DE3506954A1 - NITRODIARYL SULFOXIDE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND MEANS THEREOF - Google Patents

Description

HOFFMANN · EITLE & PARTNER QC Π RQR /

PATENT AND LAWYERS J 0 U D 3 ν) Η PATENTANWÄLTE DIPL.-ΙΝΘ. W. EITLE DR. RER. NAT. K. HOFFMANN · DIPL-ΙΝβ. W. LEHN DIPL.-ING. K. FDCHSLE. DR. RER. NAT. B. HANSEN · DR. RER. NAT. HA. BRAUNS - DIPL.-ΙΝβ. K. GORQ DIPL.-ΙΝΘ. K. KOHLMANN · LAWYER A. NETTE

41 560 u / wa

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JUDGE GEDEON VEGESZETI GYÄR RT., BUDAPEST / HUNGARY

Nitrodiaryl sulfoxide derivatives, process for their Manufacture and agents containing them

ARABELLASTRASSE 4 · D-8OOO MÖNCHEN 81 · TELEFON CO8O} Ο11Ο87 · TELEX ö-2geiS CPATHEJ ■ TELEKOPlERER 9183 JUDGE GEDEON VEGESZETI GYAR RT., BUDAPEST / HUNGARY

Nitrodiaryl sulfoxide derivatives, process for your Manufacture and agents containing them

The invention relates to new nitrodiaryl sulfoxide derivatives and a method for their production. The new compounds correspond to the general formula (i)

wherein "1

for halogen or alkoxy group with 1-6 carbon atoms and

for hydrogen, halogen, alkyl or alkoxy group each with 1-6 carbon atoms or a phenyl or phenylthio group, optionally mono- or multiply by halogen and / or nitro can be substituted.

The new compounds are pharmaceutically active and can be used especially in veterinary medicine, preferably as an antihelmintic, for example as a nematicide,

BATH ORIGINAL

used against tapeworms, etc. The compounds also have a pesticidal, in particular insecticidal and acaricidal as well as fungicidal and antimicrobial effects and are also herbicidal.

The compounds of general formula (i) are also valuable intermediaries in the production of other, new and known, biologically active aromatic Sulphoxide derivatives, for example benzimidazoles and substituted diaminosulphoxides with anthelmintic and fungicidal Activity, for example oxfendazole. These derivatives can be obtained from the compounds according to the invention by reacting with Amines, subsequent reduction and coupling with a carbamic acid derivative are produced.

The compounds of general formula (i) are prepared according to the invention by adding arylsulfonyl halides of the general formula (il)

Oo N

SO ₂ X ¹

(II)

- where the meaning of R

X stands for halogen - reduced with an alkali sulfite.

is the same as above and: an alkali sulfite reduces the obtained aryl sulfinate of the general formula (ill)

SO ₂ M

(in)

- 10 -:

- wherein the meaning of R is the same as above and M stands for alkali metal atom - treated with an acid, the resulting arylsulfinyl derivative of the general formula (iv)

(iv)

- in which the meaning of R is the same as above - or the arylsulfinate of the general formula (ill) with a halogenating agent and the resulting arylsulfinyl halide of the general formula (v)

-SOX '

(ν)

- in which the meaning of R is the same as above and X is halogen - in the presence of a metal halide catalyst with Lewis acid properties with benzene derivatives of the general formula (vi)

(VI)

- in which the meaning of R is the same as above -reacts.

The compounds of general formula (i) are

New. In the formula of the previously confessed, also a nitro

group containing diarylsulfoxides is the Nitro group on one phenyl ring not in meta position with respect to the sulfoxide group, and also the type The number and position of the other substituents is different than in the case of the compounds according to the invention; a compound with meta-nitro group was known, however otherwise it had no substituents. These diarylsulfoxides, which differ somewhat from the compounds according to the invention are generally carried out using a different method ren than that given here, namely by oxidation of the corresponding diaryl sulfides (ßer. 41, 2836/1908 /; O.Am.Chera.Soc. 70.1381 / 1948 /).

In the general formula (i), R and R stand for

Halogen atom such as fluorine, chlorine, bromine or dodatom. preferential

1 2 wise chlorine atom. The C, -C _& -alkoxy groups R and R can be straight or branched, examples are the methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert.- Butoxy, i-butoxy, n-pentoxy, i-pentoxy, n-hexoxy called i-hexoxy group; the methoxy group is preferred. If R stands for an alkyl group with 1-6 carbon atoms, it is a straight or branched alkyl group, for example methyl, ethyl, n-propyl, i-propyl, η-butyl, sec-butyl , tert-butyl, i-butyl, n-pentyl, i-pentyl, n-hexyl and i-hexyl groups.

