DE3935494A1 - New o-hydroxy-ethyl-thio-sulphinyl-, or -sulphonyl-aniline cpds. - are intermediates for azo and tri:phen-di:oxazine dyestuffs - Google Patents

Abstract

New o-(hydroxyethylthio)-, o-(hydroxyethylsulphinyl), or o-(hydroxyethylsulphonyl)- N-(hydroxyethyl)formanilides or N-(hydroxyethyl)- acetanilides (I) have formula (1). E = H or Me; X = S, SO, or SO2; Y = N (sic, H), NHCOR, or, if X = SO2, also NO2; R = H, 1-6C alkyl, cycloalkyl, 2-6C alkenyl, 1-6C alkyl-aryl, Ph, naphthyl, PhO, 1-4C alkoxy, amino, 1-6C alkylamino, 2-6C alkenylamino, cycloalkylamino, 1-6C alkyl-arylamino, phenylamino, NHA, (CH2)0-6CONHA, or C6H4, where A = gp. of formula (2). USE - (I) are intermediates for azo and triphen-dioxazine dyestuffs (DE3512340, EP153599,279351).

Description

The present invention relates to substituted Hydroxyethylanilines of the formula (I)

wherein
E = H, CH₃
X = S, SO, SO₂
Y = N, NHCOR or, if X = SO₂, also NO₂
R = H, C₁-C₆-alkyl, cycloalkyl, C₂-C₆-alkenyl, C₁-C₆-alkylaryl, phenyl, naphthyl, phenoxy, C₁-C₄-alkoxy, amino, C₁-C₆-alkylamino, C₂-C₆-alkenylamino, Cycloalkylamino, C₁-C₆ alkylarylamino, phenylamino;

wherein

and a process for their preparation, thereby ge indicates that benzothiazoles of the formula (II)

wherein
Y ′ = H, NHCOR ′, NHCONHA ′, NHCO (CH₂) _0-6 CONHA ′,

With
R ′ = H, C₁-C₆-alkyl, cycloalkyl, C₂-C₆-alkenyl, C₁-C₆-alkylaryl, phenyl, naphthyl, phenoxy, C₁-C₄-alkoxy, amino, C₁-C₆-alkylamino, C₂-C₆-alkenylamino , Cyclo alkylamino, C₁-C₆ alkylarylamino, phenylamino;

in an aqueous medium with ethylene oxide to give compounds of Formula (III)

implements what
Y ′ ′ = H, NHCOR ′, NHCONHA ′ ′, NHCO (CH₂) _0-6 CONHA ′ ′,

With

and then, if necessary without intermediate insulation, in a neutral to alkaline range with Oxyda tion agents, optionally in the presence of oxides tion catalysts (e.g. Na tungsten) to the sulfones or sulfoxides of the formula (IV)

wherein
X ′ = SO, SO₂

oxidized and optionally the compounds (IV) with X ′ = SO₂ and Y ′ ′ ′ = H to give compounds of the formula (1, X = SO₂, Y = NO₂) nitrided. These as well as connections (IV) with X '= SO₂ are then optionally Compounds of the formula (V),

wherein
Z = H, NO₂ or NH₂, acid hydrolyzed.

The compound (V) with Z = NH₂ is also usual Reduction of the compound (I) (Y = NO₂, X = SO₂) and subsequent acidic hydrolysis available (see also EP 153 599).

Another method variant can also be used, after which compounds of the formula (III) with E = H initially under gentle neutral to alkaline Conditions for compounds of formula (IIIa), also The invention relates to

wherein  

hydrolyzed and subsequently to compounds of the formula (IVa), which are also the subject of the invention,

wherein

oxidized. Acylamino compounds (IVa) are then added acid hydrolyzed to the amino compound (V, Z = NH₂).  

The alkyl, cycloalkyl, Alkenyl, alkylaryl, phenyl, naphthyl, Alkoxy and phenoxy radicals can be common substituents exhibit.

