CH635561A5 - Process for the preparation of 2-aryl-1,3-cyclohexanediones - Google Patents

Abstract

The 2-aryl-1,3-cyclohexanediones of formula I, the symbols of which are defined in Claim 1, have pesticidal activity. They are obtained either by condensation of a corresponding 2-diazo-1,3-cyclohexanedione with a corresponding benzene, or by condensation of a corresponding 1,3-cyclohexanedione with a corresponding fluoro- or chlorobenzene. <IMAGE>

Description

The subject of the present invention is the processes defined in claims 1 and 2 for the preparation of new 2-aryl-1,3-cyclo-55 hexanediones endowed with pesticidal activity and corresponding to the formula:

(I)

where: Z, Z ', Z "and Z

'' represent, individually, hydrogen or

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

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

R2, R3, R4j R5, R6 and R, represent, individually, hydrogen or a substituted or unsubstituted alkyl or phenyl group, the admissible substituents comprising one or more alkyl, cyano, halogeno, nitro, alkoxy, alkylthio radicals, alkylsulfinyl, alkylsulfonyl or dialkylamino; or any two of the substituents R2, R3, R4, Rs, R6 or R7 can together form an alkylene or alkenylene chain having 2 to 20 carbon atoms and forming the complement of a 3,4, 5, 6 or 7 ring links;

provided that Rt, R2, R3, R4, Rs, Re> R ?, Z, Z ', Z "and Z'" cannot individually contain more than 10 aliphatic carbon atoms.

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 ', 4', 6'-trimethylphenyl) -1,3-cyclohexanedione 2- (2'-cyano-4 ', 6'-dichlorophenyl) -1, 3- cyclohexanedione 2- (2'-isopropyl-6'-cyanophenyl) -4,6-dimethyl-1,3-cyclohexanedione 2- (2'-trifluoromethyl-6'-methyl) -4-trichloromethyl-1,3-cyclohexane- dione 2- (2 ', 4'-dimethylphenyl) -5.5-dimethyl-1,3-cyclohexanedione triethylammonium salt of 2- (2', 4'-dichlorophenyl) -5.5- dimethyl-1,3-cyclohexanedione piperidinium salt of 2- (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione salt of 1-adamantanammonium of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione pyridinium salt of 2- (2'-methylphenyl) -5,5-dimethyl-1,3-cyclo-hexane dione 2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3,5-cyclohexanedione morpholinium salt of 2- (2', 4'-dimethylphenyl) -5,5- dimethyl-1,3-cyclohexanedione dicyclohexylammonium salt of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione salt of N, N-diethylanilinium of 2- (2 ', 4'- dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione 2-picolinium salt of 2- (2 ', 4'-dichlorophenyl) -5,5-dimethyl-1,3-cyclohexanedione piperazinium salt of 2 - (2 ', 5'-dimethylphenyl) -5,5-dimethyl-1,3-cyclohexanedione imidazolium salt of 2- (2'-chlorophenyl) -5,5-dimethyl-1,3-cyclo-hexanedione

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

2- (2'-trichloromethyl-6'-cyanophenyl) -5,6-dimethyl-1,3-cyclohexane-dione

2- (2 ', 6'-dimethyl-4'-tertio-butylphenyl) -5,5-dimethyl-1, 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-l, 3-cyclohexanedione

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-cyclohexane-dione

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

5- (3'-P-methoxyethylphenyl) -2- (2 ', 4 /, 6'-trimethylphenyl) -1,3-cyclo-hexanedione

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-cyclohexane-dione

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'-methoxyphenyl) -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-cyclo-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-cyclohexanedione

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

2- (2'-methyl-4'-trifluoromethylphenyl) -5,5-dimethyl-1,3-cyclo-

hexanedione

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

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

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

2- (2 ', 4'-dimethylphenyl) -5-phenyl-1,3-cyclohexanedione

2- (2'-methylphenyl) -5- (2'-methylsulfonylmethyl) -1,3-cyclohexane-

dione

2- (2'-methylphenyl) -5- (2'-chlorophenyl) -1,3-cyclohexanedione

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

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

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

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

hexanedione

2- (2 ', 4'-dimethylphenyl) -5- (2'-chlorophenyl) -1,3-cyclohexanedione

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

dione

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

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

3- (2'-methylphenyl) spiro [5.5] undecane-2,4-dione 3- (2 ', 4'-dimethylphenyl) spiro [5.5] undecane-2,4-dione 3- (2'-chlorophenyl) spiro [5.5] undecane-2,4-dione 3- (2 ', 4'-dichlorophenyl) spiro [5.5] undecane-2,4-dione 2- (2', 4'-dimethylphenyl) -4,5-diethyl- l, 3-cycIohexanedione

