JPH0617358B2 - Novel 3-sulfopropyl-ammonium betaine having 2-position substitution and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 3-sulfopropyl having a novel sulfinato group (sulfobetaine sulfinato) or sulfonato group (sulfobetaine sulfonato) at position 2 and optionally a methyl group. -Ammonium betaine as well as processes for the preparation of these compounds.

Sulfobetaine sulfinato is a new substance type. The production of other betaine sulfinatos is likewise unknown.

On the contrary, the preparation of sulfobetaine sulphonates of other structure has already been described. Compounds with remote sulphonic acid groups are then chemically converted in two ways between the hydroxyethylamino compound and 2 moles of propane sultone (J. Amer. Oil Chemists Soc. 55 (1978) p. 741) or triallyl-. Or tetraaryl ammonium salt 5
To react with sulfite and an oxidizing agent such as oxygen in the air at the same time in the PH value range of 8 to 8 (East German General Patent No. 20
No. 0739) can be made.

The disadvantages of these known methods are that in the first case they are very carcinogenic propane sultone and must be handled with great precautions, in the second case allyl ammonium with more than two allyl substitutions. There is a need for the use of compounds. Another drawback common to these methods is forced SO ₃ ^- is that must be different hydrocarbon residues introduced with group.

As a reaction product of an unsaturated aliphatic compound and bisulfite, various structures have been described so far. In the case of simple olefins, radical difunctionalization is carried out by reacting bisulfite under the influence of organic peroxides or air in the PH value range 4-9. With a long reaction time of 1 to several hours, a product having a sulfonic acid group at the terminal and a sulfinato group adjacent thereto at a high temperature was obtained as a probable but unproven structure (West German Patent 11).
No. 17565).

The isosulfonate was obtained from allyl ammonium salt under very similar conditions after a very long reaction time (J. Am.
er. Oil Chemists Soc. 53 (1976) p. 60).

U.S. Patent No. 4267123 No. (Example No. 1 and No. 5) propane sulfonate upon bisulfite adduct to Ariruhetero compounds induced oxygen _{(-CH 2 CH 2 CH 2 SO} 3 -) and Ropirusu Rufuinato _{(-CH 2 CH 2 CH 2 -O} -SO 2 -) and is obtained, where propylsulfanyl Huy isocyanatomethyl is known to be the major product of the reaction. In the reaction mixture containing methanol, the ratio of propylsulfinato: propanesulphonate is
80: 15%, even only 93: 3% in the aqueous reaction solution.

On the other hand, according to East German Patent No. 154443, when the reaction induced by oxygen is catalyzed by a transition metal ion, bisulfite is quantitatively added to allyl ammonium salt to give uniform 3-sulfopropyl- It produces ammonium betaine (sulfobetaine).

The present invention creates a novel 3-sulfopropyl-ammonium betaine with valuable properties, in which the introduction of a sulfonic acid group and an additional hydrophilic acid function into the allyl ammonium salt is functionalized. It is based on the task of enabling the introduction of forced additional hydrocarbon-containing residues to be omitted.

This problem is solved as described in the claims. 3-Sulfopropyl-having a new 2-position substitution
Ammonium betaine has formula I (In the formula, R is hydrogen or a methyl group, and X is SO ₂ M or SO ₃ M
M is hydrogen or an alkali gold cancer such as sodium or potassium or NH ₄ ^+, and R ¹ and R ² are independent of each other and are hydrogen, an alkyl residue having 1 to 3 carbon atoms, and hydroxyalkyl. Residue, ethylene oxide unit 10
Up to 3 oxyalkylene residues or closed ring-forming substituents, R ³ is hydrogen or 1 -carbon atom which may include -NH-CO- or -CO-NH- in the chain. To 22 alkyl residues).

The subject of the invention is also the process for the preparation of the compounds of the formula I.

The novel compounds have the general formula II (Wherein R, R ¹ , R ² and R ³ have the above meanings and Y ⁻ represents an anion, preferably chloride or bromide), and an allyl ammonium salt or methallyl ammonium salt thereof having a PH value of 2.0 to 4.0 is obtained. It is obtained by a chemical transformation in an aqueous solution in the presence of at least twice the molar amount of bisulfite in the range and peroxodisulfate, optionally in combination with other oxidizing agents.

In this case, a sulfobetaine sulfinato is formed by a chemical change in the presence of a catalytic amount of peroxodisulfate.

This difunctionalization with two oxygen-containing sulfur functions should be termed sulfosulfation. The reaction induced by this method is radically different from all the bisulfites traditionally carried out on allyl ammonium salts: bulk sulpho with substantially complete chemical transformation by difunctionalization to the double bond. Betaine sulfinato is obtained: this high degree of selectivity is surprising for reactions that proceed according to a radical mechanism. The reaction time required is significantly shorter than for other chemical changes at the allyl ammonium group. The reactions proceed in minutes or even seconds: they therefore belong to the fastest reactions known to occur in solution in organic chemistry. Initiation of sulfosulfination with peroxodisulfate simply oxidizes sulfite without other per-compounds, hydrogen peroxide or alkali perborate (see Example 12) causing similar reactions. It was surprising even if it was only a sulfate. According to the indication in West German Patent Application Publication No. 2231353 (page 4), the combination of peroxide and sulfite corresponds to an unusable open agent system.

Unlike the acquisition of 3-sulfopropyl-ammonium betaine (East German General Patent No. 154443), the components and initiator are added together at once without the components being added dropwise at the same time. This can also be done at the beginning of the residence time by mixing, so that the reaction can be carried out well and continuously. The process according to the invention has a very high space-time-yield, so that a relatively small reaction space can be used both in the discontinuous working mode and in the continuous reaction run.

The amount of initiator used is a short-chain arylammonium salt (Fig. 1).
Is slightly different from the surface-active long-chain substitute (Fig. 2). Under preferred conditions S ₂ O ₈ ^- it should be used 1 to 3 mole percent of the amount of initiator. When the amount of peroxodisulfate used is small, the chemical change may not proceed completely, while when the amount of the initiator is too large, the sulfosulfination reaction is accelerated and the reaction becomes uncontrollable (Example 9). Increased concentration of allylammonium salt in solution and increased onset temperature also have an accelerating effect; conversely dilution and cooling can moderate sulfosulfinatization (see Example 10).