In addition to the unsubstituted, for example, alkyl radicals come by OH, Cl, Br, CN, COOH, COOC₁-C₄- Alkyl, OC₁-C₄ alkyl substituted in question.

Cyclohexyl comes in particular as cycloalkyl radicals Question.

Suitable alkenyl radicals are in addition to the unsubstituted for example -CH = CH-COOH.

Suitable phenyl residues, naphthyl residues and phenoxy residues In addition to the unsubstituted, for example, C₁-C₄-alkyl, halogen, COOH, NO₂, SO₃H, COOC₁-C₄-alkyl, C₁-C₄ alkoxy substituted.

Suitable alkylaryl radicals are in particular optionally by the substituents specified for the phenyl radicals substituted benzyl radicals.

The compounds (V) with Z = NH₂ or NO₂ are important Intermediates for the production of dyes (see EP 01 53 599, DE-A 350 22 991).

Preferred compounds (I) are those with Y = H, NHCOCH₃, NHCOC₆H₅ and X = S or SO₂.  

The starting compounds (II), such as. B. benzothiazole, 2- Methylbenzothiazole, 6-acetylaminobenzothiazole, etc. mostly known from the literature. Derivatives with Y ′ = NH-CO-R, NH-CO-NH-A ′,

are by acylation methods commonly used Implementation of 6-aminobenzothiazole or 6-amino-2-methyl benzthiazoles with aliphatic or aromatic car acid chlorides, carboxylic acid anhydrides, carboxylic acid esters, Dicarboxylic acid chlorides, dicarboxylic acid anhydrides or dicarboxylic acid esters, with phosgene, chloroformic acid alkyl or phenyl esters, carbonic acid esters or with aliphatic or aromatic isocyanate derivatives available.

The implementation of these compounds (II) with excess Ethylene oxide is preferred in water at temperatures between 20-120 ° C, preferably between 40-80 ° C, and carried out in an autoclave under a pressure of 0.2-2.0 bar. The ethylene oxide is metered in such a way that sets a pH of 8-12, preferably 9.0-10.5.  

The intermediate stages are likely

run through.

The benzothiazoles (II) are thus surprisingly Directly aqueous by simply adding ethylene oxide Solutions or suspensions of 2- (2-hydroxyethylmercapto) - N-acyl-N- (2-hydroxyethyl) aniline derivatives of Obtained formula (III). The ethoxylation reaction can also in a reaction medium consisting of water and a water-miscible organic solvent, such as. B. Tetrahydrofuran, dioxane, glycol etc., composed, be performed.

One selects pH values during the ethoxylation reaction above pH 11 or temperatures in the range of 80-100 ° C, so in the case of E = H hydrolysis are the formyl amino grouping and subsequent ethoxylation to Ver bonds of formula (VI) possible,

wherein

R 'has the meaning given above.

An oxidation of (VI) to the corresponding sulfones is feasible.

The oxidation of the thioethers (III) obtained can be carried out without Intermediate insulation of the same and after removal of excess ethylene oxide in aqueous medium at pH Values from 5 to 12, preferably from 7 to 10, take place. In general, at temperatures from 0 to 110 ° C, preferably at 20 to 90 ° C, worked. Next As with ethoxylation, water can also organic water-miscible solvents used proportionally will.  

Suitable oxidizing agents are besides the preferred one Hydrogen peroxide also other per compounds, such as. B. Perborates, persulfates, percarbonates and persulfonic acids, as well as oxygen, permangana or halogens.

If necessary, suitable catalysts can be added be, for example, tungstates, vanadates, molybdates or iron (III) salts. The oxidizing agents are in the generally in amounts of about 1 to 4 moles per mole of thioether used (see e.g. EP 137 417).

Under gentle reaction conditions, i.e. H. with neutral pH, temperatures from 20 to 40 ° C and a simple one Excess oxidizing agents are preferred Oxidation to the corresponding sulfoxides Formula (I) (X = SO). By increasing the temperature to 40 to 90 ° C and further addition of oxidizing agent can directly the sulfones of formula (I) (X = SO₂) are implemented.

