750 (C = 0 ester); 1680 (C = 0 ketone)

AT

AT

1

2

1

1

1

1

1

1

1

CH3A -_ (\ - /

o tH3

Cl

OCOCH20- ^ j ^ —Cl v / C \ L-

110-113

VS

AT

5

1

4

4

4

4

5

5

5

U t-H3

Ixfö

250

AT

AT

-

3

-

1

2

5

-

-

4

0 CH2CH3 II 1 0 - C - CHCH2CH3

/ 'CH-J

CH3 / \ J

SA 0

\ iiax. C * 311) •

1750 (C = 0 ester);

1678.1645 (C = 0 ketone)

AT

AT

-

2

-

1

1

5

-

-

2

u »oo

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 II

0-C (CH2> 6CH3 ch3 / 9H3

^ max. ) •

1760 (C = 0 ester); 1680 (C = O ketone)

AT

AT

3

5

2

3

3

5

5

3

4

0 II

0-C (CH2) 14CH3

36-38

AT

AT

-

2

-

1

1

5

-

-

3

OCO (CH2) 6Clt3

W (cm "1):

1750 (C = 0 ketone)

AT

AT

-

5

-

2

2

5

-

-

5

OCO (CH2) aCH3

/ 04

Q — O chj

W (cm-1):

1758 (C = 0 ester);

1678.1640 (C = 0 ketone)

AT

AT

-

1

-

2

2

5

-

-

3

OJ

-o o \ w

W SO

Table II (continued) Sì

W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Oco mustard <>

/

c »3 — çy — f ~ \ - ™ 3

Xo

'■ max. C0111) •

5.82 (C = 0 ester); 6.02, 6.10 (C = 0 ketone)

AT

AT

1

5

1

2

1

5

-

2

2

ch2ch3

ococh (ch2) 3ch3 / CH3

cH3 ~ Q-0

0

^ raax. ) •

1755 (c = 0 ester); 1660 (C = O ketone)

a a

2

3

1

1

1

2

2

1

1

/? ctt3 ch3_ ^ <Hh.ch3

143-145

a a

2

3

1

3

1

5

5

3

3

d ^ na ^

j ch3

chH0 — Ò c "3

0

> 250

a a

-

3

-

2

2

5

-

-

3

4 ^ ©

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Oco mustard (ch2) ^ ch3 0

^ max. (cm).

1758 (C = 0 ester);

1678.1650 (c = 0 ketone)

AT

at

-

5

-

2

3

5

-

-

4

çh2ch3

ococh (ch2) 3ch3

1 f "3

CH3CH2 / - \} V

Y ^ r \ _CH3

ch3ch2 \ / \ - /

W (an_1):

1750 (C = 0 ester); 1678.1655 (C = O ketone)

AT

at

-

5

-

1

1

1

-

'-

1

0c0 (ch9) ach3

1 f "3

CHnCH, J i J v

.U = Q-Ö—

\ nax. ) •

1758 (C = 0 ester); 1678.1650 (C = 0 ketone)

a a

-

3

-

1

1

5

-

-

3

OCOCHj / CH3

C »3-Q — C„ 3

O

Nnax. (Çïïl) •

1760 (C = 0 ester); 1675 (C = 0 ketone)

a a

-

5

-

2

2

5

-

-

5

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (= C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard ococh2ch3

c „3

Xmax. (cm-1):

1760 (C = 0 ester); 1678 (C = 0 ketone)

AT

AT

-

5

-

2

3

5

-

-

5

OCO (CH2) 3CH3

'' max. (cm) •

1758 (C = 0 ester); 1678.1642 (C = 0 ketone)

AT

AT

-

5

-

2

2

5

-

-

5

0 tl

Û-C ^

135-136

B

B

2

1

1

1

2

1

1

1

1

0 ch2ch3 u 1

0-c-ch (ch2) 3ch3

'' max. (t1) ■

5.75 (C = 0 ester); 6.00,6.08 (C = 0 ketone)

AT

AT

1

3

1

1

1

1

1-

1

1

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

CHj

"H-h

167-169

VS

VS

2

1

1

2

2

1

1

1

1

\ / \ ~ /

0 II

0-C-CH (CH2) 3CH3 / <* 3

o-o-

'■ max. (t1) •

5.75 (C = O ester); 7.00, 6.10 (C = 0 ketone)

AT

AT

1

3

1

1

1

1

1

1

1

H

OCOCH3

/ CH3

(/ VV-CH3

W. (t *):

5.75 (C = O ester); 6.05,6.10 (C = O ketone)

AT

AT

3

3

1

2

1

1

-

1

2

CH-i t P CH3

184-185.5

VS

AT

1

1

1

1

1

5

3

1

2

M w

-t ". U)

o \

u

W vo

"T

Table II (continued) g}

Or

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 CH2CH3 II 1

O-C-CH (CH2) 3CH3 / C "3

vs

'max. (cm).