It is also possible to start with less peroxodisulfate and then to act on air or oxygen to complete the reaction (see Example 9 / Figure 1, Example 27 / Figure 2).

As shown, when air is passed through, the emission of sulfur dioxide changes both the molar ratio of components and the PH value, and the simultaneous production of 3-sulfopropyl-ammonium betaine begins (see Example 11). In the PH range above 4, a considerable amount of this by-product is obtained. The strong influence of the PH value on the ratio of sulfobetaine sulphinato to sulfobetaine produced is shown in Examples 3 to 8 of Table 1 and Examples 19 to 21 of Table 2.

For the production of sulfobetaine sulfinus it is desirable to mix the solution of allyl ammonium salt or methallyl ammonium salt with about 35 to 40% solution of bisulfite solution in an aqueous solution with the highest possible concentration of the reaction components. Alternatively, work is performed by adding an initiator as a solid. In other cases, the solid alkali metal pyrosulfite M ₂ S ₂ O ₅ is dissolved in the substituted allyl ammonium salt solution to make it as concentrated as possible for work. Solubilizing agents in the form of lower alcohols can be used if necessary; they do not influence the direction of the reaction. Cooling of the reaction mixture is usually not necessary. Starting at room temperature, the maximum temperature rise is about 30-40
Because it is ℃. The initial PH value can be adjusted if necessary, eg by adding some inorganic acid when the industrial bisulfite solution contains some neutral sulfite (see Examples 9 and 10). The resulting sulfobetaine sulfinato can be isolated or further chemically modified without isolation as an intermediate product.

The reaction can likewise be carried out in the presence of a molar amount of peroxodisulfate, in which case sulfobetaine sulphonate is formed: The reaction induced by this working method is also fundamentally different from the bisulfite addition conventionally performed on allyl compounds in the course and in the final product. Bifunctionalization of the rose double bond upon completion of a chemical transformation with short reaction times of a few minutes gives 2.3-disulfopropylammonium betaine: This high degree of selectivity is related to reactions that follow a radical mechanism Is surprising. In the absence of an allyl compound, peroxodisulfate reacts with bisulfite in a generally known rapid redox reaction to form a sulfate, so that the allyl double bond is quantitative with high selectivity and collection. It was unexpected to undergo proximity bifunctionalization.
Furthermore, it is a surprising result that this reaction is specifically associated with the presence of peroxodisulfate. Other per-compounds, such as hydrogen peroxide or alkali metal perborate, simply oxidize sulfites to sulfates without causing comparable reactions.

However, in special cases it may be necessary to use peroxodisulfate and other percompounds and even other oxidizing agents in common, so that the amount of peroxodisulfate required per mole of allyl compound is less than the molar amount. It is possible.

Hydrogen peroxide, chlorine, chlorates, bromates and the like are suitable for this purpose.

Preferably, according to the method of the present invention, an allyl ammonium salt is mixed with 2 molar equivalents of bisulfite in an aqueous solution to adjust the PH value to 2 to a maximum of 4 and 1 molar equivalent of peroxodisulfate is added with stirring. The reaction which then proceeds is recognized by the rapid temperature rise of the reaction mixture, which can reach boiling. The substituted long-chain allyl ammonium salts give rise to the surface-active sulfobetaine sulphonates, which can be easily isolated from the reaction mixture in the working procedure described above and isolated in pure form. it can. In other cases, the sulfuric acid formed is neutralized prior to treatment, and the sulfobetaine sulfonate is extracted if necessary and separated from the inorganic salt portion.

The continuous implementation of the method according to the invention in a suitable device
It is possible when a fixed amount of the X-ray component is supplied at the beginning of a certain residence time at the indicated molar ratio.

It has been found that these novel sulfobetaine sulfinatos can be used as active intermediates, and both sulfobetaine sulfinato and sulfobetaine sulfonato can be used as effective surfactants in a wide PH range. .

EXAMPLES The ¹³ C-NMR spectra shown in the following examples were measured in D ₂ O and served as an external standard.
It is TMS. The numerical value indicated by the carbon atom symbol in the structural formula corresponds to the chemical shift (PPm).

Examples 1 to 8 Pure sodium dimethyl (2-sulfinato) -3-sulfopropyl-ammonium betaine by converting dimethylallylamine hydrochloride to sulfosulfinato in relation to initial PH value (R ¹ = R ² = C
^{_{H 3, R = R 3 =}} H, X = SO 2 N a) and therewith dimethyl-3
General formula for preparing a mixture with sulfopropyl-ammonium betaine (R ¹ = R ² = CH ₃ , R = R ³ = H, X is replaced by H in general formula I) Stirrer, In a three-necked flask equipped with a thermometer and a glass electrode, 6 of dimethylallylamine hydrochloride prepared by dissolving newly distilled dimethylallylamine in concentrated hydrochloric acid was prepared.
185 g (1 mol) of a 5.65% solution, 516.5 g (2.0 mol) of a 40.7% solution of industrial sodium bisulfite having an iron content of 60 mg /
2 mol) and PH shown in Table 1 at a working amount of 1 kg
Corresponding amounts of 37 so that the initial PH value of the reaction mixture from value 2 (Example 1) to PH value 6 (Example 8) is guaranteed.
% Hydrochloric acid or 33% sodium hydroxide solution and water in sequence.

When a large amount of sodium hydroxide solution is required for adjusting the PH value, the temperature of the starting solution rises, so it was necessary to cool it to room temperature prior to the chemical change in order to guarantee the same starting conditions. The thus-prepared yellowish starting solution is stirred into finely divided sodium peroxodisulfate 4.1.
When g (2 mol%) was added all at once, the peroxodisulfate was immediately dissolved and the reaction mixture warmed up, especially when the initial PH value was less than 5, -coloring blood red.

The table below shows the time course of the exothermicity of the sulfosulfinatization for a PH value of 4 (see Table 1, Example 4): After reaching the maximum temperature, the chemical change is complete. An integer-divided part of the obtained reaction solution is dried in vacuum to give a salt-like residue, the composition of which is determined by comparison of appropriate signal intensities of ¹ H-NMR spectrum.