The new compounds of formula (I) can both by sucking off or salting out / separating the oily Phase as well as by distillation or extractive up working methods are isolated. But so can directly as solutions or mixtures to compounds of formula (V) under acidic reaction conditions be hydrolyzed. To do this, add by adding Mineral acids such as hydrochloric acid or sulfuric acid pH below 1 and warmed to 80 to 100 ° C.  

The compounds (I) are used, for example for the production of interesting azo dyes, such as Example 17 from DOS 35 12 340

or Example 5 from EP 279 351

and the production of triphendioxazine dyes, as example 1 from EP 153 599

Example 1

An emulsion of 135 g of benzothiazole and 1 g of a conventional Emulsifier in 500 ml of water is heated to 60 ° C, and nitrogen is bubbled through for 1 hour. You dose over a period of approx. 12 hours then a total of about 300 g of ethylene oxide so that a pH is maintained between 9.5 and 10.5. The The reaction is monitored by thin layer chromatography as soon as less than 1% of the initial concentration of Benzothiazole are detectable, the ethylene oxide intake stopped and the reaction solution was passed through a vigorous stream of nitrogen for a further 2 hours heated to 80 ° C. After doing the rest If ethylene oxide has been removed, the about 800 ml of Re are cooled action solution to room temperature. The reaction solution contains glycol and small amounts of polyglycols relatively uniform hydroxyethyl aniline derivative of formula

and can be implemented directly.

To characterize the product, an 80 ml sample of the solution at pH 7 is worked up extractively and by distillation. The result is a viscous, colorless oil to which the above structure can be assigned on the basis of the 1 H-NMR and IR data.
IR (Nujol trituration): 1662 cm ^-1 (CO-Schw.)
1 H-NMR (d₆-DMSO): δ = 3.05 (2H, m); 3.48 (2H, m); 3.60 (2H, m); 3.65 (2H, m); 4.68 (t, OH); 4.94 (t; OH); 7.15-7.50 (m, 4H); 8.00 (s, CHO).
Mass spectrum: m / e = 241 (M⁺, 45%); 213 (M⁺-CO, 45%); 182 (65%); 164 (55%); 136 (100%).

Example 2

720 ml of the reaction solution from Example 1 are brought to pH 8 adjusted, mixed with 1 g of sodium tungstate and on Heated to 70 ° C. Now slowly 170 ml of a 35% added aqueous hydrogen peroxide solution so that due to the exothermic reaction a temperature of 80 ° C is not exceeded. The progress of the oxida tion reaction is controlled by DC. The pH should not drop below 5 (possibly soda solution addition). First of all, oxidation takes place very quickly Sulfoxide of the formula

which is then continuously oxidized to the sulfone. After the addition, the mixture is stirred at 80 ° C. for a further 3 hours. Is no longer an output connection and only a trace Detectable sulfoxide, the colorless reaction solution cooled, and the excess hydrogen peroxide z. B. destroyed with sodium sulfite.  

The aqueous reaction solution is continuously with Extracted ethyl acetate or isobutanol, and the organic phase obtained is concentrated. It results in a relatively uniform oily substance that the structure based on spectroscopic data

can be assigned.
1 H-NMR (d₆-DMSO): δ = 3.40-3.55 (m, 4H); 3.68-3.84 (m, 4H); 5.0 (broad s, 20H); 7.90 - 8.0 (m, 2H); 8.04-8.15 (m, 2H + CHO).

Example 3

800 ml of reaction solution from Example 1 are mixed with 200 ml a 70% sulfuric acid and for one Heated to 90-95 ° C for one hour. Then it is cooled and neutralized with concentrated sodium hydroxide solution with external cooling and then adjusted to pH 12.5. Here a colorless oil separates.  

(The reaction solution from Example 1 can also be alkaline be hydrolyzed by adding sodium hydroxide solution pH 12.5-13.0 and heated to 80-85 ° C for 30 minutes).