1750 (C = 0 ester);

1678, 1648 (C = 0 ketone)

AT

AT

-

1

-

1

1

5

-

-

1

0 II

0-C (CH2) 6 xo CH3

'' max. 0-0 ■

5.70 (C = 0 ester); 5.98.6.05 (C = O ketone)

AT

AT

1

5

2

2

1

5

5

2

2

CH-1 cH3

$ -b-

109-112

AT

AT

2

2

2

2

2

5

5

3

4

oco-O

CH3 /

91-92.5

AT

AT

-

3

-

2 '

2

5

-

-

3

É

raoieauii (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 ii o-c- (ch2) 6ch3 ch3 j f *

yó — o-ci

'max. (cm).

1760 (c = 0 ester); 1670 (C = O ketone)

a a

-

4

-

1

2

5

-

-

4

0 ii

0-üo-ft2) / ch3

ch3 / \

y5-O

ch ^ ch3

'' max. (rO •

5.75 (c = 0 ester); 6.05,6.15 (C = 0 ketone)

a a

1

4

1

1

2

5

3

1

1

0 ii

0-C (c.tt2) 6ch3

c »3 J f *

CHi

W. (y -) '-

5.75 (c = 0 ester); 6.02,6.13 (C = O ketone)

a a

1

3

1

1

2

5

4

1

1

0

° -c—

122-23

a a

-

1

-

1

1

4

-

-

1

-u u)

o \

w

W VO 4 ^.

Table II (continued) 2>

N U)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. ("C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

1!

O-C-CH3

/ vCH2CH3

> Q-Ö

'■ max. C * 311) •

1765 (C = 0 ester);

1675 (C = 0 ketone)

VS

VS

-

5

-

2

4

5

-

-

3

OCO (CH2) gcil3

/ CH3 CHJCH-JCMJ ", y \

v \ s / v «3

U

'' IIKLX. fc1 * 1) •

1758 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

1

4

1

2

2

5

5

1

3

OCO 0 / ch3

CH3C: H2CH2 / V

> Cy Oc "3

CHi ~ \> k

'' max. ).

1738 (C = 0 ester); 1680.1655 (C = 0 ketone)

AT

AT

-

3

-

2

2

5

-

-

3

c »3

D

119-120

B

VS

-

2

-

1

1

1

-

-

1

4 ^ on

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

C »3

: xf-ö -

78-81

AT

AT

-

2

-

2

2

5

-

-

3

OCOCH3

• yî-b -

cnf w /

'' max. (cm).

1760 (C = 0 ester); 1778.1745 (C = 0 ketone)

AT

AT

-

5

-

2

2

3

-

-

1

OCO (CH2) 4CH3 0

'■ max. (cm) •

1758 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

-

3

-

2

1

1

-

-

1

CH2CH3 OCOClI (Cll2) 3Cj (3

:> 0-Ö -

xc

\ nax. (cm) •

1750 (C = 0 ester); 1678.1645 (C = O ketone)

AT

AT

-

1

-

1

1

1

-

-

1

-j

ON W N> W VO -U

Table II (continued) 5>

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones ^

Formula

P.F. f C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

OCO (CH2> ^ ACH3

rx ^ -ô -

'' max, (cm).

1758 (C = 0 ester);

1678.1645 (C = 0 ketone)

AT

AT

-

1

-

1

1

1

-

-

1

0-C-CH2CH2CH3 / CH2CH3

Y>

\ nax. (C ™) •

1760 (C = 0 ester); 1670 (C = O ketone)

AT

B

-

5

-

1

3

5

-

-

2

0 "

0-C (CH2) Z, CH3

/ ch2ch3

yi-b c, <r ^ 4

'■ max. (cm) •

1755 (C = 0 ester); 1675 (C = 0 ketone)

B

B

-

5

-

1

3

5

-

2

0 II

o-c (CH2) 6CH3 CH3 j CH2CH3

CH ^ S <^

vs.

