DE3135367A1 - Process for the preparation of nitrophenyl beta -hydroxyethyl sulphide derivatives and nitrophenyl beta -hydroxyethyl sulphone derivatives - Google Patents

Abstract

A process is described for preparing nitrophenyl beta -hydroxyethyl sulphide derivatives of the general formula Ia and nitrophenyl beta -hydroxyethyl sulphone derivatives of the general formula Ib <IMAGE> in which one of the radicals Z1 and Z2 denotes a hydrogen atom or a beta -hydroxyethylthio group, one of the radicals Z3 and Z4 denotes a hydrogen atom or a beta -hydroxyethylsulphonyl group, and Y denotes a hydrogen atom or a halogen atom, characterised in that a compound of the general formula II <IMAGE> in which one of the radicals X1 and X2 denotes a hydrogen atom and the other radical denotes a halogen atom, and Y denotes a hydrogen or halogen atom, is reacted with beta -mercaptoethanol in the presence of an acid acceptor, either in an aprotic polar solvent or in the absence of a solvent or in an aqueous solvent, and the resulting sulphide of the general formula Ia is optionally oxidised to the corresponding sulphone of the general formula Ib, using tungstic acid, or a salt of this compound, containing hydrogen peroxide as the catalyst, at a pH of 3 to 8 and a temperature of 30 to 100 DEG C.

Description

The invention relates to the rena-

drew object.

The nitrophenyl-ß-hydroxyethyl sulfide derivatives of the general formula Ia are intermediate products for the preparation of the nitrophenyl-ß-hydroxyethylsulfone derivatives of the general formula Ib. The compounds of the general formula Ib are intermediates for the production of aminophenyl - hydroxya'tbylsul fon derivatives, the valuable starting compounds represent for the production of reactive dyes.

Phenyl p-amino / -ß-hydroxyethyl sulfone is known to be produced in industry according to the following reaction scheme: CIydxolysis' ° 2 2 2 The process requires several steps and the overall yield is low.

Accordingly, the invention is based on the object of producing starting compounds for aminophenyl-β-hydroxyethyl sulfone in a different, more advantageous way. This new production process is explained using the example of the production of p-aminophenyl-ß-hydroxyethylsulfone by the following reaction scheme: Xeduction F ' N024 2 2 2 (C) 2SO2 NH2tS02CH2cH20H This method is advantageous over the known method for the reasons explained below.

The known processes for the production of p-nitrophenyl-B-hydroxyethylsulfone proceed according to the following reaction scheme: Diazotize and Decompose - ClCH2CR2OH (2) N ° 2 e NH2 -> N2 e so - 2 NO2m7sH In each of processes (1) and (2), p-nitrophenyl-B-hydroxyethyl sulfide is obtained from p-nitrothiophenol. Since the yield in the preparation of this compound is very low, processes (1) and (2) are not economically interesting.

In the journal J. Rohem. Soc., 1927, p. 1668 is one method for the production of o-nitrophenyl-ß-hydroxyethyl sulfide or 2,4-dinitrophenyl-ß-hydroxyethyl sulfide by reacting an o-nitrohalobenzene or 2,4-dinitrochlorobenzene with ß-mercaptoethanol in methanol and in the presence of Ealiumhydroxid described as an acid acceptor. It is from the literature tur known that this Process on the production of p-nitrophenyl-ß-hydroxyethyl sulfide reduction and other side reactions occur and the desired product is not obtained. However, our own studies have shown that in the implementation of the compound of the general formula II with ß-mercaptoethanol in equivalent amounts and in the presence an acid acceptor in an aprotic polar solvent the compound of general formula Ia can be obtained in high yield. It was also found that that this reaction works smoothly in the presence of an acid acceptor in an aqueous one Solvent or in the absence of a solvent proceeds.

There are several processes for the preparation of nitrophenyl-β-hydroxyethylsulfone derivatives by oxidation of nitrophenylß-hydroxyethyl sulfide derivatives of the general formula Well known. The usual process consists in the oxidation of nitrophenyl-ß-hydroxyethyl sulfide with hydrogen peroxide in glacial acetic acid. In this process, the oxidation takes place æum Nitrophenyl-ß-hydroxyäthylsulfoxid quickly and smoothly, however, is for further Oxidation required for sulphone heating. At this stage of heating, inevitably considerable amounts of by-products, e.g. an acetic acid ester of Nitrophenyl-ß-hydroxyethyl sulfone. That is why the yield and quality of the Unsatisfactory product. Furthermore, this method brings difficulties in connection with the recovery of acetic acid. Accordingly, this procedure is off technical reasons not preferred.