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

In the general formulas (il) and (v), the halogen atoms X and χ include fluorine, chlorine, bromine or dodatorae, preferably chlorine atoms.

The intermediates of the general formula (v) are new compounds.

The reduction of the arylsulfonyl halides of the general Formula (II) with alkali metal sulfite is appropriate

carried out in an aqueous medium, the alkali metal sulfite being used in excess, preferably in an amount of 1.1-4 moles based on one mole of arylsulfonyl halide. The reduction is carried out at about 20-35 ⁰ C, preferably 22-28 ⁰ C, and indeed expediently under weakly basic conditions at a pH value between 7 and 9, in particular 7.5 and 8.5. The adjustment of this pH value can be done that at the same time with the alkali metal sulfite or before its addition, the hydrogen carbonate or Carbonate advantageously of the same alkali metal that is also contained in the sulfite. clogs. These basic compounds also function as acid acceptors. The alkali hydrogen carbonate, carbonate or hydroxide can the reaction mixture in solid form, in the form of a sown saturated solution or in both forms added at the same time will.

The acid treatment of the compounds of the general formula (III) is preferably carried out with a strong mineral acid, in particular with concentrated aqueous hydrochloric acid.

Sulfuric acid, etc. made. 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%) and extremely stable, very much in contrast to those previously known with arylsulfinic acids prepared by another method. Also the yield in the preparation of the compounds of the General formula (iv) is extremely high and exceeds that of the previously known processes (Houben-Weyl. Volume 9. p. 307).

Both the aryl sulfinates of the general formula (ill) as well as the aryl sulfinic acids of the general formula (iv) can be reacted with a halogenating agent; in both cases the corresponding arylsulfinyl halides of the general formula (v) are formed. Ale halogenation

Inorganic or organic halogenating agents can be used be used. As inorganic halogenating agents for example the halogen compounds of sulfur and phosphorus or their halogen-oxygen compounds in question. Examples are thionyl chloride and phosphorus trichloride. Phosgene, phosphorus pentachloride, Phosphorus oxychloride as well as phosphorus oxychloride called together with chlorine. As an organic halogenating agent For example, organic acid chlorides such as oxalyl chloride can be used. The aryl sulfonyl halides of the general formula (v) are new compounds and much more stable than the previously known ones, differently substituted arylsulfinyl 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 general formula (v) may be reacted without intermediate isolation with the compound of general formula (vi), only the upper weft of H _a logenierungsmittels is previously removed. In general, 1.1-1.8 moles of Lewis acid are calculated per mole of arylsulfinyl halide of the general formula (v). The reaction is carried out at temperatures between 0 and 80.degree. C., preferably between 25 and 42.degree.

With the process according to the invention, the nitro-diaryl-sulfoxides of the general formula (i) can be obtained in highly pure form (at least 98 %) and in very good yield (based on the corresponding arylsulfinic acid 90-96 % ± g, 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 are in per se known manner, for B _e ispiel by extracting. Filtering,

steam, precipitation with water, with solvent or by removing the excess of the reagent Decanting etc. worked up

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

The active ingredients of the general formula (i) can with the inert, non-toxic solid and / or liquid carriers and / or which are customary in pharmaceutical production and are suitable for parenteral or enteral administration Mixing auxiliary materials and making pharmaceutical preparations for be mulated. Carriers can include, for example, water, Gelatin. Lactose, starch, pectin, magnesium stearate, stearic acid, talc, vegetable oils such as peanut oil, olive oil, are used will. The active ingredients can be added to the usual dosage forms, for example solid formulations (rounded or square tablets, coated tablets, capsules such as hard gelatine capsules, pills, suppositories) or liquid Formulations (for example solutions made with oil or water, emulsions, suspensions, syrups, soft gelatin capsules, injectable solutions made with oil or water or suspensions). 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 be in Auxiliaries customary in the pharmaceutical industry, for example Preservatives, stabilizers, wetting agents and emulsifiers, salts to adjust the osmotic pressure, buffers, fragrances and contain flavorings. The formulations can furthermore optionally contain further, pharmaceutically active known compounds, without a synergistic one Effect occurs. The formulations are expediently prepared in dosage units which correspond to the desired administration

shape. The manufacture of the formulations takes place by means of the usual methods, for example by sieving, mixing. Granulating and compressing the ingredients or by dissolving them. The formulations can be subjected to further operations common in the pharmaceutical industry (e.g. sterilized).