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

2- (2'-methyl-5'-cyanophenyl) -6-methoxymethyl-1,3-cyclohexane-

dione

2- (2 ', 4'-dibromophenyl) -4- (4'-methylthiophenyl) -5-methyl-1,3-cyclo-hexanedione

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

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-cyclohexane-dione

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-1,3-cyclohexane-dione

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-l , 3-cyclohexane-dione

2- (2 ', 6'-dichloro-4'-nitrophenyl) -5- (2'-cyanoethyl) -1,3-cyclohexane-dione

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

2- (2'-chloro-6'-cyano-4'-nitrophenyl) -5,5-dimethyl-l, 3-cyclohexane-dione

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-cyclohexane-dione

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-cyclo-hexanedione

5- (3'-nitrophênyl) -2- (2'-chloro-4'-nitrophenyl) -1,3-cyclohexanedione

5-phenyl-2- (2'-methyl-6'-chloro-4'-nitrophenyl) -1,3-cyclohexane-

dione

3- (2'-chloro-6'-nitrophenyl) spiro [5.5] undecane-2,4-dione 3- (2 ', 6'-dichloro-4'-nitrophenyl) spiro [5.5] undecane-2,4- dione 2- (2'-trifluoromethyl-4'-aminophenyl) -5,5-dimethyl-1,3-cyclohexane-dione

2- (2 \ 4'-dichloro-6'-aminophenyl) -5,5-dimethyl-1,3-cyclohexane-dione

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

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

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

5- (4'-chloro-6'-nitrophenyl) -2- (2'-bromo-4'-methylsulfinyl-6'-cyano-phenyl) -1,3-cyclohexanedione

3- (2'-chloro-6'-aminophenyl) spiro [5.5] undêcane-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'-nitxophenyl) -5,5-dimethyl-1,3-cyclohexanedione

2- (2'-methyl-6'-nitrophenyl) -1,3-cyclohexanedione

2- (2'-chloro-6'-nitrophenyl) -1,3-cyclohexanedione

2- (2'-chloro-6'-methoxyphenyl) -5,6-dimethyl-1,3-cyclohexanedione

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

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

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

2- (2 ', 6'-dibromophênyl) -5,5-dimethyl-l, 3-cyclohexanedione

2- (2'-bromo-6'-aminophenyl) -1,3-cyclohexanedione

2- (2'-bromo-5'-chloro-6'-fluorophenyl) -1,3-cyclohexanedione

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

2- (2 ', 4 / -dichloro-6'-tribromomethylphenyl) -1,3-cyclohexanedione

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

2- (2 ', 4', 6'-tribromophenyl) -1,3-cyclohexanedione

3- (2'-chloro-6'-bromophenyl) spiro [5.5] undecane-2,4-dione 3- (2 ', 4', 6'-trimethylphenyl) spiro [5.5] undecane-2,4-dione 3 - (2 ', 4', 6'-trichlorophenyl) spiro [5.5] undecane-2,4-dione 2- (2'-methyl-6'-cyano-5'-ratrophenyl) -5,5-dimethyl-l , 3-cyclohexane-dione

2- (2'-methyl-6'-cyano-4'-nitrophenyl) -1,3-cyclohexanedione 2- (2'-chloro "-6'-cyanophenyl) -1,3-cyclohexanedione 2- (2'- chloro-4'-cyanophenyl) -6-trichloromethyl-1,3-cyclo-hexanedione

2- (2 ', 6'-dichloro-4'-cyanophenyl) -1,3-cyclohexanedione 5- (2', 4'-dimethoxyphenyl) -2- (2 ', 6'-dimethylphenyl) -1, 3- cyclo-hexanedione

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

5- (3'-ethylsulfinylphenyl) -2- (2 ', 6'-dichlorophenyl) -1,3-cyclohexane-dione

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, acaricide, mite ovicide, pre-emergence herbicide and post-emergence 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. The acaricidal and ovicidal activity against mites is greatest in compounds which carry a hydrogen atom or an alkyl, alkoxy, cyano, trihalomethyl or halogen substituent in one of the ortho positions of the 2-phenyl group and a substituent alkyl or halo 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 these pesticidal compounds also have the property of being excellent fumigants. In addition, these compounds are relatively non-toxic to mammals when used in sufficient amounts to destroy mites, their eggs or parasitic plants.

