CH665636A5 - NITRODIARYL SULFOXYD DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF. - Google Patents

Description

DESCRIPTION The invention relates to new nitrodiaryl sulfoxide derivatives and processes for their preparation. The new compounds correspond to the general formula (I)

wherein

R 'represents halogen or an alkoxy group with 1-6 carbon atoms and

R2 represents hydrogen, halogen, an alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group, which can optionally be substituted one or more times by halogen and / or nitro.

The new compounds are pharmaceutically active and can be used in particular in veterinary medicine, preferably as an antihelmintic, for example as a nematicide, against tapeworms, etc. The compounds also have a pesticidal, in particular insecticidal and acaricidal, fungicidal and antimicrobial activity and are also herbicidally active.

The compounds of general formula (I) are also valuable intermediates in the production of other, new and known, biologically active aromatic sulfoxide derivatives, for example benzimidazoles and substituted diaminosulfoxides with antihelmintic and fungicidal activity, for example oxfendazole. These derivatives can be prepared from the compounds according to the invention by reaction with amines, subsequent reduction and coupling with a carbamic acid derivative.

The processes for the preparation of the compounds of general formula (I) are defined in claims 3 and 4.

The compounds of the general formula (I) are new. In the formula of the diarylsulfoxides known hitherto, which also contain a nitro group, the nitro group on the one phenyl ring, based on the sulfoxide group, is not in a meta position, and the type, number and position of the other substituents is also different from that in the case of the invention Links; a compound with a meta-standing nitro group was known, but it had no other substituents. These diarylsulfoxides, which differ somewhat from the compounds according to the invention, are generally produced using a method other than that specified here, namely by oxidation of the corresponding diarylsulfides (Ber. 41, 2836 (1908); J.Am.Chem.Soc. 70, 1381 (1948) ).

In the general formula (I), R1 and R2 represent halogen atoms such as fluorine, chlorine, bromine or iodine atoms, preferably chlorine atoms. The Q-Q-alkoxy groups R1 and R2 can be straight or branched, examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec.-butoxy, tert. -Butoxy, i-butoxy, n-pentoxy, i-pento-xy, n-hexoxy and i-hexoxy group; the methoxy group is preferred. If R2 for an alkyl group with 1-6

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Carbon atoms, it is a straight or branched alkyl group, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, tert.-butyl, i -Butyl, n-pentyl, i-pentyl, n-hexyl and i-hexyl group.

The alkali metal atom M in the general formula (III) can be a sodium or potassium atom.

In the general formulas (II) and (V), the halogen atoms X1 and X2 are to be understood as fluorine, chlorine, bromine or iodine atoms, preferably chlorine atoms.

The intermediaries of the general formula (V) are also new compounds and are the subject of claim 5.

These intermediates of formula V can be prepared by using arylsulfonyl halides of the general formula (II)

O

2nd

wherein the meaning of R1 is the same as above and X1 is halogen, reduced with an alkali sulfite, the aryl sulfinate of the general formula (III) obtained

wherein the meaning of R1 is the same as above and M is an alkali metal, hydrolyzes and the arylsulfamic acid of the general formula (IV) obtained

O

2nd

wherein the meaning of R 'is the same as above, or an aryl sulfinate of the general formula (III), wherein the meaning of R1 and M is the same as above, with an inorganic acid chloride.

The reduction of the arylsulfonyl halides of the formula II with an alkali metal sulfite is advantageously carried out in an aqueous medium, the alkali sulfite being used in excess, preferably in an amount of 1.1-4 mol, based on one mole of arylsulfonyl halide. The reduction can be carried out at about 20-35 C, preferably 22-28 C, and expediently under weakly basic conditions, at a pH between 7 and 9, in particular 7.5 and 8.5. This pH value can be adjusted by expediently adding the hydrogen carbonate or carbonate of the same alkali metal which is also present in the sulfite at the same time as the alkali sulfite or before it is added. These basic compounds also act as acid acceptors. The alkali bicarbonate, carbonate or hydroxide can be added to the reaction mixture in solid form, in the form of a saturated solution or in both forms simultaneously.