The oil is separated and as the hydroxyethylaniline formula

characterized.
1 H-NMR (d₆-DMSO): δ = 2.77 (t, 2H); 3.18 (m. 2H); 3.42 (m, 2H); 3.60 (m, 2H); 4.81 (t, OH); 4.83 (t, OH); 5.46 (t, NH); 6.50-6.63 (m, 2H); 7.15 (m. 1H); 7.30 (m, 1H).

Example 4

Increased during the ethoxylation reaction in Example 1 by adding dilute sodium hydroxide solution pH to values above pH 11, e.g. B. to 12.0 and maintains this value until the end of the reaction, so the result one mixed with small amounts of glycol aqueous solution of a trisethoxylated product of formula

The compound proves to be a viscous, colorless oil and is obtained by extracting the reaction solution with ethyl acetate.
1 H-NMR (d₆-DMSO): δ = 2.96 (t, 2H); 3.10 (m, 4H); 3.40 (m, 4H); 3.58 (m. 2H); 4.25 (t, 2x OH) 4.88 (t, OH); 7.08 (m, 2H); 7.23 (m. 2H);
Mass spectrum: m / e = 257 (M⁺, 10%); 226 (M⁺-CH₂OH, 100%).

The same oily product can be obtained by using 2-amino thiophenol ethoxylated in heat at pH 8-10 and the Reaction solution extracted accordingly.

Example 5

The emulsion of 149 g of 2-methylbenzothiazole, 1 g of one usual emulsifier and 500 ml of water in one Pressure vessel is heated to 60 ° C and it is left for 1 hour Nitrogen passed through. The autoclave is then closed and heated to 80 ° C. There will be approx. 250 g Ethylene oxide pressed in over a period of 3-4 hours, that an internal pressure of 1.5 bar and a pH is maintained between 9.5 and 10.5. Is the total added to ethylene oxide, is as long as Heated to 80 ° C until the pressure dropped to 0.1 / -0.2 bar is. It is relaxed and passed through at 80 ° C of a strong nitrogen atom the remaining ethylene oxide removed. The approx. 750 ml reaction solution are on Cooled to 20 ° C. 50 ml of this colorless solution on Rotary steamer concentrated and the remaining Oil purified by column chromatography, d. H. Glycol and Polyglycols separated. A colorless viscous is isolated Oil that spectroscopically as a compound of the formula  

is identified
1 H-NMR (d₆-DMSO): δ = 1.65 (s, COCH₃); 3.04 (dt, 1H); 3.12 (t, 2H); 3.50 (dt, 2H); 3.63 (t, 2H); 4.08 (dt, 1H); 4.60 (broad, 2 OH); 7.17-7.50 (m, 4H).
IR (Nujol): 1640 cm ^-1 (CO vibration)

Example 6

The remaining 700 ml reaction solution from Example 5 are adjusted to pH 8 with 1 g sodium tungstate added and in analogy to Example 2 with 170 ml of one 35% aqueous hydrogen peroxide solution oxidized. First there is oxidation to the sulfoxide of the formula

then continuing the reaction into the corresponding one Sulfone of the formula

is transferred. The oxidation reactions become thin tracked by layer chromatography.

The reaction solution obtained is either distilled concentrated or continuously with acetic acid extracted ethyl ester and the organic phase obtained concentrated. The sulfone of the above formula is obtained.

Acid hydrolysis of the sulfone gives analogy to Example 3 uniform 2- (2-hydroxyethylamino) phenyl- (2- hydroxyethyl) sulfone (Example 7).