W (on_1):

1760 (C = 0 ester); 1675 (C = O ketone)

AT

AT

-

5

-

1

*

2

5

-

-

2

oo

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard o ch2ch3

ii 1

o-c-chch2ch3 CH3 _ / ^ "3

> Q — Q CH3

ckf

W (cm-1):

1750 (c = 0 ester);

1678.1645 (c = 0 ketone)

a a

-

2

-

1

2

5

-

-

1

fìch3 9-c-ç-CH2CI

J fc?

CH3yCv — cvl3

125-127

a a

1

1

1

1

1

5

1

1

1

0 u

0-c- (ch2) 6ch3

/ ch3 ch3 / \

^ / ~ \\ ch3

"Tsr0

W. (f *):

5.73 (C = O ester); 6.01, 6.10 (c = 0 ketone)

a a

2

5

2

2

2

5

5

3

3

0 ii

0-c- (ch2) 8ch3

This

^ max. (l *) '

5.70 (c = 0 ester); 5.98.6.08 (C = O ketone)

a a

1

5

1

2

2

5

5

4

3

ON W K>

read

Table II (continued) w

K »W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 ch3 ii 1

o-c-çh (ch2) 5ch3

/ ch3 ch-> / ph3

C „3 / V ^ W

^ 'IIKIX. ('"o'

5.80 (C = O ester); 6,03,6,10 (C = O ketone)

AT

AT

1

1

1

1

1

1

1

1

1

0 "

o-c— <d

CH3 J V?

ch> <> - 0-ch3

\not

61-62

AT

AT

1

5

2

2

2

5

5

1

2

0 CA ™ 3

11

o-c <r c "3 / '" i-c "] o

82-84

AT

AT

1

1

1

1

1

1

1

1

1

0 ch3

0

117.5-119

AT

AT

1

4

1

4

2

5

5

3

4

o

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard ococh3

"■" ZQ-Ò- *,

W. (cm "1):

1760 (C = 0 ester);

1678.1645 (C = 0 ketone)

AT

AT

-

5

-

3

3

5

-

-

5

0c0 (ch2) 4ch3

/ f "3

ch3ch2ch2 / \

C „3

U

'■ max. (c®) •

1758 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

2

5

2

4

3

5

5

1

3

ch3ch2 0 sj

■ .xf-ò-

0

145-146

AT

AT

1

5

1

2

1

5

5

4

4

ch2ch3

ococh (ch2) 3ch3 ch3ch2 i ch3

'■ max. C®11) •

1755 (C = 0 ester); 1670 (C = O ketone)

AT

AT

1

5

1

1

2

5

1

1

2

Table II (continued) Sì

hi

Physical properties and biological activity of enolic esters of 2-aryl-1, 3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 Cl CH3CH2 // \ - ^

-rQ-O

130-131

AT

AT

1

3

1

1

2

5

5

4

4

CH2CH3 OCOCH (CH2) 3CH3

'"• iKf-Ò

'' • max. (cm).

1760 (C = 0 ester); 1675 (C = O ketone)

AT

AT

1

4

2

2

2

1

1

1

1

0 CH3

ch3r \

0

123-124

AT

AT

1

5

2

2

1

5

5

4

3

ch2ch3 OCoAufCHoKCH; " ) CH3

"3Q-Ò

v0

'• max. C0®1) ■

1765 (C = 0 ester); 1670 (C = O ketone)

AT

AT

2

5

2

2

2

1

1

1

1

K)

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Oco mustard— @

78-80

AT

AT

2

5

2

2

2

5

5

2

2

o çh3 ch3ch2 1 day

/ \ / \ c "3

ch3ch2 t)

138-139

AT

AT

-

4

-

3

3

5

-

-

4

ococh3 j ch3

ch3ch2 d l> ()

ch3chf \ <w vo

'' max. (cm) *

1760 (C = 0 ester);

1678.1650 (C = O ketone)

AT

AT

-

5

-

3

4

5

-

-

5

oco (ch2) 4ch3

ch3 / ^ v \ —ch3

'■ max. (cm) •

1758 (C = 0 ester); 1678.1643 (C = 0 ketone)

■ A

AT

-

5

-

1

2

5

-

-

5

u) u>

WE

u>

NOT)

U>

S

Table II (continued)

N>

OJ

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

OCO- ©

/ CH3

CH3 - / r \ CHj

^ max. ) •

1745 (C = 0 ester); 1675.1642 (C = 0 ketone)