The acid treatment of the compounds of the general formula (III) is preferably carried out with a strong mineral acid. made especially with concentrated aqueous hydrochloric acid, sulfuric acid, etc. The acid is preferably used in excess. The arylsulfonyl acids of the general formula (IV) obtained after the hydrolysis are highly pure (at least 98% pure) and extraordinarily stable, in contrast to the previously known arylsulfonic acids produced by another process. The yield in the preparation of the compounds of the general formula (IV) is also extremely high and exceeds that of the processes which have hitherto become known (Houben-Weyl, Volume 9, p. 307).

Both the arylsulfinates of the general formula (III) and the arylsulfinic acids of the general formula (IV) can be reacted with a halogenating agent; in both cases the corresponding arylsulfmyl halides of the general formula (V) are formed. Inorganic or organic halogenating agents can be used as halogenating agents. Examples of suitable inorganic halogenating agents are the halogen compounds of sulfur and phosphorus or their halogen-oxygen compounds. Examples include thionyl chloride, phosphorus trichloride, phosgene, phosphorus tachloride, phosphorus oxychloride and phosphorus oxychloride together with chlorine. For example, chlorides of organic acids, for example oxalyl chloride, can be used as organic halogenating agents. The arylsulfonyl halides of the general formula (V) are new compounds and much more stable than the previously known, differently substituted arylsulfmyl halides.

Any catalyst customary in Friedel-Crafts acylation can be used as the metal halide with Lewis acid character to react the compounds (V) with the compounds (VI); Aluminum trichloride is preferred. The compound of the general formula (V) can be reacted with the compound of the general formula (VI) without intermediate isolation, only the excess of the halogenating agent has to be removed beforehand. In general, 1.1-1.8 mol of Lewis acid are expected for 1 mol of arylsulfinyl halide of the general formula (V). The reaction can be carried out at temperatures between 0 and 80 C, preferably between 25 and 42 C.

With the processes according to the invention, the nitro-diaryl sulfoxides of the general formula (I) can be obtained in highly pure form (at least 98% strength) and in very good yield (based on the corresponding arylsulfinic acid 90-96% strength, based on the corresponding arylsulfonyl halide) about 95%). The individual operations of the method according to the invention can also be carried out easily on an industrial scale.

The reaction mixtures can be worked up in a manner known per se, for example by extraction, filtration, evaporation, precipitation with water, with solvent or by removing the excess of the reagent, by decanting, etc.

If desired, the compounds of general formula (I) obtained can be further purified, for example by recrystallization. The circle of solvents used for recrystallization is determined by the solubility and the crystallization properties of the substance to be crystallized.

The active compounds of the general formula (I) can be mixed with the inert, non-toxic solid and / or liquid carriers and / or excipients customary in parenteral or enteral administration, and formulated into medicinal products. For example, water, gelatin, lactose, starch, pectin, magnesium stearate, stearic acid, talc, vegetable oils such as peanut oil, olive oil can be used as carriers. The active ingredients can be the usual ones

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Dosage forms, for example solid formulations (rounded or square tablets, coated tablets, capsules such as hard gelatin capsules, pills, suppositories)

or liquid formulations (for example solutions prepared with oil or water, emulsions, suspensions, syrups, soft gelatin capsules, injectable solutions or suspensions prepared with oil or water).

The amount of solid carriers can be varied within wide limits, a dosage unit preferably contains 25 mg to 1 g of carrier. The formulations can optionally contain auxiliaries customary in the pharmaceutical industry, for example preservatives, stabilizers, wetting agents and emulsifiers, salts for adjusting the osmotic pressure, buffers, fragrances and flavors. The formulations can furthermore optionally contain further pharmaceutically active compounds without a synergistic effect. The formulations are expediently prepared in dosage units which correspond to the desired administration form. The formulations can be prepared by the customary methods, for example by sieving, mixing, granulating and pressing the constituents or by dissolving. The formulations can be subjected to further operations which are customary in the pharmaceutical industry (for example sterilized).

For use as pesticides, the active compounds of the general formula (I) can be converted into the customary formulations, for example solutions, emulsions, soluble powders, suspensions, dusts, aerosols, suspension and emulsion concentrates, mordants. The active ingredients can be used to impregnate natural and synthetic substances; together with polymers and coating compositions, they can be processed into microcapsules. The formulations can be provided with fuel sets, for example smoke cartridges, cans and spirals. The active ingredients can also be used in warm or cold atomizable ULV preparations.