Process for the production of sulfones by oxidation of 2-nitrophenyl-ß-hydroxyethyl sulfide and 4-Ni trophenyl-ß-hy droxyäthylsulfid are from JP-AS 24 661/68 and DE-PS 944 607 known. The method described in JP-AS 24 661/68 is characterized in that that 2-nitrophenyl ß-hydroxyethyl sulfide with hydrogen peroxide at 50 to 45 ° C oxidized in aqueous sodium bicarbonate solution. The oxidation to the 2-Nitrophenyl-ß-hydroxyethyl sulfoxide runs smoothly, but the sulfone is formed practically not. Even with the addition of further amounts of hydrogen peroxide or after increasing the oxidation proceeds insufficiently at the reaction temperature.

According to the method described in DE-PS 944 607, the Oxidation with hypochlorous acid in an aqueous solution of a basic inorganic Link. The exemplary embodiments of the patent specification were repeated, and it the oxidation was found not to proceed smoothly, substantial amounts be obtained on the starting compound and the yield and purity of 2-nitrophenyl-ß-hydroxyethyl sulfone was insufficient.

The invention is therefore based on the object of a method for Production of nitrophenyl-ß-hydroxyethyl sulfone derivatives from the corresponding Nitrophenyl-ß-hydroxyethyl sulfide derivatives develop that smoothly and in high Yield runs. This object is achieved according to claims 5 to 10.

In the oxidation of a compound of the general formula Ia with hydrogen peroxide in an aqueous solution of tungstic acid or its salt as a catalyst for a pH 3 to 8 and a temperature of 30 to 100 ° C will be smooth and in high Yield and purity of a compound of general formula Ib obtained. After the This connection cannot easily be established using conventional methods.

The method according to the invention differs favorably from the known process in that 2-nitrophenyl-ß hydroxyethyl sulfone is very high in purity can be easily obtained. In the production of 4-nitrophenyl-ß-hydroyäthylsulfon the implementation is smoother than in the known process.

Examples of halogen atoms in the compounds of the general formula II are? Luor, chlorine, bromine or iodine atoms. Chlorine and bromine atoms are preferred. Specific examples of compounds of the general formula II are p-nitrochlorobenzob, p-nitrobromobenzene, o-nitrochlorobenzene, o-nitrobromobenzene, 2,5-dichloronitrobenzene and 2,5-dibromaitrobenzene. o- and p-nitrochlorobenzene are preferred.

As acid acceptors, e.g. alkali metal hydroxides, such as potassium and sodium hydroxide, and alkali metal carbonates and bicarbonates such as sodium and Potassium bicarbonate as well as sodium and potassium carbonate in question. Preferred acid acceptors are sodium and potassium carbonate and bicarbonate.

When carrying out the reaction in the presence of an acid acceptor in an aprotic polar solvent, the acid acceptor can be added all at once will. If the acid acceptor has a relatively good solubility in the solvent possesses, it is advisable to use the acid acceptor in proportions one after the other admit.

When carrying out the reaction in the absence of a solvent Sodium and potassium carbonate are particularly preferred as acid acceptors. Because potassium carbonate is particularly reactive, it is added once. The implementation is violent, and control of the reaction temperature becomes difficult. Potassium carbonate is preferred added over a period of about 1 hour.

The acid acceptor is used in an amount of about 5% excess the equivalent amount is used. Satisfactory results can be obtained. When using larger amounts of acid acceptor, disadvantages are sometimes found.

Suitable aqueous solvents are water and mixtures of water with a water-immiscible solvent. Specific examples of water-immiscible solvents are benzene, toluene, xylene, ethylbenzene, isopropylbenzene, chlorobenzene, dichlorobenzene and p-cumene. Furthermore, the aqueous solvent can be a phase transfer catalyst such as or a dispersant can be added to the aqueous solvent.