Table 1 shows the relationship between the time required to reach the maximum temperature after the start of sulfobetaine sulfinato yield, the temperature difference reached (from the starting temperature to the maximum temperature), and the PH value adjusted each time.

So pure sulfobetaine sulfinato had an initial PH value of 2.
The higher the PH value that can be obtained only below 5, (Examples 3 to 8), the proportion of dimethyl-3-sulfopropylammonium betaine subsequently increases. It is true that in all the examples the maximum temperature is reached 2 minutes after the start, but especially in Examples 6 to 8 the chemical changes remain incomplete, as can be seen from the measured temperature difference. The chemical change can be completed by increasing the initiator concentration or by the inclusion of additional atmospheric oxygen: but at these PH values no improvement in the yield of sulfobetaine sulfinato could be demonstrated.

Example 9 Disclosed Agent Sodium-Dimethyl- (2-sulfinato) dimethylallylamine hydrochloride under varying concentration
-3-Sulfopropylammonium betaine (general formula I
In which R ¹ = R ² = CH ₃ , R = R ³ = H, X = SO ₂ Na) is subjected to sulfosulfinato reaction. Time elapsed for the exothermic sulfosulfinatization of dimethylallylamine hydrochloride (1 mol) and sodium bisulfite (2.1 mol) and the amount of the initiator (sodium peroxodisulfate = APS) used (0 mol%
To 8 mol% and fluctuation). The entire result is shown in FIG.

In the range of less than 0.5 mol% peroxodisulfate, the reaction can be initiated in the starting phase by the percompound and then further led by the action of oxygen. It takes much longer to complete the chemical change by initiation by oxygen in the air. After 50 minutes the temperature is indeed highest, but at this point the chemical change is still not complete (see Example 12). With higher peroxodisulfate concentrations, for example 8 mol%, only 20 seconds are required to complete the chemical change. Higher initiator concentrations lead to explosive boiling of the mixture immediately after addition. Describes starting from this series of experiments using ammonium peroxodisulfate 2 mol% as a representative; stirrer, 65.65% dimethyl allylamine hydrochloride solution 85 g (1 mol) in a three-necked flask equipped with a thermometer and a glass electrode, F _e ^{+ +} Content 8mg /
61.35 g of 35.33% industrial sodium bisulfite solution (2.
1 mol), 10 g of 37% hydrochloric acid and 171.5 g of water are mixed together with stirring. The PH value of the solution is 2.5. Then water 10.44
A solution of 4.55 g (2 mol%) ammonium peroxodisulfate in g is added at once. The solution colored red and reached the maximum temperature after 3 minutes, indicating the end of the sulfosulfination. The table below shows the course of fever: EXAMPLE 10 This example sodium dimethyl allyl amine hydrochloride - dimethyl - (2-Surufuinato) -3-sulfopropyl - in betaine (formula ^{I R 1 = R 2 = CH} 3, R = R 3 = H, It is intended to show an improvement in the rate of the sulfosulfinatization reaction with X = SO ₂ Na) when the concentration of the component used increases and a decrease when the starting temperature decreases.

To make a solution with a PH value of 2, 65.65% dimethylallylamine hydrochloride solution 185 g (1 mol) 40.9% industrial sodium bisulfite solution 534.3 g (2.1 mol) and 37% hydrochloric acid
21.4 g are mixed with one another. Subsequently, with stirring, 4.8 g (2 mol%) of finely divided sodium peroxodisulfate are added at once. The reaction solution momentarily turns red and the temperature rises from 22 to 50 ° C within 1 minute, whereby the chemical change is quantitative. However, when the same experiment is repeated at a starting temperature of 0 ° C., the yellowish reaction solution first turns red after 1.5 minutes and reaches a maximum temperature after 4 minutes. The time course at different starting temperatures is as follows: 2 ml of water are evaporated from the reaction solution in a vacuum to remove residual sulfur dioxide. Neutralize with sodium hydroxide solution and add a few drops of 30% H ₂ O ₂ . After separation of iron hydroxide III, the colorless reaction solution is concentrated in vacuo. ¹³ NMR spectrum The sodium salt is well treated with a sufficient amount of concentrated hydrochloric acid to isolate the free dimethyl (2-sulfinic acid) -3-sulfopropylammonium betaine. Then the inorganic salts-mainly sodium chloride-are separated off and the solution is concentrated in vacuo. At that time, sulfinic acid crystallizes as a colorless substance. It can be recrystallized from water with ethanol added. ¹³ C-NMR-spectrum N-CH ₃ groups different sodium salt connexion sulphinic acid is not equivalent.

If necessary, the sulfinic acid can be neutralized with an arbitrary base to recover the respective salts (sulfobetaine sulfinato or sulfinatosulfonato) purely according to the chemical formula.

Example 11 This example and the following show the initiation of sulfosulfinatization of dimethylallylamine hydrochloride with other initiators such as oxygen, hydrogen peroxide and sodium perborate, which are of the present invention. It tries to reveal that it is inferior to the method.

Sulfosulfinatoization while stirring and mixing oxygen In the same manner as in Example 10, a solution having a PH value of 2 was prepared from 1 mol of dimethylallylamine hydrochloride, 2.1 mol of sodium bisulfite and hydrochloric acid. Stir vigorously to mix oxygen in the air into the solution so that air bubbles are constantly and finely distributed in the solution to start the reaction and continue until the chemical change is completed. The time course of the exothermic sulfosulfination is shown in the table below: The maximum temperature of the chemical change has been reached after 75 minutes of reaction time, but the ¹ H-NMR-spectrum of the sample taken after 85 minutes still indicates the starting material. However, after 150 minutes the chemical change is quantitative.

The reaction time product contains 91% sulfobetaine sulfinato and 9% sulfobetaine.

The sulfosulfinato product is quantitatively obtained with a significantly short reaction time in the same consolidation of chemical reactions initiated with sodium peroxodisulfate at a PH value of 2 (Examples 1, 2 and 1). See 10).

Example 12 Sulfosulfinatization of Dimethylallylamine Hydrochloride with Hydrogen Peroxide and Sodium Perborate As described in Example 10, except that sodium peroxodisulfate was replaced with 30% hydrogen peroxide 2 mol% once. Add to the reaction solution and work. The temperature of the solution rises by 2 ° C in 10 seconds and remains constant thereafter. No chemical change to the target product occurs.