The pesticidal compositions can be prepared in a manner known per se, for example by combining the active ingredients with carriers, i.e. mixed with liquid solvents, pressurized liquefied gases and / or solid carriers and optionally surface-active substances, i.e. Emulsifier and / or dispersant and / or foaming agent are added to the mixture. Is used as an extender e.g. Water is used, organic solvents can also be used as auxiliary solvents.

The following are essentially suitable as liquid solvents: aromatic compounds, for example xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, for example chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, for example cyclohexane or paraffins such as mineral oil fractions, and also alcohols , for example butanol or glycol or their ethers and esters, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, for example dimethylformamide, dimethyl sulfoxide and water. Liquefied gaseous carriers are understood here to mean substances which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. Solid rock materials such as kaolin, alumina, talc, chalk, quartz, attapulgite, mont-morillonite or diatomaceous earth as well as synthetic rock meals such as highly disperse silica, aluminum oxide and come as solid carriers

Silicates in question. The following can be used as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkylene sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

The agents according to the invention may also contain dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The agents generally contain 0.1-95% by weight, preferably 0.5-90% by weight, of active ingredient.

The active compounds can be used in the commercially available formulations or in the form of the ready-to-use preparations prepared from them.

The use forms prepared from the commercially available formulations generally contain between 0.000 000 1 and 95% by weight, preferably 0.01-10% by weight, of active ingredient.

The application takes place in a manner corresponding to the respective type of formulation.

The invention is explained in more detail using the following examples, but is not restricted to these examples.

example 1

Sodium 4-chloro-3-nitro-benzenesulfinate

71.8 g (0.57 mol) of solid anhydrous sodium sulfite are added to the solution of 24 g of sodium hydrogen carbonate in 340 ml of water. A mixture of 58.4 g (0.228 mol) of 4-chloro-3-nitro-benzenesulfonyl chloride and 24 g of sodium bicarbonate is added uniformly to the homogeneous solution at 23-25 ° C. within 2 hours. After the metering has ended, the mixture is stirred at 23-25 ° C. for 4 hours, 200 ml of toluene are added and the mixture is stirred at 35 ° C. for a further 15 minutes. Then the mixture is cooled to 23-25 ° C and filtered. The filtered product is air dried. 56 g of sodium 4-chloro-3-nitro-benzenesulfinate are obtained, which (determined with potassium permanganate) has a purity of 85%. The remaining 15% is water. Yield: 90%.

Example 2

4-chloro-3-nitro-benzenesulfinic acid

The sodium salt prepared according to Example 1 is dissolved in 300 ml of water at 40 ° C. The solution is filtered at the same temperature. 100 ml of concentrated aqueous hydrochloric acid are added to the filtrate, which has cooled to 10-15 ° C., with vigorous stirring. The mixture is then cooled to 5 ° C., filtered and the filtered product is dried at a temperature below 40 ° C. 43 g of white crystalline 4-chloro-3-nitro-benzenesulfinic acid are obtained, which melts at 102-103 ° C. Purity: 99%.

The yield, based on the sulfonyl chloride, is 85% of theory.

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Example 3

Phenyl- (4-chloro-3-nitro-ph'enyl) sulfoxide a) 36 g (0.1625 mol) of the 4-chloro-3-nitro-benzenesulfinic acid prepared according to Example 2, 75 ml of benzene and 15.1 ml Thionyl chloride are mixed together. The reaction mixture is boiled for one hour and then distilled in vacuo at temperatures below 60 ° C. 25 ml of benzene are added to the residue and the solvent is removed again. This is repeated again. To the residue (40 g of crude 4-chloro-3-nitro-benzenesulfonyl chloride, nd24 = 1.6240) are added 20 ml of dichloroethane and then with cooling at a temperature of less than

40 C 28.2 g (0.21 mol) of aluminum chloride. At 40 ° C., 35 ml of benzene are added within half an hour and the mixture is then stirred at 40 ° C. for 2 hours. Finally, the mixture is diluted with 50 ml of benzene, poured onto a mixture of 100 g of ice and 50 ml of water, then the organic phase is separated off and the aqueous phase is washed with 50 ml of benzene. The organic phase combined with the washing liquid is clarified with 5 g of charcoal, filtered and the solvent is removed in vacuo. 45 g (96%) of white phenyl- (4-chloro-3-nitro-phenyl) sulfoxide are obtained, which melts at 86-87 ° C. Purity (HPL-chromatographic): 98%.

