DE2352059A1 - 1-AMINOBENZENE-5-BETA-SULFATOETHYLSULFONE-2,4-DISULFONIC ACID, ITS 5-VINYLSULPHONE COMPOUND AND THEIR ALKALINE SALT, AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

FARBWERKE HOECHST AG formerly Master Lucius & Brüning

File number: HOE 73 / F 316

Date: October 16, 1973 Dr Mü / Ha

l-aminobenzene-5-ß-sulfatoätfrylsulfon-2,4-disulfonic acid, their 5-vinyl sulfone compound and its alkali salt, and methods for their manufacture

The present invention relates to novel compounds of the general Formula 1)

Y - O ₂ S- ^ Λ -SO ₃ X (1)

¹ SO ₃ X

in which Y is one of the groupings of the formulas

XO ₃ S- 0 - CH ₂ - CH ₂ - (2) or

CH ₂ = CH - (3)

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and X. is a hydrogen, alkali or alkaline earth metal atom, and a process for their preparation in good yields by adding 1-aminobenzene-3-ß-sulfatoethylsulfone or 1- aminobenzene-3-ß-hydroxyethylsulfone in either (a) anhydrous sulfuric acid (monohydrate) dissolved between about -15 ° C and + 4O ⁰ C, preferably between about 10 C and 20 C or suspended, then sulfur trioxide dissolved in anhydrous sulfuric acid, preferably a sulfuric acid / sulfur trioxide mixture of a mixture ratio of 30 ": 70 adding 10 in the aforementioned temperature range, or (b) immediately / sulfur trioxide mixture enters into a sulfuric acid containing up to 30 weight percent sulfur trioxide, and then cooled to about 100 ⁰ C to about 150 ° C, preferably 125 C-135: 90 ° C, heated, and optionally the l-aminobenzene-5-ßsulfatoäthylsulfon-2,4-disulfonic acid or its salt formed in an aqueous solution at pH 2.5 to 7 to about 30 ° C to about 6O C exp The sulfuric acid split off is neutralized by adding an acid-binding agent and the 1-aminobenzene-5-vinylsulfone-2,4-disulfonic acid formed is isolated in the form of the alkali metal or alkaline earth metal salt.

The sulfonation on the benzene nucleus, which takes place in the first stage, results in the intermediate monosulfonation product 1-aminobenzene-5-ß-sulfatoethylsulfone-2-sulfonic acid.

To isolate the after disulfonation in sulfuric acid / Sulfur trioxide mixture obtained l-aminobenzene-5-ß-sulfatoethylsulfonic-2,4-disulfonic acid in the form of the free acid, the sulfonation mixture is converted into a mixture of ice and potassium chloride stirred in, the said disulfonic acid precipitating in the form of the free acid and can be filtered off as such.

For the isolation of l-aminobenzene-5-ß-sulfatoethylsulfonic-2,4-disulfonic acid the sulfonation mixture is in salt form on ice

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poured and the excess sulfuric acid with an alkali or Alkaline earth hydroxide or carbonate neutralized. After filtering off the precipitates of alkali or alkaline earth metal sulfate can be said disulfonic acid in the form of alkali metal, for example of the sodium or potassium salt, obtained by spray drying v / er dent.

The yield of l-aminobenzene-5-ß-sulfatoethylsulfonic-2,4-disulfonic acid, converted to free acid, is 70 to 90 % of theory,

For the isolation of l-aminobenzene-5-vinylsulphone-2,4-disulphonic acid in salt form, the procedure can be that the l-aminobenzene-5-ßsulfatoethylsulfon-2,4-disulfonic acid is removed from the previous process according to the heating split off sulfuric acid by adding an acid-binding agent, for example one Alkali or alkaline earth hydroxides or carbonates, preferably sodium hydroxide or sodium carbonate, neutralized and the alkali salt, for example the sodium salt, by spray drying the neutral solution separates. The alkali salts of the compound mentioned can also be isolated by adding 1-aminobenzene-5-vinylsulfonic-2,4-disulfonic acid deposited from the resulting solution with alkali halides.

The duration of the disulfonation, i.e. the treatment of the starting products in the sulfuric acid / sulfur trioxide mixture, can be between 1 hour and about 20 hours «

l-aminobenzene-5-ß-sulfatoethylsulfone-2,4-disulfonic acid, 1-aminobenzene-5-vinylsulfone-2,4-disulfonic acid and their alkali salts provide new, valuable diazo components !! for making more valuable Azo dyes.

In the manufacture of azo dyes from the inventive Amines as a diazo component and those customary for azo dyes Azo components are obtained fiber-reactive azo dyes that

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have valuable coloring properties in various respects. Such azo dyes are produced in a known manner by diazotization and coupling.

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example 1

281 g (1 mole) of l-aminobenzene-3-ß-sulfatoethyl sulfone are under Cooling and stirring and with the exclusion of atmospheric moisture in 843 g of sulfuric acid monohydrate introduced proportionally at 15 ° C to 20 ° C. After stirring for 60 minutes, 350 g of oleum are nit a SO «content of 65 percent by weight was slowly added dropwise, the temperature also being kept at 15 ° C. to 20 ° C. by external cooling will. Then heated »for 12 hours to 130 C. The cooled reaction geraisch is then in a mixture of ice and Potassium chloride stirred in, the l-aainobenzene-5-ß-sulfatoethylsulfonic-2,4-disulfonic acid the formula

fails. It is filtered off and dried. The yield is 75% of theory.