Even if sodium perborate is used as the initiator, only the starting material is recovered in the same process. Only if additional peroxodisulfate is added to the reaction solution, a quantitative chemical conversion to sulfobetaine sulfinato is achieved, as already described in Example 10.

Example 13 N, N-Dimethyl-2-methallylamine hydrochloride sulfosulphinatoation Working as described in Example 10, N, N-dimethyl-2-
3.7 g of methallyl ammonium chloride (30 mmo
l), sodium bisulfite 65 mmol, hydrochloric acid, tap water and a solution of 5 mol% of sodium peroxodisulfate are combined, and the total amount of 56 g is chemically changed at a PH value of 2.1. The reaction solution heats up to 6.5 ° C when the chemical change is initiated at room temperature.

After completion of the chemical change, the solution is adjusted to PH value 11 with sodium hydroxide and investigated by ¹³ C-NMR spectroscopy. Also, the spectrum is not a uniform product but 1-dimethylamino-2-sulfinato-
It shows that it consists of 3-sulfonato-2-methylpropane-disodium salt and 1-dimethylamino-2-methyl-3-sulfonatopropane sodium salt. ¹³ C-NMR-spectrum (PPm) (all signals are> 15% strong compared to the main signal at 45.6 ppm): 64.9; 60.8;
60.1; 56.6; 55.9; 49.4; 49.0; 45.6; 39.9; 28.5; 1
9.5; 16.5 Example 14 Sodium-didiethyl- (2-sulfinato) -3-sulfopropyl-ammonium betaine by sulfosulfinatonization of diethylallylamine hydrochloride (in the general formula I, R ¹ = R ² = C ₂ H ₅ , R = R ³ =
_{H, X = SO 2 Na)} .

Working according to Example No. 10, a total of 855 g of a solution of 1 mol of diethylallylamine hydrochloride, 2.1 mol of sodium bisulfite, hydrochloric acid and 2 mol% of sodium peroxodisulfate are chemically reacted with one another at a PH value of 2.5. . The exothermic sulfosulphinatonation takes the following time course; after about 1 minute the reaction solution is colored blood red: ¹³ C-NMR spectrum of reaction product Free diethyl- (sulfinic acid) -3-sulfopropyl-ammonium betaine can be isolated according to the procedure described in Example 10. It is a colorless crystalline substance which can be recrystallized from water with ethanol and exhibits the following ¹³ C-NMR-spectra: The ethyl group of free sulfinic acid is not equivalent to the sodium salt.

Example 15 Sodium (-2-sulfinato) 3-sulfopropylammonium betaine by sulfosulfinatization of allylamine hydrochloride (R = R ¹ in the general formula I)
= R ² = R ³ = H, H = SO ₂ Na) Working as described in Example 10, 1 mol of allylamine hydrochloride, 2.05 mol of sodium bisulfite, hydrochloric acid and 2 mol% of sodium peroxodisulfate 2 mol% solutions The total amount of 715 g of the above is chemically changed from each other. The time course of the temperature rise of the exothermic sulfosulphinatonation is shown in the table below: ¹³ C-NMR spectrum of reaction product Free (2-sulfinic acid) -3-sulfopropyl-ammonium betaine can be isolated as a crystalline substance according to the procedure described in Example 10. ¹³ C-NMR-spectrum Example 16 to 22 These examples trimethyl - allyl - pure sodium trimethyl from ammonium chloride - (2-Surufuinato) -3- sulfopropyl betaine (in the general formula ^{I R = H, R 1 =} R 2 = R ³ = CH ₃ , X = S
O ₂ Na) and trimethyl-3-sulfopropylammonium betaine (R ¹ = R ² = R ³ = CH ₃ , P = X = H in the general formula I) and sulfosulfination and initial PH value. Describe the relationship between. Working as described in the general working rules of Examples 1 to 8, 1 mol of trimethylallylammonium chloride, 2.02 mol of sodium bisulfite and peroxodisulfate at initial PH values as listed in Table 2 2 mol% sodium or potassium (both per Kg of reaction mixture)
To chemically change each other.

As a representative of this series of experiments, describe the sulfosulfinatization at a PH value of 4: 39.7% trimethylallylammonium chloride solution 341.
6 g (1 mol), 40.7% industrial sodium bisulfite solution (iron content 60 mg /) 516.5 g (2.02 mol), 37% hydrochloric acid 2 g and tap water 134.5 g potassium peroxodisulfate
A chemical change is carried out with 5.4 g (2 mol%).

After starting the reaction solution is heated as follows: A part of the obtained reaction solution, which is divided into integers, is concentrated in a vacuum to form a salt-like residue, and the composition is determined by comparison of appropriate signal intensities of ¹ H-NMR-spectra.

Table 2 shows the relationship between the sulfobetaine sulfinato yield, the time until the mixture reaches its maximum after the start and the achieved temperature difference between the starting temperature and the maximum temperature and the adjusted PH value in each case.

So sulfobetaine sulfinato can be made pure only if the PH value is less than 2.

The chemical conversion product obtained in Example 17 has the following ¹³ C-
NMR, show spectrum: As the PH value increases (Examples 18 to 22), the proportion of trimethyl-3-sulfopropylammonium betaine continuously increases. In all the examples, the maximum temperature is certainly reached 3 to 8 minutes after the start-especially in the examples
In 16 and 22-as the conclusion can be made from the measured temperature difference, the change is not perfect for the moment. The chemical change can only be completed by increasing the concentration of the disclosing agent or by stirring in additional oxygen in the air. No improvement in the yield of sulfobetaine sulfinato could be observed at these PH values.

Examples 23 to 27 Sodium alkyl dimethyl- (2-sulfinato) -3-sulfopropylammonium betaine by sulfosulfinatization of alkyldimethylallyl ammonium salts (in the general formula I, R ¹ = R ² = CH ₃ , R ³ = Alkyl, R = H, X = SO ₂ Na) Working according to one of the above examples, the combined solution of the respective alkyldimethylallylammonium salt, aqueous sulfite ammonium or -alkali was chemically changed with ammonium peroxodisulfate or -alkali at a PH value of 2. Let In that case, a crystalline alkyldimethylallylammonium salt can also be used. In the case of the hexadelammonium salt, the bisulfite solution must be heated to about 40 ° C to dissolve the salt.