b) 36 g (0.1625 mol) of those prepared according to Example 2

4-Chloro-3-nitro-benzenesulfinic acid, 20 ml dichloroethane, 13.5 ml (22 g, 0.185 mol) thionyl chloride and 0.1 ml triethylamine are mixed together. The sulfinic acid dissolves with the evolution of gas. The reaction mixture is heated to 50 ° C for one hour, then to

5-10 C cooled, and 28.2 g (0.21 mol) of aluminum chloride are added to the solution, care being taken by cooling to ensure that the temperature does not rise above 40 ° C. Then the mixture is mixed with 40 ml of benzene at 40 ° C within half an hour. The reaction mixture is stirred at 40 ° C. for a further 2 hours, then diluted with 50 ml of benzene and poured onto a mixture of 100 g of ice and 50 ml of water. The organic phase is separated off and the aqueous phase is extracted with 50 ml of benzene. The combined benzene phases are clarified with 5 g of charcoal, filtered and concentrated in vacuo. When the substance begins to precipitate, the benzene is driven off with methanol at atmospheric pressure, the reaction mixture being said to contain about 60-70 ml of methanol. Then the reaction mixture is allowed to cool slowly. Crystal precipitation begins at 40-50 ° C. If the product already forms a thick crystal suspension, slowly let 100 ml of water of the same temperature flow in at 40-50 ° C. The loose, finely divided suspension is slowly cooled to 15-20 ° C with constant stirring. The product is filtered off and dried. You get

45 g of the title compound, which corresponds in all physical properties to the product according to variant a).

Example 4

Phenyl (4-chloro-3-nitro-phenyl) sulfoxide

23 g (0.08 mol) of the 84.7% sodium 4-chloro-3-nitro-benzenesulfinate prepared according to Example 1 are dissolved in 50 ml of benzene. The mixture of 9.2 ml (0.112 mol) of phosphorus trichloride and 10 ml of benzene is added to the solution within 9C minutes at a temperature of less than 30 ° C. with constant stirring. Then the mixture is stirred at 22-25 ° C for a further 2.5 hours and the benzene solution of the sulfmyl chloride derivative is decanted or suction filtered. The solution is freed from the solvent in vacuo. 20 ml of benzene are distilled off twice from the residue. The pale yellow, oily

Sulfinyl chloride derivative (nD24 = 1.6250) is diluted with 18 ml of benzene. The solution obtained is added at a temperature of less than 15 ° C. to the suspension of 11.34 g (0.085 mol) of aluminum chloride in 18 ml of benzene. 5 After the addition, the temperature of the reaction mixture is allowed to rise to 40 ° C. and the mixture is stirred at this temperature for 2 hours. The reaction mixture is then poured into 100 ml of ice water. The aqueous phase is separated off and extracted with 25 ml of benzene. The combined io benzene phases are clarified with activated carbon, filtered and then evaporated in vacuo. 21 g (95%) of phenyl (4-chloro-3-nitro-phenyl) sulfoxide are obtained, which melts at 86-87 ° C.

15 example

(4-Chloro-3-nitro-phenyl) - (4-methylphenyl) sulfoxide-The approximately 40 g of 4-chloro-3-nitro-benzenesulfinyl chloride prepared according to Example 3 are freed from benzene and thionyl chloride and then at 20 ° C while cooling with 100 ml of toluene and then mixed with 28.2 g (0.21 mol) of aluminum chloride. The reaction mixture is stirred at 35 ° C. for 90 minutes and then worked up in the manner described in Example 3. 42 g (87%) of the title compound are obtained, which melts at 82-84 ° C.

Example 6

(4-Chloro-3-nitro-phenyl) - (4-chlorophenyl) sulfoxide The procedure described in Example 5 is followed, with the difference that chlorobenzene is used instead of toluene and the reaction mixture is stirred at 50 ° C. for 4 hours. The title compound, which melts at 110-112 ° C., is obtained in a yield of 89%.