Preferred for their higher degrees of acaricidal, ovicidal against mites and herbicidal activity and because of their ability to be used as intermediate compounds in the preparation of other substances endowed with pesticidal activity, the compounds in the formula of which :

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Z, Z ', Z "and Z'" represent, individually, hydrogen or an alkyl, alkoxy, cyano, halo or trihalogenomethyl radical; Rj is an alkyl radical or a halogen atom;

R2, R3j R4, R5, Re and R, represent, individually, hydrogen or an alkyl group. 5

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;

Rj is a methyl group or a halogen; io

R2, R3, R4, R5i R6 and R, represent, individually, hydrogen or a methyl or ethyl radical.

The methods according to the invention are illustrated by the reaction schemes given below, in which R], 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:

FIGURE IV

Z '"z"

z '

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

DIAGRAM V

40

In Scheme V, Z 'is an alkylsulfonyl group or a nitro group; or Z 'can also be an alkyl or alkoxy group when R 1 or Z' "is a nitro group.

The procedure illustrated in scheme IV involves the photosensitized decomposition of a 2-diazocycloalkane-1,3-dione in an aromatic solvent, in the presence of a photosensitizer, preferably benzophenone. In this process, a 2-diazocyclo-

suitably substituted alkane-1,3-dione is photochemically decomposed to form the corresponding triplet carbene which, in turn, reacts with a suitable aromatic solvent to form the desired 2-arylcycloalkane-1,3-dione. The photolysis reaction is carried out under the action of ultraviolet rays having a wavelength of more than 290 nm. Ultraviolet rays can be produced using any conventional source of ultraviolet light of the type known to specialists in the field of photolysis. Examples of suitable sources of ultraviolet light production include high and low pressure mercury arc lamps, germicidal lamps, black light sources, etc.

Preferably, the reaction illustrated in scheme V is carried out by contacting equivalent quantities of the reactants in a suitable solvent, in the presence of at least one equivalent of an organic or inorganic base. Examples of suitable reaction solvents are dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, etc. Examples of bases which can be used in carrying out this reaction include carbonates or bicarbonates of alkali metals such as sodium bicarbonate or potassium carbonate; alkali metal hydrides such as lithium hydride, sodium hydride or potassium hydride or alkali metal alcoholates or hydroxides such as sodium hydroxide, sodium methylate or tertiary butylate potassium. The basis of choice is anhydrous potassium carbonate.

The reactions according to schemes IV and V are not sensitive to temperature or pressure and can be carried out 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 at 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 2-diazo-1,3-cyclohexanediones used as reactants in the reaction according to scheme IV can be prepared by treatment of a properly substituted cyclohexane-1,3-dione 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.

The following practical examples illustrate more particularly the process 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 up

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at 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 C14H14C1N04.1 / 2H20:

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 ', 6'-dichloro-4'-nitrophenyl) -S, 5-dimethyl-l, 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-cyclo-hexanedione and 76.36 g (0.553 mol ) anhydrous potassium carbonate in 300 ml of dimethylformamide. The 3,4,5-trichloronitro-benzene (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. An intense red solution is formed and, when the addition is complete, the temperature is raised to 100 ° C. and the mixture is stirred for approximately 16 h at this temperature. Most of the dimethylformamide is removed by distillation under vacuum 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. 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 C14H13C12N04:

Calculated: C 50.93 H 3.97 N 4.24%

Found: C 50.09 H 3.79 N 4.26%

Example 3:

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 n) 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 diazo ketone is observed 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 shows no clouding when acidified. 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 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 to give 1.96 g of 2- ( 2 ', 4', 6'-

trimethylphenyl) cyclohexane-1,3-dione in the form of white crystals, melting at 196-198 ° C.

Analysis for CiSHI802:

Calculated: C 78.23 H 7.88%

Found: C 77.94 H 8.20%

Examples 4 and 5:

Preparation of 2- (2 ', 4'-dimethylphenyl) -5,5-dimethylcyclohexane-1,3-dione and la2- (2', 6'-dimethylphenyl) -5,5-dimethylcyclohexane-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 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 C16H20O2:

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 C16H20O2:

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 6:

Preparation of 2-diazo-5-phenylcyclohexane-1,3-dione

A solution of 20.0 g (0.106 mol) of 5-phenylcyclohexane-1,3-dione in 75 ml of ethanol is cooled to -10 ° C. 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.

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for 1 h at 0-5 ° C. The solvent is removed in vacuo at a temperature below 40 ° C. 200 ml of ether are added to the residue and the mixture is extracted with a solution containing 3.1 g of hydroxide potassium in 200 ml of water. The ether solution is dried over anhydrous magnesium sulfate, 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.