After the sulfosulfinatization has been carried out, the sulphinatos crystallize out of the reaction solution, in particular those with long chains, which are allowed to cool.

Separation of pure sulfobetaine sulfinato from inorganic salts can also be performed by extracting the concentrated solution with 80% aqueous ethanol.

Recovery of free sulfinic acid can also be performed according to the method described in the above-mentioned Example. The sulfobetaine sulphonic acid can be neutralized with any base to make each salt chemically pure.

Example 28 Sodium-N-dodecyl / tetradecylaminocarbonylmethyl-N by sulfosulfinatization of N-dodecyl / tetradecylaminocarbonylmethyl-N, N-dimethylallylammonium chloride under varying initiator concentrations N-dimethyl (2-sulfinato) -3-sulfopropylammonium betaine (in general formula I
_{^{R 1 = R 2 = CH 3}} ; R 3 = CH 2 -CONH-C 12 H 25 / C 14 H 29;
R = H; X = SO ₂ Na (see FIG. 2) Synthesis of Raw Materials N-Methoxy-carbonylmethyl-N, N-dimethylallylammonium chloride Allyldimethylamine (850 g, 10 mol) was placed in the reactor first. 1085 g (10 mol) of chloroacetic acid methyl ester are added dropwise thereto. The temperature rises slowly during the addition, occasionally cooling and keeping at 60-70 ° C. The reaction product thus obtained is clear and viscous after a quantitative chemical change reached after about 30 minutes.

N-dodecyl / tetradecylaminocarbonylmethyl-
N, N-Dimethylallylammonium Chloride The above methyl ester-ammonium chloride is mixed with a liquid dodecyl / tetradecylamine mixture (Coco
samin, component ratio approximately 1: 1) 1990 g (10 mol) are added dropwise, so that the reaction temperature does not exceed 70-80 ° C. A very viscous end product with a PH value of 7 is obtained.

In a similar manner as already described in Example 9, 1 mol of allyl ammonium chloride prepared according to the above recipe is used with 2.1 mol of sodium bisulfite in 1.1 Kg of a reaction mixture (PH value 2.2) to produce an exothermic sulfosulfur. The relationship between the time required for finatization and the concentration of the initiator was investigated.

Ammonium peroxodisulfate (A used as an initiator
The PS) concentration varies from 0 mol% to 8 mol%. The starting temperature in each case is 20 ° C.

The overall result is shown in FIG. When compared with FIG. 1 (Example 9), a very similar process, that is, an increase in reaction rate, is shown at an initiator amount of 0.5 to 8 mol%. When it is less than 0.5 mol%, sulfosulphinatonation is certainly started in the initial phase, but completion of the chemical change can be achieved only by stirring and mixing additional oxygen in air, while oxygen in air is industrially used. The rate of possible chemical change is not reached.

For example, the following table shows the time course of sulfosulfination with 2 mol% APS: The initially yellowish suspension turned orange immediately after the initiator was added, became homogeneous and then appeared milky white due to the agitated air bubbles. The reaction solution which has been allowed to cool is a homogeneous, clear syrupy yellowish solution.

Separation of pure sulfobetaine sulfinato from the inorganic salt with a melting point of 192 ° C. (decomposition) can be carried out by extraction of the concentrated solution with about 80% aqueous alcohol.

Example 29 Sodium -N- hexadecyl / octadecyl amino carbonyl methyl -N, N-dimethyl - (2-Surufuinato) -3-sulfopropyl - R in ammonium betaine (formula _{^{I 1 = R 2 = CH 3}} , R 3 = _{CH 2 -CO-NH-C 16} H 33 / C
₁₈ H ₃₇ , R = H, X = SO ₂ Na) N-hexadecyl / octadecylaminocarbonylmethyl-N, N-dimethylallylammonium (1 mol) required as a raw material is N, N-dimethylallylamine, chloroacetic acid methyl ester and hexadecyl- / octatadecyl-amine according to Example 28. Of 2.1 liters of sodium bisulfite and 1.6 mol of a reaction mixture with a PH value of 2.1 in the presence of 2.5 mol% of ammonium peroxodisulfate and a starting temperature of 40 ° C.

Sulfobetaine sulfinato precipitates substantially completely from the cooled reaction solution.

Melting point of 90% ethanol 128 ° C. (decomposition) Example 30 Sodium-N [di- (dodecyl / tetradecylaminocarbonyl)]-methyl-N, N-dimethyl- (2-sulfinato-3-sulfopropyl-ammonium Betaine (in the general formula I, R ¹ = R ² = CH ₃ , R ³ = CH (CONH
_{-C 12 H 25 / C 14 H} 29) 2, R = H, X = SO 2 Na) The allyl ammonium required as a raw material is made as follows: 85 g (1 mol) of dimethylallylamine is added to 20 parts of ethanol.
Dissolve in 0 ml. 239 g (1 mol) of brommalonic acid diethyl ester are added dropwise to this solution at 20 ° C. with stirring and then heated to 78 ° C. for a further 4 hours. Subsequently, 298 g (2 mol) of dodecyl / tetradecylamine mixture (Cocosamin, component ratio 1: 1) are gradually added to this solution. Most of the solvent is expelled in vacuo after heating to 80 ° C. for a further 6 hours to complete the chemical change. 2.1 mol of sodium bisulfite, water and concentrated sulfuric acid are added to the remaining allyl ammonium bromide so that 1.6 kg of a homogeneous raw material solution having a PH value of 2.3 is produced. The mixture is heated to 40 ° C. and, after addition of 3 mol% ammonium peroxodisulfate, the sulfosulfinatization is carried out as described in the previous examples.

Upon cooling, the sulfobetaine sulfinic acid begins to crystallize from solution as a yellowish product.

The sample recrystallized from ethanol has a melting point of 74-76 ° C.