For use as pesticides, the active ingredients of the general formula (i) can be converted into the usual formulations, for example solutions, emulsions, soluble powders, suspensions ions, dusts, aerosols, suspensions and emulsions concentrates, pickling agents are transferred. The active ingredients can be used to impregnate natural and synthetic materials; they can be processed into microcapsules together with polymers and coating materials. The formula lations can be provided with burners, for example smoke cartridges, cans and spirals. The active ingredients can also be used in warm or cold dustable ULV preparations.

The pesticidal agents are known per se Manufactured in a manner, for example, by mixing the active ingredients with carriers, i.e. liquid solvents Pressurized liquefied gases and / or solid carriers mixed and optionally surface-active Substances, i.e. emulsifiers and / or dispersants and / or foaming agents are added to the mixture. Will If water is used as an extender, organic solvents can also be used as auxiliary solvents, The following essentially come into question as liquid solvents: aromatic compounds, for example Xylene, toluene or alkyl naphthalenes, 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, 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 carrier substances are to be understood here as substances that are at normal temperature and normal pressure are gaseous, for example aerosol propellants such as halogenated hydrocarbons, butane, propane, Nitrogen and carbon dioxide. Natural rock flour, for example kaolin, clay, Talc, chalk. Quartz, attapulgite, montmorillonite or diatomaceous earth as well as synthetic rock powder such as highly dispersed silica, aluminum oxide and silicates are possible. The following can be used as solid carriers for granulates: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granulates made from inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foam-generating agents are suitable: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as a dispersant come into question: e.g. lignosulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as

Gum arabic. Polyvinyl alcohol, polyvinyl acetate.

The formulations according to the invention can also 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 substances such as salts of iron, manganese, boron, copper, Contains cobalt, molybdenum and zinc.

The formulations generally contain 0.1-95

% By weight, preferably 0.5-90% by weight, active ingredient.

The active ingredients can be used in the commercially available formulations or in the form of those prepared from them Preparations are used.

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 with reference to the following examples, but is not restricted to these examples .

example 1

Sodium 4-chloro-3-nitrobenzenesulfinate 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. To the homogeneous solution at 23-25 ⁰ C is added uniformly in the course of 2 hours a mixture of 58.4 g (0.228 mol) of 4-chloro-3-nitro-benzenesulfonyl chloride and 24 g of sodium hydrogen carbonate. After termination of the dosage, the mixture is stirred at 23-25 ° C for 4 hours, treated with 200 ml of toluene and stirred for an additional 15 minutes at 35 ⁰ C. Then, the mixture is cooled to 23-25 ⁰ 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 degree of purity of 85 % . The remaining 15 % are water. Yield: 90%.

Example 2

4-chloro-3-nitro-benzenesulfinic acid sodium salt prepared according to Example 1 is dissolved at 40 ⁰ C in 300 ml of v / ater. The solution is the

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. It is then cooled to 5 ° C., filtered and the filtered product is dried ^{at a temperature below 40 ° C.} This gives 43 g of white, crystalline 4-chloro-3-nitro-benzenesulfinic acid, melting at 102-103 ⁰ C. Degree of purity: 99 %. The yield, based on the sulfonyl chloride, is 85 % of theory.

Example 3

Phenyl (4-chloro-3-nitro-phenyl) 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 of 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 one more time. To the residue (40 g of crude 4-chloro-3-nitro-benzenesulfinyl-

p A

chloride, n _Q ■ l, 624O) are added to 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 freed from the solvent in vacuo. 45 g (96 %) of white phenyl (4-chloro-3-nitro-phenyl) sulfoxide, which melts at 86-87 ° C., are obtained. Purity (HPL chromatography): 98 %.

b) 36 g (0.1625 mol) of the ^{4-chloro-3-nitro-benzenesulfinic acid prepared according to B} , 20 al dichloroethane, 13.5 ml (22 g, 0.185 mol) thionyl chloride and 0.1 ml