Example 7

Phenyl- (4-methoxy-3-nitro-phenyl) sulfoxide 4-methoxy-3-nitro-benzenesulfonyl chloride (melting point: 66 ° C.) is reduced with sodium sulfite in the manner described in Example 1, and the sodium 4- obtained methoxy-3-nitro-benzenesulfinate is reacted in the manner described in Example 4. The title compound, which melts at 135-137 ° C., is obtained in a yield of 88%.

Example 8

2-Chloro-5-nitro-benzenesulfinic acid 312 g (4.7 mol) of chlorosulfonic acid and 79 g (0.5 mol) of 4-chloro-nitrobenzene are mixed together. The reaction mixture is stirred at 130 ° C. for 6 hours,

then cooled to below 10 ° C and slowly poured into 750 ml of ice water. It is filtered at room temperature. The product on the filter is washed acid-free with about 2 liters of water. The crude 2-chloro-5-nitro-benzenesulfonyl chloride is used in the next reaction step without intermediate cleaning. 118 g (0.935 mol) of anhydrous sodium sulfite and 20 g of sodium hydrogen carbonate are dissolved in 250 ml of water. The crude 2-chloro-5-nitro-benzenesulfonyl chloride and 20 g of sodium bicarbonate are added to this solution at 23-25 ° C. within one hour. The reaction mixture is stirred at the specified temperature for 2 hours, then 200 ml of toluene are added, the mixture is stirred for a further 15 minutes and then filtered at 25 ° C. The product filtered off is washed with 100 ml of toluene.

The sodium 2-chloro-5-nitro-benzenesulfinate obtained is dissolved in 400 ml of water at 40 ° C., the solution is stirred with 65-200 ml of toluene and the toluene phase is separated off after the solution has been filtered. The aqueous phase is cooled to 10 ° C., acidified with 100 ml of concentrated aqueous hydrochloric acid, and the crystals which have precipitated are filtered off

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and then dried. 61 g of 2-chloro-5-nitrobenzenesulfonic acid are obtained, which melts at 128-130.degree. The yield based on 4-chloro-nitrobenzene is 55%. The product has a purity of 98% (determined with potassium permanganate).

Example 9

Phenyl- (2-chloro-5-nitro-phenyl) sulfoxide 36 g (0.1625 mol) of 2-chloro-5-nitro-benzenesulfinic acid, 60 ml of benzene and 36 ml of thionyl chloride are mixed together. The reaction mixture is boiled for one hour and then worked up in the manner described in Example 3; instead of benzene, dichloroethane is used for dilution and extraction. 40 g (85%) of white, microcrystalline phenyl (2-chloro-5-nitro-phenyl) sulfoxide are obtained, which melts at 150-152 ° C. The product has a purity (determined by HPL chromatography) of 97%.

Example 10 4- (4-chloro-3-nitro-benzenesulfinyl) bifenyl The procedure described in Example 5 is followed, with the difference that biphenyl is used instead of toluene. The title compound, which melts at 98-99 ° C., is obtained in a yield of 90%.

Example 11

4- [(4-chloro-3-nitro-phenylthio) phenyl] - (4-chloro-3-nitro-phenyl) sulfoxide

36 g (0.1625 mol) of the 4-chloro-3-nitro-benzenesulfinic acid prepared according to Example 2, 35 ml of benzene, 10.5 ml (0.143 mol) of thionyl chloride and 0.1 g of anhydrous ice-ene (III) chloride cooked for an hour. 28.2 g (0.21 mol) of aluminum chloride are added to the solution, which is cooled to below 40.degree. The reaction mixture is stirred at 40 ° C. for 2 hours and then worked up in the manner described in Example 3. The oil obtained is dissolved in boiling acetone, the solution is mixed with aqueous methanol, the oil which separates is redissolved in boiling acetone and again with Aqueous methanol precipitated, the oily part is separated off and crystallized by the addition of acetone to give 11.4 g (30%) of the title compound, which melts at 144-146 ° C.