Specific examples of aprotic solvents are N, N-dimethylformamide, N, N-dimethylacetamide, W-methylpyrrolidone and N-methylimidazolidinone. Are preferred N, N-dimethylformamide and N dimethylacetamide. The solvent is usually in 1/10 to 2 times the amount of the compound of general formula II is used. Using a small amount of the aprotic polar solvent can for better dissolution of the compounds of general formula II and for dispersion of the acid acceptor is still an aromatic hydrocarbon such as benzene, a halogenated one aromatic compound such as chlorobenzene, dichlorobenzene, trichlorobenzene, alkylated aromatic compounds such as toluene, xylene, ethylbenzene, isopropylbenzene or p-cumene or mixtures of at least two of the components mentioned can be used. Further can also be a mixture of at least two different aprotic polar solvents be used.

The ß-mercaptoethanol can be used together with p-nitrochlorobenzene and optionally be heated to the reaction temperature with a solvent. It can also a process can be used in which half of the ß-mercaptoethanol used first added and the other half in proportions and at certain time intervals is admitted. The ß-mercaptoethanol can also be used in proportions at the reaction temperature be added from the beginning of the reaction. When using excess amounts ß-mercaptoethanol can be p-nitrophenyl-ß-hydroxyethyl sulfide with good quality and the yield, based on p-nitro- chlorobenzene, is increased. However, the yield, based on β-mercaptoethanol, is reduced.

A method can be used in which ß mercapto ethanol is used in an amount of 150 to 250% of the equivalent amount. After finished Implementation, the unreacted ß-mercaptoethanol is recovered. Furthermore can a process can be used in which the ß-mercaptoethanol in an equivalent amount used and the unreacted p-nitrochlorobenzene by steam distillation or is separated at a later stage. To suppress the oxidation of ß-mercaptoethanol a weak reducing agent such as sodium bisulfite or sodium sulfite can be added will.

When using excess ß-mercaptoethanol, the mother liquor after separating the reaction product with a suitable reducing agent treated to recover β-mercaptoethanol. If the reaction is in a aprotic polar solvent or carried out in the absence of a solvent the reaction temperature is usually from 30 to 15,000, preferably from 60 to 1200C, when carrying out the reaction in an aqueous solvent the reaction temperature is usually in the range of 45 to 950 ° C., below the oxidation of the compounds of general formula Ia to the compounds the general formula Ib described.

In the absence of metals, such as iron or copper, the hydrogen peroxide catalytically decompose, an equivalent amount of hydrogen peroxide is sufficient for oxidation even at high temperatures, such as 80 to 900C. In the presence of such metals to suppress the decomposition of the hydrogen peroxide, preferably a gelling agent, like EDTA, added.

The usual aqueous solutions are used in the process according to the invention of hydrogen peroxide with a concentration of 30 to 35% hydrogen peroxide used. However, aqueous solutions with other hydrogen peroxide concentrations can also be used can be used. Tungstic acid or a salt of this compound is in the form of a aqueous solution or used as a colloidal suspension. Examples of suitable Tungstic acid salts are sodium tungstate and ammonium tungstate.

Preferably the catalyst is used in an amount of at least 0.005 Moles per mole of sulfide of the general formula Ia are used.

The pH of the liquid reaction mixture is usually 3 to 8, preferably 5 to 7, and the reaction temperature is usually in the range from 30 to 1000C, preferably from 60 to 950C.

The examples explain the process according to the invention.

Example 1 9.1 g of p-nitrochlorobenzene are dissolved in 21 ml of toluene and a solution of 4.9 g of sodium bicarbonate in 65 ml of water is added. Then 6 g of ß-mercaptoethanol and 1.8 g of tributylbenzylammonium chloride are used as the phase transfer catalyst admitted. The temperature is increased and the mixture is refluxed for 10 hours heated. The reaction mixture is then cooled and the toluene by steam distillation severed. The resulting precipitate is filtered off and dried. It will be 7.2 g of p-nitrophenyl-ß-hydroxyethyl sulfide with a melting point of 57 to 60 ° C. were obtained. The yield is 62.6% based on p-nitrochlorobenzene.

Example 2 A mixture of 31.5 g of p-nitrochlorobenzene, 32.9 g of B-mercaptoethanol and 20 ml of water is heated to 70 to 75 ° C. in a stream of nitrogen. Then be in 5 shares within 3 hours a total of 35 g of potassium carbonate registered. When the addition of the potassium carbonate is complete, the reaction mixture becomes heated for a further 2 1/2 hours to 70 to 7500 and then cooled. The mixture the precipitated solid and liquid are treated with hydrochloric acid. It will obtained a solid. The substance is filtered off and dried. It will 29.3 g of p-nitrophenyl-ß-hydroxyethyl sulfide from B. 57 to 60 ° C. The yield is 73.6 5 'based on p-nitrochlorobenzene.