Triethylamine are mixed together. The sulfinic acid goes into solution with evolution of gas. The reaction mixture is heated to 50 ° C. for one hour, then cooled to 5-10 ° C., and 28.2 g (0.2 l mol) of aluminum chloride are added to the solution, care being taken that the temperature does not increase by cooling rises above 40 ^{° C.} Then the mixture is mixed ^{with 35 μl 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 strongly concentrated in vacuo. When the substance begins to precipitate, the benzene is driven off at atmospheric pressure with methanol, the reaction mixture being said to contain about 60-70 ml of methanol. The reaction mixture is then allowed to cool slowly. Crystal precipitation begins at 40-50 ° C. If the product already forms a thick crystal suspension, 100 ml of water at the same temperature are slowly poured in at 40-50 ° C. The loose, finely divided suspension is cooled, stirring slowly to 15-20 ⁰ C. The product is filtered off and dried. 45 g of the title compound are obtained, which agrees in all physical properties with the product according to variant a).

Example 4

Phenyl (4-chloro-3-nitrc-phenyl) sulfoxide 23 g (0.08 mol) of the 84.7% strength sodium 4-chloro-3-nitro-benzenesulfinate prepared according to Example 1 are dissolved in 50 ml of benzene . The mixture of 9.2 ral (0.112 mol) of phosphorus trichloride and 10 ml of benzene is added to the solution within 90 minutes at a temperature of less than 30 ^{° C. with constant stirring.} Then, the mixture is stirred at 22-25 ⁰ C for a further 2.5 hours, decant the benzene solution of the Sulfinylchloridderivates or

sucked off. The solution is removed in vacuo from the solvent freed. Twice more 20 ml of benzene each time are distilled off from the residue. The pale yellow, oily sulfinyl chloride

O A

derivative ( ⁿ _D ■ 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. After the addition, the temperature of the reaction mixture is allowed to rise to 40 ° C. and 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 benzene phases are clarified with activated charcoal, filtered and then evaporated in vacuo. 21 g (95 %) of phenyl (4-chloro-3-nitrophenyl) sulfoxide, which melts at 86-87 ° C., are obtained.

Example 5

(4-chloro-3-nitro-phenyl) - (4-methylphenyl) The -sulfoxyd about 40 g 4-chloro-3-nitro-benzene-sulfinyl chloride produced according to Example 3 are free of benzene and thionyl chloride and then at 20 ⁰ C while cooling with 100 ml of toluene and then 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. This gives 42 g (87%) of the title compound, melting at 82-84 ⁰ C.

Example 6

(4-chloro-3-nitro-phenyl) - (4-chlorophenyl) sulfoxide The procedure described in Example 5 is used

The only difference is 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 in the manner described in Example 1 with sodium sulfite, and the sodium 4-methoxy-3-nitro-benzenesulfinate obtained 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 with one another. 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 purification. 118 g (0.935 mol) of anhydrous sodium sulfite and 20 g of sodium hydrogen carbonate are dissolved in 250 ml of water.

To this solution at 23-25 ⁰ C in one hour, the crude 2 ~ chloro-5-nitro-benzenesulfonyl chloride and 20 g of sodium hydrogen carbonate. The reaction mixture is stirred at the stated 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.degree. The filtered product is washed with 100 ml of toluene.

The sodium-2-chloro-5-nitro obtained benzenesulfinate ~ is dissolved at 40 ⁰ C in 400 ml of water, stirring the solution with 200 ml of toluene and the toluene phase separated after filtration of the solution. The aqueous phase is cooled to 10 ⁰ C, acidified with 100 ml concentrated aqueous hydrochloric acid, and the precipitated crystals are filtered off and then dried. This gives 61 g of 2-chloro-5-nitrobenzolsulfinsäure that schnilzt at 128-130 ⁰ C. The yield based on 4-chloro-nitrobenzene is 55 %. That

Product has a purity (determined with potassium permanganate) of 98 %

Example 9

Phenyl (2-chloro-5-nitro-phenyl) sulfoxide 36 g (0.1625 mol) of 2-chloro-5-nitro-benzenesulfinic acid, 60 ral benzene and 36 ral thionyl chloride are mixed with one another. The reaction mixture is boiled for one hour and then worked up in the manner described in Example 3; Instead of benzene, however, dichloroethane is used for dilution and extraction. 40 g (85 %) of white, microcrystalline phenyl (2-chloro-5-nitro-phenyl) sulfoxide, which melts at 150-152 ° C., are obtained. 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 repeated, with the difference that biphenyl is used instead of toluene. This gives the title compound, melting at 98-99 ⁰ C, 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 ral benzene, 10.5 ml (0.143 mol) thionyl chloride and 0.1 g anhydrous iron (III) chloride are used for one hour long cooked. 28.2 g (0.21 mol) of aluminum chloride are added to the solution, which has been cooled to below 40 ^{° C.} 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, aqueous methanol is added to the solution, the oil which separates out is redissolved in boiling acetone and reprecipitated with aqueous methanol. The oily part is separated and by adding

Acetone crystallizes. This gives 11.4 g (30%) of the title compound, melting at 144-146 ⁰ C.