AT

AT

-

5

-

2

2

5

-

-

3

ch2ch3 1

OCOCH (CH2) 3CH3 /

c "3 ~ Q — 0-c%

o

^ max. (cm) •

1760 (C = 0 ester); 1670 (C = O ketone)

AT

AT

2

5

2

1

1

3

3

2

1

164.5-166

AT

AT

2

3

1

2

1

5

5

4

3

ch2ch3 ococh (ch2) ch3

'' max. ):

1760 (C = 0 ester); 1670 (C = O ketone)

AT

AT

1

1

1

1

1

2

2

1

1

Ul

4 ^

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0

He _

o-c-O

No

'"• max. (Cm) •

1730 (C = 0 ester); 1670 (C = 0 ketone)

AT

AT

1

5

1

1

1

3

-

2

2

CH3

C6 »5 (? \

.X3-0

198-200

VS

VS

-

2

-

1

1

5

-

-

1

OCOCH (CH3) 2

82-83.5

VS

AT

-

1

-

1

1

5

-

-

2

O CH

C6 "5 r-U V—.

X3-Ö- *

181-182

AT

AT

1

3

1

1

2

5

5

3

4

Table II (continued) w

NOT

W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. ('C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

OCOCH3

'Snax. (m *) •

5.65 (C = O ester); 5.97.6.05 (C = O ketone)

AT

AT

1

5

1

4

3

5

5

3

4

CH2CH3 OCOCH (CH2) CH3

XK> -

o

^ max. (f4) •

5.73 (C = 0 ester); 5.98.6.05 (C = 0 ketone)

AT

AT

1

4

1

1

1

5

1

1

1

ch,

o 3 ch3ch2 il \

j o ch3

147-149

AT

AT

1

1

1

1

1

5

4

2

2

.OCO (CH2) 4CH3

DQ-Ô- ".

'■ max. (cm).

1758 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

-

5

-

3

3

5

-

-

5

Lft

WE

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

çh2ch3 ocû (: h (cii2) 3ch3

DC £ -Ô-.

* 0

\ nax. (cni).

1750 (c = 0 ester); 1678.1645 (c = 0 ketone)

a a

-

4

-

1

1

4

-

-

1

oco (ch2) uch3 / chj

DOrà--

\ nax. (cm) *

1758 (c = 0 ester);

1678.1645 (c = 0 ketone)

a a

-

5

-

3

3

5

-

-

4

/ g h, ch3

ococh (chokcho cii3ch2ch2 / r „3 3

^ • max. (C®1) •

1750 (C = 0 ester); 1678.1650 (C = O ketone)

a a

1

4

1

1

1

4

3

1

1

n-c9H19 o CH3

v // 1

/ q <> 3 CH3 x— \

0

72-73

VS

VS

-

-

-

-

-

-

-

-

-

Table II (continued) w

K "

w

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard n "CtJH19 0 CH3

79-81

VS

VS

-

-

-

-

-

-

-

-

-

0 CH-. c6H5 // x /

CH> 0-0-CH3

^ 0

147-147.5

vs

AT

1

3

1

4

1

5

5

2

3

OCOCH3

'■ max. (i1) •

5.65 (C = 0 ester); 5.95 (C = 0 ketone)

AT

AT

2

5

1

4

3

5

5

1

3

ococh2ch3

'max. (t1) •

5.69 (C = 0 ester); 5.98, 6.05 (C = O ketone)

AT

AT

-

5

-

3

3

5

-

-

3

L / W 00

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 c »3

XK>

152-156

AT

AT

-

2

-

1

1

5

-

-

5

. OCOCHo rJ "iL

DQ-Ö

0

'max. (cm) •

1760 (C = 0 ester);

1670.1645 (C = O ketone)

AT

AT

-

4

-

2

2

5

-

-

4

ÇH2CH3. OCOCHCH2CH3

DC ^ -0

^ 0

'max. (cm).

1750 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

-

3

-

1

1

4

-

-

1

OCOfCHj ^ CJ ^

xfè

'' max. (cm).