Example 12

(4-Chloro-3-nitro-phenyl) - (4-methoxyphenyl) sulfoxide The thionyl chloride is removed from the reaction mixture obtained according to Example 3b), which contains the 4-chloro-3-nitrobenzene sulfinyl chloride, by vacuum distillation. 50 ml of dichloroethane and 21.6 g of anisole are added to the residue and the mixture is cooled to -5 ° C. Then 33.4 g of aluminum chloride are added in portions, taking care that the temperature does not rise above 20 CC. The reaction mixture is left to stand at 20 ° C. for 4 hours, then poured into 300 ml of ice water, extracted with dichloroethane and the solvent is removed from the organic phase in vacuo. 46.5 g (92%) of the title compound are obtained, which melts at 124-126 ° C.

Example 13

(4-Chloro-3-nitro-phenyl) - (4-ßuorphenyl) sulfoxide From about 40 g of the crude 4-chloro-3-nitro-benzenesulfonyl chloride prepared according to Example 3, benzene and thionyl chloride are removed. Then 90 ml of fluorobenzene and then 33.6 g of aluminum chloride are added with cooling. The reaction mixture is stirred at 55 C for 5 hours and then worked up in the manner described in Example 3, with the difference that the dilution with benzene is omitted. 42 g (86%) of the title compound are obtained, which melts at 84-85 ° C.

Example 14

(4-Bromophenylj- (4-chloro-3-nitrophenylj-sulfoxide

100 ml of bromobenzene are added to about 40 g of the crude 4-chloro-3-nitro-benzenesulfmyl chloride prepared according to Example 3. 33.6 g of aluminum chloride are added to the mixture while stirring, then the mixture is stirred at 50 ° C. for three hours and finally worked up in the manner described in Example 3, with the difference that, after pouring into ice water, benzene is added and the excess of the bromobenzene is obtained by distillation at 30-40 Torr pressure and 60-70 C is removed. 54.5 g (93%) of the title compound are obtained, which melts at 138-140 ° C.

Example 15

(4-chlorophenyl) - (2-chloro-5-nitro-phenyl) sulfoxide

36 g (0.1625 mol) of the 2-chloro-5-nitro-benzenesulfinic acid prepared according to Example 8 are converted to 2-chloro-5-nitrobenzenesulfinylchloride in the manner described in Example 3. The chloride is freed from benzene and thionyl chloride, mixed with 100 ml of chlorobenzene and then with cooling with 28.2 g of aluminum chloride. The reaction mixture is then stirred at 55 ° C. for 5 hours and worked up in the manner described in Example 3, with the difference that the dilution with benzene only takes place after pouring it into ice water. 44 g (86%) of the title compound are obtained, which melts at 142-144 ° C.

Example 16

(4-Àthoxy-3-nitrophenyl) phenyl sulfoxide

The procedure is as described in Example 7, but 4-ethoxy-3-nitrobenzenesulfonyl chloride is used as the starting substance, and sodium 4-ethoxy is prepared from it in the manner described in Example 1 by reduction with sodium sulfite in 70% yield -3-nitrobenzenesulfinate and processes this further in the manner described in Example 4. The title compound is obtained in 86% yield. Mp: 119-121 ° C.

Example 17

1- (4-bromophenyl) -4- (4-chloro-3-nitro-phenylsulfinyl) benzene

The procedure described in Example 5 is followed, with the difference that 4-bromobiphenyl is used instead of toluene. The title compound, which melts at 173-175 ° C., is obtained in 80% yield.

Example 18

(4-chloro-3-nitro-phenyl) - (4-methylthiophenyl) sulfoxide

The procedure is as described in Example 5, but thioanisole is used instead of toluene.

Example 19

1- (4-nitrophenyl) -4- (4-chloro-3-nitro-phenylsulfinyl) benzene

The procedure described in Example 5 is followed, with the difference that 4-nitrobifenyl is used instead of toluene. The title compound, which melts at 220-222 ° C., is obtained in 50% yield.