Example 12
(4-ChloΓ-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.degree. 33.4 g of aluminum chloride are then added in portions, taking care that the temperature does not rise above 20 ^° C. The reaction mixture is stirred at 20 ⁰ C for 4 hours left standing, then poured into 300 ml ice water, extracted with dichloroethane, and the organic phase was removed in vacuo from the solvent. 46.5 g (92 %) of the title compound, which melts at 124-126 ° C., are obtained.

Example 13
(4-Chloro-3-nitro-phenyl) - (4-fluorophenyl) -sulfoxide Benzene and thionyl chloride are removed from about 40 g of the crude 4-chloro-3-nitro-benzenesulfonyl chloride prepared according to Example 3. 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 it is not diluted with benzene. 42 g (86 %) of the title compound, which melts at 84 ° -85 ° C., are obtained.

Example 14

(4-Bromophenyl) - (4-chloro-3-nitrophenyl) sulfoxide 100 ml of brorabenzene are added to about 40 g of the crude 4-chloro-3-nitro-benzenesulfinyl chloride prepared according to Example 3. 33.6 g of aluminum chloride are added to the equipment 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 bromobenzene is removed by distillation at 30-40 torr pressure and 60-70 ° C. This gives 54.5 g (93%) of the title compound, melting at 138-140 ⁰ 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 added in the manner described in Example 3 2-chloro-5-nitrobenzenesulfinyl chloride reacted. The chloride is freed from benzene and thionyl chloride, 100 ml of chlorobenzene and then 28.2 g of aluminum chloride are added while cooling. 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 it has been poured into ice water. This gives 44 g _(86/3) of the title compound, melting at 142-144 ⁰ C.

Example 16
(4-Ethoxy-3-nitrophenyl) -phenyl-sulfoxide

The procedure described in Example 7 is used

Way, but uses 4-ethoxy-3-nitro-benzenesulfonyl chloride as the starting substance, produces from this in the manner described in Example 1 by reduction with sodium sulfite in 70% yield sodium 4-thoxy-3-nitrobenzenesulfinate and processes it further the manner described in Example 4. The title compound is obtained in a yield of 86%. Mp. 119-121 ⁰ 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. This gives the title compound which melts at 173-175 ⁰ C, in 80% yield. ·

example

(4-Chloro-3-nitro-phenyl) - (4-methylthiophenyl) sulfoxide The procedure described in Example 5 is followed, but using thioanisole instead of toluene.

5 Example 1- (4-Nitrophenyl) -4- (4-chloro-3-nitro-phenylsulfinyl) -benzene

The procedure described in Example 5 is followed, with the difference that 4-nitro-10-bifenyl is used instead of toluene. This gives the title compound, melting at 220-222 ⁰ C, in 50% yield ± ger.

Claims (13)