Example 3 Example 2 is repeated, but 20 ml Chlorobenzene was added, which was separated off by steam distillation after the reaction will. 30.8 g of p-nitrophenyl-β-hydroxyethyl sulfide from B. 58 to 6000 are obtained. The yield is 77.3 5 ', based on p-nitrochlorobenzene.

Examples 4 to 6 Example 3 is among those listed in Table I. Reaction conditions repeated. The results are also summarized in this table. The yield is based on p-nitrochlorobenzene.

Table I. Ü 0 1 H 0 0 ' HO tr PI 0 approx 0 0 q, 0 ao .0 rLIo tX solvent ""1 "1 , "S o3 S sh 3 ap 'O PI 4 4 31.5 329 K2C03, flOO ml of water and 70-75 6 58-60 75.8 15 20 ml o-dichloro g benzene 5 31.5 32.9 NaHCO3, 10 ml water and - 70-73 5 57-60 76.5 17.6 g 20 ml xylene - 6 31.5 23.4KCO, 5 mol water and 20 ml 70-75 10 55-60 73.7 15 g chlorobenzene Example 7 Example 2 is repeated, but 35 g of p-nitrobromobenzene are used instead of 27 g of p-nitrochlorobenzene.

There are 25.6 g of p-nitrophenyl-ß-hydroxyethyl sulfide from B. 58 to 6000 received. The yield is 74.2 5 ', based on p-nitrobromobenzene.

B e i 5 p i e 1 e 8 and 9 Examples 2 and 3 are identical Repeatedly, but 404 g of p-nitrobromobenzene are used instead of 31.5 g of p-nitrochlorobenzene used. There are 31.3 g or 31.7 g of p-nitrophenylß-hydroxyethyl sulfide from F. 58 to 600C obtained. The yields are 78.6 and 79.6 5 ', based on p-nitrobromobenzene.

Example 10 A mixture of 36.4 g of p-nitrochlorobenzene, 30 g of N, N-dimethylformamide and 19 g of 95 percent ß-mercaptoethanol is heated to 40 to 450C. Then will the resulting solution with 12.9 g of finely powdered anhydrous sodium carbonate offset. The temperature is increased and the mixture is at 1000C for 5 1/2 hours heated. Then the pressure is reduced to 100 to 110 Torr and the water distilled off at 70 to 800C. The pressure is then further reduced and the N, N-dimethylformamide distilled off. Finally, the residue is heated to 1200C / 15 torr for 30 minutes and then cooled. The reaction product is dissolved with hot water. When cooling down 4-nitrophenyl-ß-hydroxyethyl sulfide solidifies at room temperature. The product is ground in a mortar, filtered and dried. There are 42.5 g of product obtained from F. 59 to 600C. The yield is 93.296. N, N-dimethylformamide is recovered in a yield of 98%.

Example 11 A mixture of 46.6 g of p-nitrobromobenzene, 20 g of N, N-dimethyl formamide and 19 g of 95 percent ß-mercaptoethanol is heated to 50 to 6000. Then will the resulting solution with 12.9 g of anhydrous finely powdered sodium carbonate offset. The temperature is increased and the mixture is heated to 90 ° C. for 5 hours. The aftertreatment is carried out as in Example 10. 43.2 g of product from F. 59 Preserved to 600C.

The yield is 93.9 5 '.

A mixture of 36.4 g of p-nitrochlorobenzene, 30 g of N, N-dimethylformamide and 20 g of 95 percent ß-mercaptoethanol is heated to 40 to 450C. Then will 20.4 g of sodium bicarbonate are added to the resulting solution. The temperature will and the mixture was heated to 90 ° C. for 5 1/2 hours.

The aftertreatment takes place as in Example 10. 42.7 g of product are obtained received from F. 59 to 6006. The yield is 92.8 5 '.

Example 13 A mixture of 36.4 g of p-nitrochlorobenzene, 30 g of N, N-dimethylacetamide and 20 g of ß-mercaptoethanol is heated to 40 to 45 ° C. Then the obtained 16.8 g of anhydrous potassium carbonate are added to the solution. The temperature is increased and heated the mixture to 10,000 for 5 hours. The aftertreatment is carried out according to the example 10. 42.5 g of product with a melting point of 59 to 60 ° C. are obtained. The yield is 92.4 5 '.