Example 31 Sodium -N- octanoyl amide ethyl -N, N-dimethyl (2-Surufuinato) -3-sulfopropyl - in betaine (formula ^{R 1} = R ² = CH
₃ , R ³ = C ₇ H ₁₅ CONH-CH ₂ -CH ₂ R = H, X = SO ₂ Na) The allyl ammonium chloride needed as a raw material can be made from octanoic acid methyl ester, N, N-dimethylethylenediamine and allyl chloride.

1 mol of allyl ammonium chloride, 2.1 mol of sodium hydrogen sulfite, hydrochloric acid and water for adjusting the PH value to 2.2 are combined to make a 1.6 kg solution, and 2 mol% of ammonium peroxodisulfate is added. The reaction mixture was 20-33 within 2.5 minutes.
The temperature was raised to 5 ° C, and the chemical change was completed.
Melting point 20 after treatment and recrystallization from 80% aqueous ethanol
Sulfobetaine sulfinato at 9 ° C (decomposition) could be isolated in a substantially quantitative yield.

Example 32 Sodium preventor dec over Fluor - octanoyl amide ethyl -N, N-dimethyl (2-Surufuinato) -3-sulfopropyl - R in ammonium betaine (formula _{^{I 1 = R 2 = CH 3}} , R 3 = C ₇ F ₁₅ CONH-CH ₂ CH ₂ , R =
H, X = SO ₂ Na) The allyl ammonium chloride required as a raw material can be made from bentadecafluorooctanoic acid chloride, N, N-dimethylethylenediamine and allyl chloride. Allyl ammonium chloride (0.1 mol), sodium hydrogen sulfite (0.21 mol), hydrochloric acid for adjusting the PH value to 2.2 and water were combined to form a 160 g solution, which was mixed with 2 mol% of ammonium peroxodisulfate. The reaction mixture was heated to 20 to 35 ° C. within 2 minutes, whereby the chemical change was complete.

After treatment and recrystallization from acidic 50% aqueous ethanol, sulfobetaine sulfinic acid with a melting point of 138 to 140 ° C. could be isolated in a substantially quantitative yield. (This sodium salt of sulfobetaine sulfinic acid is strongly hygroscopic.) Example 33 Sodium-dimethyl-2.3-sulfopropyl-ammonium betaine (in the general formula I, R ¹ = R ² = CH ₃ ,
^{R = R 3 = H, X} = SO 3 Na), those from dimethylallylamine hydrochloride.

39.2% of dimethylallylamine hydrochloride in a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer.
% Aqueous solution 310 g (1 mol), industrial sodium hydrogen sulfite 39% solution (iron-containing 9 mg / solution) 533.6 g (2 mol)
The pH value (glass electrode) was 2.15 as a homogeneous solution by mixing 37% hydrochloric acid.

The yellowish yellow starting solution thus prepared was treated with 238.1 g (1 mol) of sodium peroxodisulfate (Na ₂ S ₂ O ₈ ) and 357.
A 40% aqueous solution of sodium peroxodisulfate prepared from 15 g was added without interruption. After 2 minutes, about 60% of this solution had been sent in, and the solution that turned red began at 21 ° C.
The temperature was raised to 94 ° C. As the oxidant was continuously fed, the reaction solution gradually became lighter in color, and eventually about 90% of the peroxodisulfate solution was obtained.
After feeding, it became colorless. Excessive heat of reaction of the solution, which had boiled during that time, could be easily removed by reflux cooling, and after 4 minutes, the feeding of the peroxodisulfate was completed.

The table below shows the time course of the exothermic reaction during the oxidant delivery phase: The ¹ H-NMR-spectra made on this solution at this point confirmed the quantitative and selective chemical conversion of the allyl ammonium salt to sulfobetaine sulfinato.
After neutralizing the strongly acidic reaction solution with 33% sodium hydroxide, the iron salt contained in it was aggregated as iron hydroxide III by using industrial sodium bisulfite, and most of the crystallized sodium sulfate was I was able to separate.

The colorless liquid showed the following ¹³ C-NMR spectrum (N-CH ₃ groups are not equivalent).

When the sulfobetaine sulfonate is completely separated from the entrained inorganic salt and the free dimethyl- (2-sulfonic acid) 3-sulfopropyl-ammonium betaine is to be isolated, work as follows: After evaporating the reaction solution to dryness, the residue obtained is mixed with a sufficient amount of hydrochloric acid and treated well, the insoluble sodium salt is removed and the hydrochloric acid-acidified sulfobetaine sulfonic acid solution is evaporated to dryness under reduced pressure. Soon sulfonic acid begins to crystallize as a white substance. It can be easily recrystallized from water. 12
It begins to decompose slowly at 0 ° C.

The ¹³ C-NMR spectrum of this acid is the same as that of the corresponding sodium salt.

If necessary, the sulfonic acid can be neutralized with an arbitrary base to form each salt (sulfobetaine sulfonate or disulfonato) pure according to the chemical formula. For example, using 2 molar equivalents of sodium hydroxide solution, disodium-3-dimethylaminopropane-1.2-disulfonate is obtained with the following ¹³ C-NMR spectrum: Example 34 Sodium-N, N-dimethyl-2-methyl-2.3-disulfopropylammonium-betaine Working as described in Example 33, instead of dimethylallylamine, N, N-dimethyl-2-methallylamine Initial PH value consisting of 7.4 g (30 mmol) of 50% aqueous solution of hydrochloride, 65 mmol of 39% sodium bisulfite solution and hydrochloric acid 2.
0 homogeneous solution and 40% sodium peroxodisulfate solution 6
Chemically change 5 mmol with each other.