The analysis shows a ratio of carbon to sulfur of 2 to 1 according to the formula CgH ₁ -NO ₁₉ S ₄ . The two protons located in the benzene nucleus can be detected in nuclear magnetic resonance spectroscopy (NMR spectroscopy).

Example 2

281 g (1 mol) of l-aminobenzene-3-ß-sulfatoäthyleulfon are proportionately with cooling and stirring and with exclusion of humidity in 1193 g oleum with an SO ₃ content of 19 percent by weight. wise entered at 15 ° C to 20 ⁰ C. After stirring for 60 minutes, the mixture is heated to 130 ° C. for 12 hours. The reaction mixture obtained

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is then stirred into a mixture of ice and potassium chloride, the l-aminobenzene-S-ß-sulfatoethylsulfone - ^ .- l-disulfonic acid formula

HO ₃ S -f ^ (-)

* * Λ SO ₃ -CH-CH ₂ -OSO ^

aueffcllt. It is filtered off and dried. The yield in 1- aeinobenzene-5-ß-eulfatoethylsulfon-2,4-disulfonic acid is 70 % of theory.

Example 3

201 g (1 mol) l-aminobenzene-3-ß-hydroxyethylsulfone are added with cooling and stirring and under exclusion of atmospheric moisture g of sulfuric acid monohydrate in 723 anteilsweise.bei 15 ° C to 20 ⁰ C. The mixture is stirred for 3 hours and then 473 g of oleum with an SO ₃ content τοη 65 percent by weight are slowly added, the temperature being kept at 15 ° C. to 20 ° C. by external cooling. It is then heated to 130 ° C. for 12 hours. The cooled reaction mixture is then stirred into a mixture of ice and potassium chloride, the l-aminobenzene-S-ß-eulfatoethylsulfon-A ^ -disulfonic acid of Foxnel

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WSfrwr

fails. It is filtered off and dried. The yield is 75% of the theory ·.

Example "4

441 g (1 mol) of 1-aminobenzene-5-ß-eulfethoethylsulfonic-2,4-disulfonic acid are introduced into 1500 al of water at pH 6 to 7. The pH is then adjusted to 6 to 7 with sodium carbonate and the mixture is warmed to 50 ° C to 60 ° C. Further addition of sodium carbonate becomes the sulfuric acid which is split off is neutralized. After 10 minutes the reaction has ended. The disodium salt of 1-aminobenzene-5-vinylsulfone-2,4-di-sulfonic acid can be obtained by spray drying the neutral solution.

The analysis of the new compound shows a ratio of carbon to sulfur of 8 to 3 according to the empirical formula CgH ₇ NO-S ₃ Na ₂ . The signals of the vinyl protons in the NMR spectrum are in the range from «Γ = * 6.0 to 6.4.

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Claims (3)

HOE 73 / F 316 - 8 - claims 1. Compounds of the general formula NH
2 Y - O ₂ S- / ~ Λ_ SO ₃ X (1) in which Y is one of the groupings of the formulas XO ₃ S - O - CH ₂ - CH ₂ - (2) or CH ₂ = CH - (3) and X is a hydrogen, alkali or alkaline earth metal atom represents. 2, process for the preparation of compounds of general formula ¥ - O ₄₅ S - / ζ J -SO ₃ X '(1) SO ₃ X in which Y is one of the groupings of the formulas 509817/120 XO ₃ S- 0 - CH ₂ - CH ₂ - (2) or CH ₀ -CH- (3) and X represents a hydrogen, alkali or alkaline earth metal atom, characterized in that 1-arenobenzene-3-ß-sulfatoethylsulfone or l-aminobenzene-3-ß «hydroxyäthylsul" hair dryer either (a) in anhydrous sulfuric acid (monohydrate) between about -15 C and about +40 C dissolves or suspends, then sulfur trioxide, dissolved in anhydrous sulfuric acid, im above-mentioned temperature range admits, or (b) immediately in a sulfuric acid / sulfur trioxide mixture with a content introduces up to 30 percent by weight of sulfur trioxide, and then heated to about 100 C to about 150 ° C, and optionally the l-aminobenzene-5-β-sulfatoethylsulfonic-2,4-disulfonic acid formed in this way or the salt thereof is heated in aqueous solution at ρΗ2.5 to 7 to about 30 ° C. to about 60 ° C., which is then split off Sulfuric acid neutralized by adding an acid binding agent and the l ~ aminobenzene ~ 5 ~ vinylsulphone-2,4-disulphonic acid formed isolated in the form of the alkali or alkaline earth salt. 3. The method according to claim 2, characterized in that the 1-aminobenzene-3-ß-sulfatoethylsulfone or 1-arainobenzene-3-ß-hydroxyethylsulfone Dissolves or suspends in anhydrous fungal acid (monohydrate) at temperatures between 10 C and 20 C and then a sulfur isic acid / sulfur It riO3: id mixture Mixing ratio of 30:70 to 90:10 is added and then heated to temperatures between 125 ° C and 135 ° C. 509817/1204