Example 14 A mixture of 36.4 g of p-nitrochlorobenzene, 30 g of N-methyl-2-pyrrolidone and 19 g of 95 percent ß-mercaptoethanol is heated to 40 to 450C. Then will 16.0 g of anhydrous potassium carbonate are added to the resulting solution. The temperature is increased and the mixture is heated to 10,000 for 5 1/2 hours. The aftercare takes place according to Example 10. 43.2 g of product with a melting point of 59 to 60 ° C. are obtained. The yield is 93.9 5 '.

Example 15 A mixture of 36.4 g of p-nitrochlorobenzene, 20 g of N-methylimidazolidinone and 19 g of ß-mercaptoethanol is heated. Then the resulting solution with 20.4 g sodium bicarbonate added. The temperature is increased and the mixture is 5 1/2 hours heated to 90 0C. The aftertreatment is carried out as in Example 10. It becomes 41.9 g of product obtained from m.p. 59 to 600C. The yield is 91.06%.

Example 16 Example 10 is repeated, but 46.6 g of p-nitrobromobenzene are obtained used instead of 36.4 g of p-nitrochlorobenzene.

42.6 g of product with a melting point of 59 to 60 ° C. are obtained. The yield is 92.6 46 of theory.

Example 17 A mixture of 36.4 g of p-nitrochlorobenzene and 19 g of 95 percent strength ß-mercaptoethanol is heated. Then the homogeneous solution becomes fine with 12.9 g added powdered sodium carbonate. The temperature is increased to 1000C and that The mixture was heated at this temperature for 8 hours. Thereafter, the reaction mixture mixed with warm water and heated to 900C for 10 minutes. Thereupon the reaction mixture cooled, filtered and dried. 41.6 g of product are obtained. Because of the gas analysis analysis consists of 86.5 5 'of the product from p-nitrophenyl-ß-hydroxyethyl sulfide and 12.7% from p-nitrochlorobenzene.

Example 18 A mixture of 31.2 g of β-mercaptoethanol and 31.5 g of o-nitrochlorobenzene is heated to 4500. The solution obtained is with 35 g of a 50 percent aqueous Potassium carbonate solution is added dropwise over the course of 15 minutes. Simultaneously the solution is heated to 45 to 500C. Then another 35 g are 50 percent aqueous potassium carbonate solution was added dropwise at 50 to 5500 in the course of 1 hour. To terminate- ter addition, the mixture is heated to 50 for a further 4 hours 55 ° G heated. After the reaction has ended, the temperature is increased to 70.degree. The mixture is then cooled to room temperature. Yellow crystals separate which are filtered off, washed with water and dried. Yield: 38.0 g of 2-nitrophenyl-B-hydroxyethyl sulfide with a melting point of 102 to 10300. The yield is 95%.

Example 19 Example 18 is repeated, but 38.4 g of 2,5-diehlornitrobenzene are used used instead of o-nitrochlorobenzene.

There are 44.6 g of 2-nitro-4-chlorophenyl-ß-hydroxyethyl sulfide from F. 92 to 93 ° C obtained. The yield is 95.5 5 '.

Example 20 70 ml of water are mixed with 31.5 g of o-nitrochlorobenzene, 26.5 g ß-mercaptoethanol and 18 g sodium carbonate are added. The mixture is 5 hours heated to 60 to 700C. The reaction mixture is then continued for a further 5 hours 900C heated.

After the reaction has ended, 100 ml of water are added and the mixture is cooled to room temperature. The crystallized product is filtered off, washed with water and dried. There are 35.4 g of 2-nitrophenyl-ß-hydroxyethyl sulfide obtained from m. 102 to 1030C. The yield is 89 5 '.

Example 21 40 ml of water are mixed with 51.5 g of o-nitrochlorobenzene, 36 g of potassium carbonate and 0.3 g of Smulgen 147 are added, and the mixture is heated to 650.degree. Then 20.3 g of β-mercaptoethanol are added dropwise within 2 hours, the suspension is heated to 65 to 700C during this time. When the addition is complete, the The mixture was heated to 70 ° C. for a further 6 hours.

When the reaction has ended, 65 ml of water are added and the mixture is cooled to room temperature. The excellent different crystals are filtered off, washed with water and dried. Yield: 37.4 g of 2-nitrophenyl-β-hydroxyethyl sulfide from m. 102 to 10300. The yield is 94 5 '.