After the chemical change is complete, the solution is PH with 33% sodium hydroxide solution.
Was adjusted to 11, separating the sodium sulfate to crystallize, ¹³ C-
NMR-spectroscopy. Its spectra are 1-dimethylamino-2,3-disulfonato-2-methylpropane-disodium salt and 1-dimethylamino-2-methyl-3-
The mixed substance with sulfonatopropane-sodium salt is shown. ¹³ C-NMR-spectrum (ppm), (all signals are 27.9 ppm
75.5; 64.2; 63.8; 58.8; 58.6; 57.1; 56.2; 54.4; 4
9 .; 45.5; 45.2; 45.1; 45.0; 27.9; 21.5; 19.2; Sodium from Example 35 trimethyl allyl ammonium - trimethyl -2.3- di sulfopropyl betaine (formula I in ^{R 1 = R 2 = R 3} = CH 3, R = H, X = SO 3 Na) Example 33 36.7% trimethylallylammonium chloride solution 341.6 g (1 mol), 39% sodium-allyl ammonium chloride solution 533.6 g (2 mol) and 37% hydrochloric acid 33 g are mixed together into a homogeneous solution. , Its PH value was 2.0. 40% sodium peroxodisulfate solution was added to this solution over the course of 5 minutes.
595.25 g was added dropwise. The table below reveals the time course of the exothermic reaction during the oxidant delivery phase: The chemical conversion to sulfobetaine sulphonate is at this point quantitatively and selectively carried out as determined by ¹ H-NMR-spectroscopy. ¹³ C-NMR of neutralized reaction solution
-Spectrum: However, if the PH value of the homogeneous reaction solution is adjusted to> 2 at the beginning, the selectivity of the proceeding reaction is reduced and trimethyl-2.3-
In addition to disulfopropyl-ammonium betaine, more and more trityl-3-sulfopropylammonium betaine is also produced, the latter possibly being the main product of the chemical transformation.

This situation will be illustrated by the following example: Example 36 Working according to example 35, 1 mol trimethylallylammonium chloride solution and 2 sodium bisulfite solution 2
The moles were mixed with each other. 1 mol of a 40% sodium peroxodisulfate solution was fed into the homogeneous solution having a pH value of 4.0 as described above. The quantitative composition of the neutralized reaction solution was determined by ¹ H-NMR-spectroscopy by comparison of appropriate signal intensities, and trimethyl-2-sulfopropylammonium betaine 59% as well as trimethyl-3-sulfopropylammonium were determined. It was found that 41% of betaine could be obtained (East German General Patent No. 1
See 154443).

Example 37 This and the following examples are intended to demonstrate the suitability of oxidizing agent combinations.

Working according to Examples 33 and 35, make a homogenous solution with a PH value of 2.0 from 1 mol of trimethylallylammonium chloride solution, 2 mol of sodium bisulfite solution and hydrochloric acid and first make 50% ammonium peroxodisulfate in about 1 minute. 15 mol% of the solution was subsequently added with 30% hydrogen peroxide at such a rate that the exothermic reaction could be dominated by reflux cooling, for which it took about 4 minutes. ^{By 1} H-NMR-spectroscopy, it could be proved that the allyl ammonium salt was quantitatively converted into sulfobetaine sulfonate.

Repeating this experiment with rose hydrogen peroxide as the oxidant did not change the raw material, it was merely the oxidation of sulfite to sulfate.

Example 38 Working according to example 37, substituting 85 mol% hydrogen peroxide with chlorine as oxidant. Only sulfobetaine sulphonite could be verified by ¹ H-NMR spectroscopy. On the other hand, repeated experiments using only bulk chlorine as the oxidant could not give sulfobetaine sulphonate: only oxidation of sulphite to sulphate.

Sodium from Example 39 diethylallylamine hydrochloride - diethyl -2.3- di sulfopropyl - ammonium betaine (in the general formula ^{I R 1 = R 2 = C} 2 H 5, R = R 3 = H, X = SO 3 Na) An equivalent solution was made from 1 mole of diethylallylamine hydrochloride, 1 mole of sodium pyrosulfite (Na ₂ S ₂ O ₅ ) and 37% hydrochloric acid according to the procedure of the previous example. ¹³ C-NMR-spectrum (N-ethyl groups are not equivalent) Diethyl- (2-sulfonic acid) -3-sulfopropyl-
The isolation of ammonium betaine could be carried out according to the procedure described in Example 33. Initially the sulphonic acid was obtained as a very viscous colorless oil which, after standing for several days, began to crystallize faster upon inoculation. ¹³ C-NMR-spectrum is virtually the same as that of sodium salt.

When sulfobetaine sulfonic acid or sulfobetaine sulfonate is neutralized with sodium hydroxide solution, the following ¹³ C-NMR
-Spectral disodium-3-diethylaminopropane-1.2-disulphonate is obtained: Example 40 Sodium-triethyl-2.3-disulfopropyl-ammonium betaine from triethylallylammonium bromide (R ¹ = R ² = R ³ = C in general formula I)
₂ H ₅ , R = H, X = SO ₃ Na) A homogeneous solution having a PH value of 2.0 was prepared from 1 mol of triethylallyl ammonium ammonium bromide, 2 mol of sodium bisulfite and hydrochloric acid, and one of the preceding examples was prepared. I worked accordingly. Sulfobetaine sulfonate was obtained quantitatively and
¹³ C-NMR-spectrum shown: Example 41 Sodium from allylamine hydrochloride-2.3-
Di sulfopropyl - (in formula ^{I R = R 1 = R 2} = R 3 = H, X = SO 3 Na) ammonium betaine allylamine 1 mole, the homogeneous solution of PH value from 2.0 sodium bisulfite 2 moles and hydrochloric acid Construction Worked according to Example 37.

After neutralization and insoluble iron hydroxide III which was present in the traces, it was allowed to cool and the sulfobetaine sulfonate immediately began to crystallize from the colorless reaction solution. Quantitative crystallization can be achieved by adding ethanol. The product can be recrystallized very well from water. ¹³ C-NMR-spectrum: Free (2-sulfonic acid) -3-sulfopropyl-ammonium betaine can be isolated according to the procedure described in Example 33. A colorless crystalline substance is obtained, which can likewise be easily recrystallized from water to which ethanol has been added. The ¹³ C-NMR spectrum of free sulphonic acid is virtually identical to that of sulfobetaine sulphonate.

Sulfobetaine sulfonic acid or sulfobetaine sulfonate is neutralized with sodium hydroxide solution, and the following ¹³ C-NMR-
Disodium with a spectrum-3-aminopropane-
1.2-disulfonato is obtained: Examples 42-46 Sodium-alkyl-dimethyl-2.3-disulfopropyl-ammonium betaines from alkyl-dimethyl-allyl ammonium salts (R = H in general formula I,
R ¹ = R ² = CH ₃ , R ³ = alkyl, X = SO ₃ Na) Working according to one of the preceding examples, a homogeneous solution of pH 2.0 was prepared from 1 mol of alkyl-dimethyl-allylammonium salt, 2 mol of bisulfite, hydrochloric acid and water. In the case of long-chain alkyl-dimethylallylammonium salts (alkyl> C ₁₄ ) the initial suspension is about 40
It had to be heated to 0 ° C. in order to obtain a homogeneous starting solution.