Example 7

128 g of the sulfide from Example 3 and 0.5 g of a ge customary emulsifier are 400 ml of water at 35 ° C. warmed and after adding 2 g of sodium tungstate dropwise with 80 ml of a 35% aqueous hydrogen peroxide solution added. The reaction is slightly exothermic. The oxidizing agent is added in such a way that a temperature of 40 ° C is not exceeded. The pH should be above pH 6. After encore is stirred for 2 hours at 60 ° C and 3 hours at 80 ° C. The colorless reaction solution is cooled as soon as the oxidation is complete. (If necessary, again add hydrogen peroxide solution (approx. 30-40 ml) will). From the cooled reaction solution small amounts differ after several hours yellowish minor component by filtration be separated. The solution is with ethyl acetate, a  alcohol immiscible with water or a mixture of both extracted. Remove the solvent a dark viscous oil results on the rotary evaporator, that slowly crystallizes. The connection comes on spectroscopic data the following structure:

1 H-NMR (d₆-DMSO): δ = 3.24 (m, 2H); 3.37 (t, 2H); 3.64 (m, 4H); 4.86 (broad s, 20H); 6.33 (t, nH); 6.75 (m. 1H); 6.88 (m, 1H); 7.45 (m 1, H); 7.55 (m, 1H).

Example 8

The suspension of 192 g of 6- (acetylamino) benzothiazole, 1 g of a common emulsifier and 500 ml of water is heated to 60 ° C in an autoclave. First of all nitrogen passed through for 1 hour, then the temperature increased to 80 ° C and the autoclave closed. It about 250 g of ethylene oxide over a period of 3-4 Hours so pressed that a pressure of 1.5 bar and a pH of 9.0-10.5 is maintained. Is the Amount of ethylene oxide is added as long as the reaction continued at 80 ° C until the pressure reached 0.1-0.2 bar has dropped. It comes with an absorption system  Sodium bisulfite solution relaxed and at 80 ° C Passing a strong stream of nitrogen through the rest Removed ethylene oxide. If necessary, too Sodium sulfite to remove the remaining ethylene oxide be added. The colorless reaction solution (approx. 750 ml) is cooled to 20 ° C. A 50 ml sample of this Solution is concentrated on a rotary evaporator and the remaining oil from the adhering column chromatography Glycol free. The result is an oily Liquid, which based on spectroscopic data formula

can be assigned.
1 H-NMR (d₆-DMSO): δ = 2.10 (s, 3H); 2.95-3.15 (m, 4H); 3.62 (m. 2H); 4.04 (m, 2H); 5.05-5.15 (broad, 2 OH); 7.25 (d. 1H); 7.48 (dd, 1H); 7.70 (d, 1H); 7.98 (s, CHO); 10.33 (s, NH).

Example 9

700 ml of the reaction solution from Example 8 are at pH 8 heated to 70 ° C after the addition of 1 g of sodium tungstate. 180 ml of 35% aqueous water are slowly added peroxide solution added. The temperature should be there do not rise above 85 ° C, the pH does not fall below 6 fall. The progress of the oxidation reaction becomes thin tracked by layer chromatography. It happens first the oxidation to the sulfoxide of the formula is very rapid

which is then continuously oxidized to the sulfone. After the addition of the oxidizing agent, another 3 hours stirred at 80-85 ° C. Is not an outgoing connection more and only one hour of sulfoxide detectable, the colorless reaction solution is cooled and that excess hydrogen peroxide destroyed.

A 50 ml sample of the Reak tion solution extracted at pH 7 or worked up by distillation. A colorless crystalline ver results bond to which the structure below can be assigned can  

1 H-NMR (d₆-DMSO): δ = 2.08 (s, 3H); 3.25 (m. 2H); 3.40 (t, 2H); 3.60-3.75 (m, 4H); 4.85 (t, OH); 4.98 (t, OH); 7.35 (d. 1H); 8.0 (dd, 1H), 8.13 (s, CHO); 8.25 (d, 1H); 10.65 (s, NH).

The reaction solution can without isolation of the Sulfones can be directly implemented further.