-Jt- Claims i 1. / Process for the preparation of nitrodiarylsulfoxides of the general formula (i) wherein R ¹ 15 R for halogen or alkoxy group with 1-6 carbon atoms and for hydrogen, halogen, alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group, which optionally can be substituted one or more times by halogen and / or nitro, characterized in that one arylsulfonyl halides of the general formula (il) (II) - in which the meaning of R is the same as above and X is halogen - reduced with an »alkali metal sulfite, the obtained aryl sulfinate of the general formula (ill) SO ₂ M (in) - wherein the meaning of R is the same as above and M stands for alkali metal - treated with an acid that Arylsulfiny derivative of the general formula (iv) obtained (IV) - in which the meaning of R is the same as above or the arylsulfinate of the general formula (ill) - wherein the meaning of R and M is the same as above reacts with a halogenating agent and the obtained Arylsulfiny! Halide of the general formula (v) O ₂ N , SOX ² (ν) - wherein the meaning of R is the same as above and 2
X stands for halogen - in the presence of a metal halide catalyst with Lewis acid properties with benzene derivatives of the general formula (vi) (VI) wherein the meaning of R is the same as above reacts. 2. The method according to claim 1, characterized in that the reduction to 1 mole of arylsulfonyl halide of the general formula (II), in which the meanings of R and X are the same as in claim 1 is, 1.1-4 moles of alkali metal sulfite is used. 3. The method according to claim 1 or 2, characterized in that the arylsulfonyl halide of general formula (il), in which the meaning of R and X is the same as in claim 1, at temperatures reduced between 20 and 50 ° C. 4. The method according to any one of claims 1-3, characterized in that the arylsulfonyl halide of the general formula (II), wherein the meaning of R ¹ and X is the same as in claim 1, reduced in a weakly basic medium. 5. The method according to claim 1, characterized in that that one the arylsulfinate of the general formula (ill), wherein the meaning of R and X the same as above is treated with an excess of a strong mineral acid. 6. The method according to claim 1, characterized in that that one the arylsulfinyl halide of the general formula (v), wherein the meaning of R and X the same as in claim 1, after removing the excess of the halogenating agent without intermediate separation, directly to the benzene derivative of the general formula (vi), wherein the meaning of R is the same as in claim 1 is implemented. 7. The method according to claim 1 or 6, characterized in that that one in the reaction of the Arylsulfinylhalogenide of the general formula (v), in which the meaning 1 2 of R and X is the same as in claim 1, with the Benzene derivative of the general formula (vi), wherein the loading Interpretation of R is the same as in claim 1, as Lewis acid based on 1 mole of arylsulfinyl chloride 1.1-1.8 moles of aluminum chloride used. 8. The method according to any one of claims 1, 6 and 7, characterized in that the arylsulfinyl halide of the general formula (v) - wherein the meaning of 1 2 R and X is the same as in claim 1 - with the Benzene derivative of the general formula (vi) - wherein the 2 Meaning of R is the same as in claim 1 - at temperatures between O ⁰ C and 80 ⁰ C implemented. 9. Nitrodiarylsulfoxides of the general formula (i) (I) wherein
R ¹ for halogen or alkoxy group with 1-6 carbon atoms and for hydrogen, halogen, alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio group, which optionally can be substituted one or more times by halogen and / or nitro. 10. A compound selected from the following group: Phenyl (4-chloro-3-nitrophenyl) sulfoxide, (4-chloro-3-nitrophenyl) - (4-methylphenyl) sulfoxide, (4-ChIoΓ-3-nitrophenyl) - (4-chlorophenyl) sulfoxide, Pheny1- (4-methoxy-3-nitrophenyl) sulfoxide, Phenyl- (2-chloro-5-nitrophenyl) sulfoxide, (4-chloro-3-nitrophenyl) -4-biphenylyl sulfoxide, (4-chloro-3-nitrophenyl) -4-methoxyphenyl-sulfoxy d, (4-chloro-3-nitrophenyl) -4-fluorophenyl sulfoxide, 4-bromophenyl- (4-chloro-3-nitrophenyl) sulfoxide, 4-chlorophenyl- (2-chIoΓ-5-nitrophenyl) sulfoxide, (4-Athoxy-3-nitrophenyl) -phenyl-sulfoxide, 1- (4-bromopheny1) -4- (4-chloro-3-nitrophenylsulfinyl) benzene, l- (4-nitrophenyl) -4- (4-chloΓ-3-nitrophenylsulfonyI) benzene, 4-C (4-chloro-3-nitrophenylthio) phenyl] -4-chloro-3-nitrophenyl) sulfoxide. 11. Medicinal preparations containing as active ingredient a compound of the general formula (i), wherein the 1 2 Meaning of R and R the same as in claim is, together with pharmaceutical carriers and / or excipients. 12. Pesticidal agents containing as active ingredient a compound of the general formula (i) wherein for halogen or alkoxy group with 1-6 carbon atoms and R is hydrogen, halogen, alkyl or alkoxy group each having 1-6 carbon atoms or a phenyl or phenylthio which may be optionally alogen by ^H and / or mono- or polysubstituted nitro, together with solid and / or liquid extenders and carriers and optionally other additives. 13. Composition according to claim 12, containing as active ingredient a compound of the general formula (i). wherein the meaning of R and R is the same as in claim 12, _t in a concentration of 0.1-95 wt -%.