1978 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

-

5

-

2

3

5

-

-

4

Ul o

ON W NJ

U>

so u

Table II (continued) S

K>

ij *

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

ÇH2CH3 ^ ^^ OCOCH (CH2) 3CH3

'■ max. (c111) •

1750 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

-

5

-

1

1

1

-

-

1

OCO (CH2) 8cH3

_ / CH3

ocvb

\ nax. (c®1) ■

1758 (C = 0 ester); 1678.1645 (C = 0 ketone)

AT

AT

-

5

-

1

3

5

-

-

3

OCO C (CH 3) Q

/ CH)

'■ max. (t1) •

5.73 (C == 0 ester); 6.00 (C = O ketone)

AT

AT

1

5

1

3

2

5

1

1

1

ÇH-JCH3 0C0CH "(CHO) 3CHO

cH3A_y W "ch3

W. (M-):

5.73 (C = 0 ester); 6.05 (C = O ketone)

AT

AT

1

3

1

1

1

1

1

1

1

On o

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

OCO (CH2) 6CH3 C6 "5 / &

-> o

'' 'max. (f *) •

5.70 (C = 0 ester); 6.00 (C = O ketone)

AT

AT

1

5

1

3

2

5

4

1

1

oco-O

Dcf-Ô

127-129

AT

AT

-

2

-

1

2

5

-

-

3

r-i

DQrÖ-

159-161

AT

AT

1

5

1

3

2

5

5

3

5

ococh3 / C "3

DCH> -

0

'' ■ max. (cm).

1762 (C ^ O ester); 1678.1645 (C = 0 ketone)

AT

AT

-

5

-

3

3

5

-

-

5

Bone

Table II (continued) w

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones ^

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 ch2ch3 ii 1

o-c-ch (ch2) 3CH3

ch3

\ nax. W •

5.72 (C = O ester); 5.98.6.05 (C = O ketone)

b b

2

2

1

1

2

1

1

1

1

0 ii o-c— (Q

Ó-Ò

122-123

b b

1

1

1

1

2

1

1

4

1

ch j 0

—O-O

172-173

AT

AT

1

1

1

1

1

5

5

2

2

- / \ ^ - '

0

o-c-0

c "; J n

CH3> q— ^

0

113-115

AT

AT

1

1

1

1

1

5

5

3

3

On to

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 CH-, ”/

C "3

98-100

AT

AT

1

4

1

2

2

5

4

1

1

VS\

O-C-0 01

/ CH3

nN

120-22

AT

AT

1

1

1

1

1

4

4

2

2

0 JH

r-Q,

CHj J <* 3 ^ Û2

> q — b> -c ^

I

80-82.5

AT

AT

1

4

1

3

1

5

5

3

4

0 II

O-C- {SK: (CI1]) 3

::AT-

û

124-26

AT

AT

1

3

1

1

1

5

1

1

2

Table II (continued) Oi

N> <jì

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Biological activity

Formula

P.F. (° C) or infrared spectrum

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 II

p-this

CH /

65-67

AT

AT

1

4

1

2

2

5

4

1

3

0 Cl

"\ o-c CH2O - @ - GH3

^ H3 /

'' max. (vs* ) •

1780 (C = 0 ester); 1670 (C = O ketone)

AT

AT

5

4

4

4

5

5

5

5

5

O CH (CHo), II 1

0-C-CH-®-Cl

J

J o

'' max. (t1) •

5.72 (C = 0 ester); 5.98, 6.05 (C = 0 ketone)

B

AT

1

1

1

1

1

1

1

1

1

Ü CH (CH3) 2 m i o-c-ch-®-och3 C "3 / ^

J o

^ 'max. (f) •

5.75 (C = 0 ester); 6.00,6.10 (C = O ketone)

B

AT

1

3

1

1

1

5

1

1

2

Table II (continued)

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones

Formula

P.F. (° C) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Mustard

0 CH (CH3), II 1 i O-C-CH-ßV-CHi

C-3 J C »3

) Q_5-C »3

CH3 'No

'• max. (H-) •

5.75 (C = 0 ester); 6.00, 6.10 (C = O ketone)

AT

AT

1

1

1

1

1

1

1

1

1

0

m

0-C (CH2) 3CH3

in / ^

'• max. (cm).

1760 (C = 0 ester); 1680 (C = 0 ketone)

AT

AT

-

4

-

2

3

5

-

-

4

0 II

0-C (CH2) 5CH3 CH3 J r

Xr ~ -ö here

'' • max. (cm). 1760 (C = O ester); 1680 (C = O ketone)

AT

AT

-

5

-

2

2

5

-

-

4

Bone

Table II (continued) ^

W

Physical properties and biological activity of enolic esters of 2-aryl-1,3-cyclohexanediones £ ".