Example 10

Gentle alkaline hydrolysis (pH 12.5 / 60-80 ° C) of the Sulfones from Example 9 provide the partially saponified (2-hydroxyethyl) aniline derivative of the formula

that melts at 134 ° C and is characterized by the following data.
1 H-NMR (d₆-DMSO): δ = 2.0 (s, 3H); 3.20 (m, 2H); 3.38 (t, 2H); 3.60-3.70 (m, 4H); 4.87 (t, OH); 4.92 (t, OH); 6.10 (t, NH); 6.85 (d. 1H); 7.68 (dd, 1H); 7.87 (d. 1H); 9.88 (s, NH).

This connection is also obtained by using the Sul fid from Example 8 under alkaline conditions (pH 12 / 60-80 ° C) gently saponified and subsequently without Intermediate insulation with hydrogen peroxide analogous to Example 7 oxidized.

Example 11

The colorless reaction solution from Example 9 is added Hydrochloric acid adjusted to a pH below 0.5 and heated under reflux for 3 hours. After hydrolysis, the mixture is cooled and the reak neutralized with dilute sodium hydroxide solution. The resulting [5-amino-2- (2-hydroxyethylamino) - phenyl] - (2-hydroxyethyl) sulfone of the formula

can either be isolated (mp. 130 ° C) or, as also described in EP 153 599, directly in solution or suspension can be converted to the dye.

By acid hydrolysis of the partially saponified sulfone Derivative from Example 10 is this important dye intermediate product also available.

Example 12

Example 8 is used instead of 6- (acetylamino) - benzothiazole now an equimolar amount of 6- (Acetylamino) -2-methylbenzothiazole and sets with analog Ethylene oxide, so you get in solution or in substance a bisacetyl derivative of the formula

The substance proves to be a tough, high-boiling oil.
1 H-NMR (d₆-DMSO): δ = 1.70 (s, 3H); 2.12 (s, 3H); 2.90-3.20 (m, 4H); 3.64 (m. 2H); 4.05 (m. 2H); 5.10 (broad m, 20H); 7.23 (d. 1H); 7.42 (dd, 1H); 7.68 (d. 1H); 10.17 (s, NH).

Example 13

In analogy to Example 9, the bisacetyl derivative is made Example 12 with hydrogen peroxide solution to the sulfone formula

oxidized.

Example 14

68.8 g of the bisacetylaminosulfone from Example 13 are in 250 ml water and 150 ml conc. Stirred hydrochloric acid and heated for about 3-4 hours under reflux conditions. After complete hydrolysis is abge cools and by adding dilute potassium hydroxide solution to pH 8 neutralized. The resulting [5-amino-2- (2-hy droxyethylamino) phenyl] (2-hydroxyethyl) sulfone can then directly, e.g. B. with chloranil, are further implemented (see Example 11). But it can also be used after salting out Potassium chloride can be isolated, giving 51 g of product receives.  

Example 15

The suspension of 254 g of 6- (benzoylamino) benzothiazole, 1 g of a common emulsifier, 500 ml of water and 200 ml glycol is in an autoclave at 80 ° C with approx. 250 g of ethylene oxide in analogy to Example 8 implemented. The colorless reaction solution obtained is cooled and corrected to pH 7.

The solution of the N-formyl (2-hydroxyethyl) aniline derivative of the formula

can be directly implemented further.
1 H-NMR (d₆-DMSO): δ = 2.78 (t, 2H); 3.20 (m, 2H); 3.50 (m. 2H); 3.61 (t, 2H); 4.8 (broad s, 2 OH); 6.58 (d. 1H); 7.45-7.65 (m, 4H); 7.75 (d. 1H); 7.9-7.95 (m, 2H); 8.01 (s, CHO); 9.95 (broad NH).

Example 16

The neutral reaction solution from Example 15 is on Rotary evaporator to a residual volume of 400 ml  concentrated. At 25 ° C is made with dilute sodium hydroxide solution to pH 3 and stir for 24 hours at room temperature. The crystalline product which has separated out is separated off, washed with water, dried and as one Compound of formula

characterized with the melting point 150 ° C.
1 H-NMR (d₆-DMSO): δ = 2.80 (t, 2H); 3.18 (m. 2H); 3.51 (t, 2H); 3.63 (t, 2H); 4.84 (broad s, 2 OH); 5.34 (t, NH); 6.63 (d. 1H); 7.45-7.60 (m, 4H); 7.78 (d. 1H); 7.94 (m, 2H); 9.97 (broad NH).