Example 22 26 g of X, dimethylformamide are mixed with 31.5 g of o-nitrochlorobenzene and 15.7 g of ß-mercaptoethanol added and stirred. Thereafter, 11.2 g of anhydrous finely powdered sodium carbonate is added and the temperature is increased. The reaction is carried out at 1000C for 7 hours. After implementation is complete the pressure is reduced to 100 to 110 torr and the water is distilled off at 70 to 80.degree. The pressure is then reduced further and the N, -dimethylformamide is distilled off.

The residue is heated to 12000/15 torr for 30 minutes and thereafter cooled down. The solidified crystals are crushed in a mortar with water washed, filtered and dried. There are 39.1 g of o-nitrophenyl-ß-4ydroxyäthylsulfid obtained from F. 102 to 10300. The yield is 98.2 5 '.

Example 23 Example 22 is repeated, but 40.4 g of o-nitrobromobenzene are used used instead of o-nitrochlorobenzene. There are 38.7 g of o-nitrophenyl-ß-hydroxyethyl sulfide obtained from m. 102 to 1030C. The yield is 97.3 5 '.

Example 24 20 g of N-methylimidazolidinone are mixed with 31.5 g of o-nitrochlorobenzene and 15.7 g of ß-mercaptoethanol are added. The mixture is heated to a solution. 17.7 g of sodium bicarbonate are then added and the temperature is increased and the reaction was carried out at 900G for 5 1/2 hours. The follow-up treatment takes place according to Example 22. There are 36.4 g of o-nitrophenyl-ß-hydroxyethyl sulfide from B. 102 up to 1030C keep. The yield is 91.5 5 '.

B e i s p i e 1 2 5 A mixture of 31.5 g of o-nitrochlorobenzene and 15.7 g of ß-mercaptoethanol is heated. Then the resulting solution with 14.5 g finely powdered potassium carbonate added within 1 hour. This is the temperature kept below 90 ° C by cooling. When the addition is complete, the temperature is increased to 1 * 05 ° C within about 30 minutes and the reaction at this temperature Carried out for 4 hours. Then hot water is added to the reaction mixture and the mixture is heated to 1000C for 10 minutes. The mixture is then cooled and the resulting solid is filtered off and dried. There are 37.0 g of crystals obtained, which consist mainly of o-nitrophenyl-ß-hydroxyäthylsuflid.

The crystals exist based on the gas chromatographic analysis 91.8% from o-nitrophenyl-ß-hydroxyethyl sulfide and 7.12 5 'from o-nitrochlorobenzene.

3Example 26 A mixture of 31.5 g of o-nitrochlorobenzene and 15.7 g ß-mercaptoethanol is heated. Then the resulting solution becomes fine with 11.2 g added powdered sodium carbonate and the temperature increased to 12,000. At this Temperature, the reaction is carried out for 8 hours. Thereafter, the reaction mixture mixed with hot water and the mixture heated to 100 ° C for 10 minutes and then cooled down. The resulting crystals are filtered off and dried. It will 96.0 g of crude product were obtained. Based on the gas chromatographic analysis the product to 86.5% from o-nitrophenyl-ß-hydroxyätaylsulfid and to 12.7 5 'from o-nitrochlorobenzene.

Example 27 0.4 g of sodium tungstate are dissolved in 100 ml of water. The pH value is adjusted to 5.5 by adding a little acetic acid posed. Then 20 g of 2-nitrophenyl-ß-hydroxyethyl sulfide are added and the mixture is heated to 600C.

10 g of 35 percent hydrogen peroxide solution are then added within 30 minutes dripped in. The temperature is increased to 60 to 800C by external cooling with water set.

The sulfoxide formed precipitates. Then another 13 g of 35 percent strength Hydrogen peroxide solution was added dropwise within 1 hour at 80 to 900C. After finished Addition, the temperature is increased to 90 to 950C and the reaction at this temperature 8 hours carried out. After the reaction has ended, the reaction mixture is brought to room temperature cooled down. Yellowish white crystals are obtained. The product is filtered off, washed with water and dried.

Yield: 21.7 g of 2-nitrophenyl-ß-hydroxyethyl sulfone from B.

880C. The yield is 94 96.