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Claims (8)

665 636 PATENT CLAIMS 1. Nitrodiaryl sulfoxides of the general formula are reacted and the arylsulfinyl halide of the general formula (V) obtained on sox 2nd in which • R 'represents halogen or an alkoxy group with 1-6 carbon atoms and R2 represents hydrogen, halogen, an alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group which can optionally be mono- or polysubstituted by halogen and / or nitro, together with solid and / or liquid stretching and carriers. 2. Phenyl- (4-chloro-3-nitrophenyl) sulfoxide, (4-chloro-3-nitrophenyl) - (4-methylphenyl) sulfoxide, (4-chloro-3-nitro-phenyl) - (4-chlorophenyl ) sulfoxide, phenyl (4-methoxy-3-ni-20-phenol) sulfoxide, phenyl (2-chloro-5-nitrophenyl) sulfoxide, (4-chloro-3-nitrophenyl) -4-biphenylyl -sulfoxide, (4-chloro-3-nitrophenyl) -4-methoxyphenyl sulfoxide, (4-chloro-3-nitrophenyl) -4-fluorophenyl sulfoxide, 4-bromophenyl- (4-chloro-3-nitrophenyl) -sulfoxide, 4-chlorophenyl- (2-chloro-5-nitrophenyl) -sulfoxide, (4-ethoxy-3-nitrophenyl) -phenyl sulfoxide, l- (4-bromophenyl) -4- (4-chloro-3- nitrophe-nylsulfmyl) benzene, 1- (4-nitrophenyl) -4- (4-chloro-3-nitrophenylsulfonyl) benzene, 4 - [(4-chloro-3-nitrophenylthio) phenyl] -4-chlorine -3-nitrophenyl) sulfoxide according to claim 1. 30 3rd 665 636 reacted with a halogenating agent and the arylsulfinyl halide of the general formula (V) obtained 0. wherein the meaning of R1 is the same as above and X2 is halogen, in the presence of a metal halide catalyst having Lewis acid properties with benzene derivatives of the general formula (VI) wherein the meaning of R2 is the same as above. 3. Process for the preparation of nitrodiaryl sulfoxides of the general formula (I) wherein the meaning of R1 is the same as above and X2 is halogen, in the presence of a metal halide catalyst having Lewis acid properties with benzene derivatives of the general formula (VI) (VI) wherein the meaning of R2 is the same as above. 4. Process for the preparation of nitrodiaryl sulfoxides of the general formula (I) (I) 35 (I) where 40 R1 represents halogen or an alkoxy group with 1-6 carbon atoms and R2 represents hydrogen, halogen, an alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group which can optionally be mono- or polysubstituted by halogen and / or nitro, characterized in that arylsulfonylhalo genides of the general formula (II) wherein R1 represents halogen or an alkoxy group with 1-6 carbon atoms and R2 represents hydrogen, halogen, an alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group which can optionally be substituted one or more times by halogen and / or nitro, characterized in that arylsulfonylhalogenides general formula (II) (II) wherein the meaning of R1 is the same as above and X1 is halogen, reduced with an alkali sulfite, the aryl sulfinate of the general formula (III) obtained 50 (II) 02N S02M (III) 55 wherein the meaning of R1 is the same as above and X 'is halogen, reduced with an alkali sulfite, the aryl sulfinate of the general formula (III) obtained 60 wherein the meaning of R1 is the same as above and M represents an alkali metal, treated with an acid, the arylsulfinyl derivative of the general formula (IV) obtained (III) 65 (IV) where the meaning of R1 is the same as above and M represents an alkali metal, with a halogenating agent in which the meaning of R1 is the same as above, with a 5. Compounds of the general formula (V) 0. wherein R 'represents halogen or an alkoxy group with 1-6 carbon atoms and X2 represents halogen, as an intermediate in the process according to claim 3 or claim 4. 5 V "" (I) M (V) where 10 R1 represents halogen or an alkoxy group with 1-6 carbon atoms and R2 represents hydrogen, halogen, an alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group, which can optionally be mono- or polysubstituted by halogen and / or nitro. 6. Pharmaceutical preparations containing as active ingredient a compound of the general formula (I) wherein R1 represents halogen or an alkoxy group with 1-6 carbon atoms and R2 represents hydrogen, halogen, an alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group, which can optionally be substituted one or more times by halogen and / or nitro, together with pharmaceutical carriers and / or auxiliaries . 7. pesticide compositions containing as active ingredient a compound of the general formula (I) O 8. Composition according to claim 7, containing as active ingredient a compound of general formula (I), in which the meaning of R1 and R2 is the same as in claim 13, in a concentration of 0.1-95 wt .-%.