Example 17

In analogy to Example 9, the reaction solution is made Example 15 with excess hydrogen peroxide for Sulfone of the formula

oxidized. After removing the remaining peroxide analogously to Example 14, the benzoylamino or the formylamino Grouping hydrolyzed with hydrochloric acid. After new tralisation of the reaction mixture, the [5- Amino-2- (2-hydroxyethylamino) phenyl] (2-hydroxyethyl) - sulfone (see also Example 11).

Example 18

The neutral reaction solution of the sulfone from Example 17 after oxidation is carried out in analogy to Example 16 concentrated and partially saponified using alkali. A crystalline product separates after 24 hours from mp. 148-149 ° C, which the formula

comes to.
1 H-NMR (d₆-DMSO): δ = 3.23 (m, 2H); 3.40 (t, 2H); 3.58-3.75 (m, 4H); 4.90 (broad s, 2 OH); 6.20 (t, NH); 6.92 (d, 1H); 7.44-7.60 (m, 3H); 7.90 (dd, 1H); 7.98 (d. 2H); 8.10 (d, 1H); 10.22 (s, NH).

The same product can be obtained if you use the sulfide from example 16 with hydrogen peroxide solution and sodium tungstate,  similar to that listed in Example 9, oxidized at pH 8.5 and approx. 80 ° C.

This partially saponified sulfone is now also available already mentioned several times (Examples 11, 14 and 17) [5- Amino-2- (2-hydroxyethylamino) phenyl] (2-hydroxyethyl) - sulfonable acid saponifiable.

Claims (5)

1. Hydroxyethylanilines of the formula wherein
E = H, CH₃
X = S, SO, SO₂
Y = N, NHCOR or, if X = SO₂, also NO₂
R = H, C₁-C₆-alkyl, cycloalkyl, C₂-C₆-alkenyl, C₁-C₆-alkylaryl, phenyl, naphthyl, phenoxy, C₁-C₄-alkoxy, amino, C₁-C₆-alkylamino, C₂-C₆-Al kenylamino , Cycloalkylamino, C₁-C₆alkyl arylamino, phenylamino; wherein 2. Hydroxyethylanilines of claim 1, wherein 3. A process for the preparation of the compounds from claim 1, characterized in that benzthiazoles of the formula wherein
Y ′ = H, NHCOR ′, NHCONHA ′, NHCO (CH₂) _0-6 CONHA ′, With
R ′ = H, C₁-C₆-alkyl, cycloalkyl, C₂-C₆-alkenyl, C₁-C₆-alkylaryl, phenyl, naphthyl, phenoxy, C₁- C₄-alkoxy, amino, C₁-C₆-alkylamino, C₂-C₆-alkenylamino , Cycloalkylamino, C₁-C₆-alkyl arylamino, phenylamino, in an aqueous medium with ethylene oxide to give compounds of the formula implements what
Y ′ ′ = H, NHCOR ′, NHCONHA ′ ′, NHCO (CH₂) _0-6 CONHA ′ ′, With and then, optionally without intermediate insulation, in a neutral to alkaline range with oxidizing agents, optionally in the presence of oxidation catalysts to give the sulfones or sulfoxides of the formula wherein
X ′ = SO, SO₂ oxidized and optionally then the compounds with X ′ = SO₂ and Y ′ ′ ′ = H nitrated to compounds with Y ′ ′ ′ = NO₂ and X ′ = SO₂. 4. Hydroxyethylanilines of the formulas wherein and where R 'has the meaning given in claim 2. 5. A process for the preparation of the sulfones of claim 4, characterized in that compounds of the formula with E = H first hydrolyzed to the sulfides of claim 4, and these are subsequently oxidized.