Example 28 Example 27 is repeated, but 4-nitrophenyl-β-hydroxyethyl sulfide is used 2-nitrophenyl-ß-hydroxyethyl sulfide is also used. There are 22.1 g of 4-nitrophenyl-ß-hydroxyethyl sulfone obtained from m. 129 to 1300C. The yield is 96 5 '.

Example 29 Example 27 is treated with 23.4 g of 2-nitro-4-chlorophenyl-β-hydroxyethyl sulfide repeated. There are 24.5 g of 2-nitro-4-chlorophenyl-B-hydroxyethyl sulfone of F. 111 until 11200 received.

The yield is 92 5 '.

Example 30 100 ml of water are admixed with 0.3 g of tungstic acid. The pH is adjusted to 11 to 12 with sodium hydroxide solution. After that the pH adjusted to 5 to 6 by adding a small amount of 5 percent hydrochloric acid. The aqueous catalyst solution is treated with 21.5 g of 2-nitrophenyl-ß-hydroxyethyl sulfoxide offset. The suspension obtained is on 850C, and heated within 12 g of 35 percent hydrogen perovide solution are added dropwise for about 2 hours The temperature is kept at 85 to 950 ° C. with external cooling with water. To When the addition is complete, the reaction is carried out at 85 ° to 90 ° C. for a further 6 hours. After the reaction has ended, the reaction mixture is cooled to room temperature. Yellowish white crystals precipitate. The crystals are filtered off with Water washed and dried. Yield: 22.2 g of 2-nitrophenyl-B-hydroxyethyl sulfone from F. 880C.

The yield is 96 io, Example 31 A mixture of 36.4 g of p-nitrochlorobenzene, 30 g of N, N-dimethylformamide and 19 g of 95 percent ß-mercaptoethanol is added to 40 bis 45 ° C heated. The resulting solution is finely powdered with 12.9 g of anhydrous Sodium carbonate is added and the temperature is increased and the mixture is 5 1/2 hours heated to 10,000. Thereafter, the pressure is reduced to 100 to 110 Torr and that Water distilled off at 70 to 800C.

The pressure is then reduced further and the N, N-dimethylformamide distilled off. Finally, the reaction mixture is heated to 1200C / 15 torr for 30 minutes heated. The mixture is then cooled. Once the temperature dropped to 7000 is, the pressure is brought to atmospheric pressure and the mixture with hot water offset. The liquid is separated and it becomes 4-nitrophenyl-ß-hydroxyethyl sulfide obtain.

Separately, 0.86 g of sodium tungstate are dissolved in 216 ml of water. The pH of the solution is adjusted to 5.5. That after the one described above Process produced 4-nitrophenyl-ß-hydroxyethyl sulfide is in the aqueous solution entered, and the mixture is heated to 7,000. Then within 2 hours 50.2 g of 35 percent aqueous hydrogen / oxide solution were added dropwise. At the same time will the% mpe <kept at 75 to 800cm. Then the mixture Heated for 3 1/2 hours to 75 to 80 ° C and a further 1 1/2 hours to 90 to 950 ° C. The reaction mixture is then cooled to room temperature. The precipitated The crystals are filtered off, washed with water and dried.

There are 47.4 g of 4-nitrophenyl-ß-hydrocyäthylsulfon from F.

129 to 13000 received. The overall yield is 88.6% on a basis on p-nitrochlorobenzene.

Example '32 40 ml of water are mixed with 31.5 g of o-nitrochlorobenzene, 36 g of potassium carbonate and 0.3 g of Emulgen 147 are added. The mixture is heated to 6500. Then 20.3 g of β-mercaptoethanol are entered within 2 hours. The suspension is kept at a temperature of 65 to 700C. When the addition is complete, the Implementation carried out at 700C for 6 hours. Thereafter, the liquid reaction mixture mixed with 1.0 g of sodium tungstate, the pH value with 35 percent hydrochloric acid 5 to 6 are set, and 105 g of 35 percent aqueous hydrogen peroxide solution are added within 5 hours dripped in. During the addition, the temperature is through.

Water cooling kept at 70 to 800C. The pH is increased by dropwise Addition of 10 percent aqueous sodium carbonate solution kept at 5 to 6.

When the addition of the hydrogen peroxide solution is complete, the temperature increased to 85 to 900C and carried out the reaction for a further 2 hours. After finished Reaction, the reaction mixture is cooled to room temperature. It-fall yellowish white crystals. The crystals are filtered off, washed with water and dried. 41.1 g of 2-nitrophenyl-β-hydroxyäthylsulfon with a melting point of 880C are obtained. The overall yield is 89 5 '.