Preparation of 2- (2 ', 4', 6'-trimethylphenyl) -5-phenylcyclohexane-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 0.25M 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, flòsci mm) using a mixture of benzene and ethyl acetate, which gives 5.7 g (57%) of a white solid substance. 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 7:

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

A solution of 7.00 g (0.042 mol) of 2-diazo-5,5-dimethylcyclohexane-1,3 is irradiated for approximately 16 h with a 200 W mercury arc lamp equipped with a borosilicate glass filter. -dione in 300 ml of 5-tertiobutyl-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 8:

Preparation of 2-diazodecaline-l, 3-dione

A solution of 10.0 g (0.0768 mol) of decalin-1,3-dione in 50 ml of ethanol is stirred using a magnetic stirrer under nitrogen and cooled to -10 ° C 7.77 g (0.0768 mol) of triethylamine and then 15.14 g (0.0768 mol) of p-toluenesulfonylazide, added all at once, are added to the solution. 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.

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

A solution of 7.0 g (0.0364 mol) of 2-diazodecaline is degassed

1.3-dione and 33.18 g (0.182 mol) of benzophenone in 500 ml of toluene for 1 h under nitrogen atmosphere and it is irradiated with a 200 W mercury arc lamp equipped with a glass filter borosilicate, for about 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 chromatography on a column of silica gel (0, flòsci 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) decalin-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 9:

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 h, 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. To the reaction mixture is added dropwise while stirring and keeping the temperature at 75 ° C. a solution of 57.60 g (0.300 mol) of

3.4-dichloronitrobenzene in 100 ml of dimethylformamide. 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'-chloro-4'-nitrophenyl) -5,5-dimethyl-1,3-cyclohexanedione in the form of a white powder melting at 250-253 ° C.

Analysis for C14Hi4C1N04.1 / 2H20:

Calculated: C 55.18 H 4.96 N 4.60%

Found: C 55.53 H 4.73 N5.09%

Example 10:

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 (J.) in the infrared spectrum has completely disappeared. also the reaction 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. 11 hour period required. Mesitylene is extracted with 0.25N sodium hydroxide until a small sample no longer shows

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when it is acidified. The combined basic extracts are washed twice with 200 ml of ether and acidified (pH = 5) with IN hydrochloric acid. The 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.

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 Cj sHj 8Oz:

Calculated: C 78.23 H 7.88%

Found: C 77.94 H 8.20%

R

Claims (2)

635,561 2 1. Process for the preparation of a compound of formula: characterized by the fact that it consists in reacting a compound of formula: with a compound of formula: in the presence of ultraviolet rays of wavelength greater than 290 nm, formulas in which: Z, Z ', Z "and Z'" represent, individually, hydrogen or a polyhaloalkyl, halo, cyano, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkanoyl, amido or haloalkyl radical; R1 is an alkyl group; R2, R3, R4, R5, R6 and R represent, individually, hydrogen or a substituted or unsubstituted alkyl or phenyl radical, the possible substituents of which consist of one or more radicals such as alkyl, cyano, halogen radicals, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino; or any two of the substituents R3, R4, R5, R6, R7 and Rs can together form an alkylene or alkenylene chain having 2 to 20 carbon atoms, on which a three, four, five, six or seven-membered ring closes ; provided that the substituents Rt, R2, R3, R4, Rs, R6, R7, Z, Z ', Z "and Z'" cannot individually contain more than 10 aliphatic carbon atoms. 2. Process for the preparation of a compound of formula: characterized by the fact that it consists in reacting a compound of formula: r2 0 U with a compound of formula: R-, '/ V z ' • I 1! Z " 25 in the presence of a base, formulas in which: X represents fluorine or chlorine; Z, Z "and Z '" represent, individually, hydrogen or a polyhaloalkyl, halo, cyano, nitro, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkanoyl, amido, amino or haloalkyl radical; Z 'is a nitro or alkylsulfonyl group or Z' is an alkyl or alkoxy group when either of Z "'and Rj is a nitro group; R1 is an alkyl, haloalkyl group, a halogen or a polyhaloalkyl group; R2, R3î R4, Rs, R6 and R7 represent, individually, hydrogen or a substituted or unsubstituted alkyl or phenyl group the possible substituents of which include one or more alkyl, cyano, halo, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino or any two of the substituents R2, R3, R4, Rs, R6, R7 can together form an alkylene or alkenylene chain having 2 to 20 carbon atoms, on which a 3,4,5 ring closes , 6 or 7 links; 45 provided that the substituents R ^ R2, R3, R4, R5, Rö, R7, Z, Z ', Z "and Z'" cannot individually contain more than 10 aliphatic carbon atoms.