Formula*

P.F. (DC) or infrared spectrum

Biological activity

Miticide activity

Post-emergent herbicide activity

Pre-emergent herbicide activity

Adults

Eggs

Bean

But

Tomato

Cotton

Soy

Barley

Blood panic

Amaranth

Oco-43 mustard

DQ — Ö- ""

o

76-78

AT

AT

-

4

-

2

2

5

-

-

3

* The compound subjected to the tests consists of a mixture of two isomeric enolic esters. The main component of the mixture has the formula shown. The sign - signifies that the test has not been carried out.

Claims (9)

632394 2 CLAIMS 1. Compound corresponding to the formula: Oy contains as active substance a quantity with acaricidal, ovicidal against mites or herbicidal effect of a compound according to one of claims 1 to 6. 8. A method of combating mites and parasitic plants, characterized in that it consists in subjecting the mites, their eggs and the parasitic plants to a quantity of acaricide, ovicide against mites or herbicide of a compound according to one of claims 1 to 6. 9. Process for the preparation of a compound of formula: and its alkali metal and ammonium salts, formula in which: Z, Z ', Z "and Z'" represent, individually, hydrogen or a haloalkyl, polyhaloalkyl, halo, alkyl, al-koxy, cyano, nitro, alkylthio, alkanoyl, amido, amino, alkylsulfinyl or alkylsulfonyl radical ; q II Y is a hydrogen atom or a group —CR; R is a hydrogen or halogen atom or an alkyl, alkenyl, alkynyl, bicycloalkyl, bicycloalkenyl, cycloalkyl, cy-cloalkenyl, phenyl, phenalkyl, naphthyl or naphthylalkyl group, all these radicals, except hydrogen and halogen , which may be substituted with one or more alkyl, cyano, nitro, alkoxy, halo, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl or dialkylamino radicals; R1 is an alkyl, polyhaloalkyl or haloalkyl group or a halogen; R2, R3, R4, R5, R6 and R7 represent, individually, hydrogen or an alkyl or phenyl group unsubstituted or substituted by one or more alkyl, cyano, halo, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino; or two of the substituents R2, R3, R4, Rs, R6 or R7 together form an alkylene or alkenyl chain having 2 to 20 carbon atoms and forming the complement of a 3,4,5,6 or 7-membered ring; provided that R1 (R2, R3, R4, R5, R6, Z, Z ', Z "and Z'" do not individually contain more than 10 aliphatic carbon atoms and R does not contain more than 30 aliphatic carbon atoms . 2. Compound according to Claim 1, characterized in that R is a straight or branched chain alkyl group having 1 to 30 carbon atoms. 3. Compound according to claim 1, characterized in that Rt is a hydrogen atom. 4. Compound according to Claim 1, characterized in that Z, Z ', Z "and Z'" represent, individually, a tri-halogenomethyl group. 5. A compound according to claim 1, characterized in that Z, Z ', Z "and Z"' represent, individually, hydrogen or an alkoxy, alkyl, cyano, halo-outrihalomethyl radical; R is a hydrogen atom or a straight or branched chain alkyl group having 1 to 30 carbon atoms; R! is an alkyl group or a halogen, and R3, R4, R5, Rfi, R7 and R8 represent, individually, hydrogen or an alkyl group. 6. 3- (2-ethylhexanoyloxy) -5,5-dimethyl-2- (2 ', 4'-dimethylphé-nyl) -2-cyclohexenone, 3- (2-ethylhexanoyloxy) -5,5-dimethyl- 2- (2'-methylphenyl) -2-cyclohexenone, la (2 ', 4'-dimethylphenyl) -5,5-dimethyl-2-cyclohexanedione or la (2'-methylphenyl) -5,5-dimethyl-2- cyclohexanedione according to claim 1. 7. acaricide, ovicide against mite and herbicide composition, characterized in that it comprises an acceptable support and characterized in that it consists in treating a compound of formula: (II) 0 II > i6 0 ii c - 1 c -1 vs • 1 • çoh * 3 r5 r7 with an acid or to treat a compound of formula: z r, (III) z '// \ 0 II ? 2 * 4 > 0 1! ch2c - c -1 VS - 1 C -1 HORN) R3 r5 r7 I It with a base, formulas in which Rs represents an alkyl group, and the other symbols have the meanings given in claim 1. 55