Claims (10)

't Process for the production of nitrophenyl-ß-hydroxyethyl sulfide and -ß-hydroxyethyl sulfone derivatives 1? Claims: 1, / Process for the preparation of nitrophenyl-ß-hydroxyethyl sulfide derivatives of the general formula Ia in which one of the radicals Z1 and Z2 is a hydrogen atom and the other radical is a β-hydroxyethylthio group and Y is a hydrogen or halogen atom, characterized in that a compound of the general formula II is used in which one of the radicals X1 and X2 is a hydrogen atom and the other radical is a halogen atom and Y is a hydrogen or halogen atom, with ß-mercaptoethanol in the presence of an acid acceptor either in an aprotic polar solvent or in the absence of a solvent or in an aqueous solvent for Implementation brings. 2. The method according to claim 1, characterized in that there are compounds uses, in which the halogen atom is a chlorine or bromine atom. 3. The method according to claim 2, characterized in that as Compound of the general formula II p-nitrochlorobenzene or o-nitrochlorobenzene, as aprotic polar solvent, N, N-imethylformamide or N, N-dimethylacetamide and uses sodium or potassium carbonate or sodium bicarbonate as the acid acceptor and the reaction is carried out at a temperature of 30 to 1500C. 4. The method according to claim 2, characterized in that as Compound of the general formula II p-nitrochlorobenzene or o-nitrochlorobenzene and uses sodium or aluminum carbonate or sodium bicarbonate as the acid acceptor, used as a solvent, an aqueous solvent and the reaction at a Temperature of 45 to 95 0C performs. 5. Process for the preparation of nitrophenyl-ß-hydroxyethyl sulfone-I) derivatives of the general formula Ib in which one of the radicals Z3 and Z4 is a hydrogen atom and the other radical is a β-hydroxyethylsulfonyl group and Y is a hydrogen or halogen atom, characterized in that a compound of the general formula II in which one of the radicals X1 and X2 is a hydrogen atom and the other radical is a halogen atom and Y is a hydrogen or halogen atom, with ß-MercaptoSthBnol in the presence of an acid acceptor either in an aprotic polar solvent or in the absence of a solvent or in an aqueous solvent Formation of the nitrophenyl-ß-hydroxyethyl sulfide derivative of the general formula Ia in which one of the radicals Z1 and Z2 is a hydrogen atom and the other radical is a β-hydroxyethylthio group and Y is a hydrogen or halogen atom, and the sulfide obtained is reacted with hydrogen peroxide-containing tungstic acid or a salt of this compound as a catalyst at a pR value of 3 to 8 and a temperature of 30 to 10,000 to the sulfone. 6. The method according to claim 5, characterized in that there are compounds of the general formula II, in which the halogen atoms are chlorine or bromine atoms mean. 7. The method according to claim 6, characterized in that as Compound of the general formula II p-nitrochlorobenzene or o-nitrochlorobenzene, as aprotic polar solvent, N, N-dimethylformamide or N, N-dimethylacetamide and uses sodium or potassium carbonate or sodium bicarbonate as the acid acceptor and the implementation at an empe- temperature from 30 to 1500C. 8. The method according to claim 6, characterized in that as Compound of the general formula II p-nitrochlorobenzene or o-nitrochlorobenzene and uses sodium or potassium carbonate or sodium bicarbonate as the acid acceptor, an aqueous solvent is used as the reaction solvent and the reaction at a temperature of 45 to 950C. 9. Process for the preparation of nitrophenyl-ß-hydroxyethyl sulfone derivatives of the general formula Ib in which one of the radicals Z3 and Z4 is a hydrogen atom and the other radical is a β-hydroxyethylsulfonyl group and Y is a hydrogen or halogen atom, characterized in that a nitrophenyl-β-hydroxyethylsulfide derivative of the general formula Ia in which one of the radicals Z1 and Z2 is a hydrogen atom and the other radical is a β-hydroxyethylthio group and Y is a hydrogen or halogen atom, with hydrogen peroxide-containing tungstic acid or a salt of this compound at a pH of 3 to 8 and a temperature of 30 to 1000C oxidized. 10. The method according to claim 9, characterized in that one Compound of the general formula Ia uses, in which Y is a hydrogen, chlorine or bromine atom means.