In particular, the long-chain reaction product (alkyl C ₁₆ ) precipitates from the solution in the cold after a chemical change with 1 mol of peroxodisulfate or peroxodisulfate / oxidant combination. Depending on whether the reaction mixture was pre-neutralized it was possible to separate free sulfobetaine sulphonic acid or reaction sulphobetaine sulphonate.

In the case of short-chain sulfobetaine sulphonates they are separated from the entrained inorganic salts in order to separate the residue from which the solutions have been evaporated off with an ethanol / water mixture (1: 1 to 2:
Extraction was performed using 1).

Example 47 Sodium-aminocarbonylmethyl-dimethyl-2.3
- In di sulfopropyl betaine (formula ^{I R = H, R 1 =} R 2 = CH 3, R 3 = CH 2 -CO-NH
₂ , X = SO ₃ Na) Working according to Example 37, 1 mol of aminocarbonylmethyl-dimethylallylammonium chloride made from dimethylallylamine and chloroacetamide, 2 mol of sodium bisulfite and PH value from hydrochloric acid The 2.0 homogeneous solution was chemically transformed with ammonium peroxodisulfate / hydrogen peroxide with external cooling so that the reaction temperature did not exceed 60 ° C. Immediately after the end of the chemical change,
It was neutralized with sodium hydroxide solution to prevent hydrolysis of the acid amide function.

However, as in Example 33, when an attempt was made to make a chemical change using only peroxodisulfate, approximately 10 mol% of the peroxodisulfate solution was introduced into the allyl ammonium salt and then the remaining peroxodisulfate was added. At the same time as the sulphate (90 mol%) 2 molar quantities of sodium hydroxide solution had to be added, keeping the temperature at 60 ° C. and outside.

The sulfobetaine obtained could be separated from the accompanying inorganic salts by extracting the residue obtained by concentrating the reaction solution with an ethanol / water mixture (1: 1). The sulfobetaine sulfonate obtained at a substantially quantitative yield was as shown below at a decomposition point of 276 ° C.
¹³ C-NMR-spectrum shown: Example 48 Sodium - dodecyl / tetradecyl amino carbonyl methyl - dimethyl -2.3- di sulfopropyl - in betaine (formula ^{I R = H, R 1 =} R 2
^{_{= CH 3, R 3 = CH}} 2 -CO-NH-C 12 H 25 / C 14 H 29, X = SO 3 N
a) Working according to Example 47, dodecyl- / tetradecylaminocarbonylmethyl-dimethyl made from dimethylallylamine, chloroacetic acid methyl ester and dodecyl- / tetradecylamine mixture (COcosamin, component ratio approximately 1: 1). Allyl ammonium chloride was quantitatively changed to sulfobetaine sulphonate with a melting point of 158 ° C (decomposition). Extraction of sulfobetaine sulphonate was carried out with aqueous ethanol (70%) from the residue after evaporation of the solution to dryness.

Example 49 Sodium-di (dodecyl- / tetradecylaminocarbonyl) methyl-dimethyl-2.3-disulfopropyl-
Ammonium betaine (in the general formula I, R = H, R
_{^{1 = R 2 = CH 3,}} R 3 = CH (CO-NH-C 12 H 25 / C 14 H 29) 2,
X = SO ₃ Na) Working according to Example No. 47, dimethyl-allylamine,
Reacting di (dodecyl- / tetradecylaminocacarbonyl) methyl-dimethyl-allyl ammonium bromide made from prom-malonic acid diethyl ester and dodecyl- / tetradecylamine-mixture (Cocosamin, component ratio approximately 1: 1) It was quantitatively changed to sulfobetaine sulfonate at a temperature of 40 ° C. On cooling the reaction mixture the sulfobetaine sulphonate thus produced precipitated: it was separated and recrystallized from ethanol. Melting point 155 ° C
(Decomposition).

Example 50 Sodium-octanoylamidoethyl-dimethyl-2.
3-disulfopropyl ammonium betaine (general formula I
In ^{R = H, R 1 = R} 2 = CH 3, R 3 = CH 2 -CH 2
_{-NH-CO-C 7 H 15} , X = SO 3 Na) Working according to Example 47, octanoylamido-ethyl-dimethyl-allylammonium chloride made from octanoic acid methyl ester, dimethylethylenediamine, and allyl chloride was quantitatively (recrystallized from 70% aqueous ethanol). The decomposition point was changed to sulfobetaine sulfonate> 186 ° C.

Sodium EXAMPLE 51 - pentadecanoyl Fluor - octanoyl amide ethyl - dimethyl -2.3- di sulfopropyl betaine (formula I in ^{R = H, R 1 = R} 2 =
_{^{CH 3, R 3 = CH 2}} -CH 2 -NH-CO-C 7 F 15, X = SO 3 Na) Working according to Example 47, pentadecafluorooctanoylamidoethyl-dimethyl-allylammonium chloride made from pentadecafluorooctanoic acid chloride, dimethylethylenediamine and allyl chloride was determined quantitatively from 70% aqueous ethanol. Recrystallized and melting point 248
Changed to crystalline sulfobetaine sulphonate at ° C (decomposition).

[Brief description of drawings]

Figure 1 shows sodium-dimethyl- (2-sulfinato).
Fig. 2 shows the relationship between the reaction time for the formation of 3-sulfopropylammonium betaine and the amount of the initiator (APS) used. Fig. 2 shows the reaction time for the formation of N-dodecyl- / tetradecylaminocarbonylmethyl-N, N-dimethylallylammonium chloride. The relationship between the dose and the initiator (APS) dose is shown.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jochen Roussier, Federal Republic of Germany 1136 Berlin Hans Rothsjostraße 263 (72) Inventor, Roland Ohme, Federal Republic of Germany 1180 Berlin Wald Schuttraße 6

Claims (5)

[Claims] 1. A novel formula I with a substitution at the new 2 position. (Wherein R represents hydrogen or a methyl group, X represents SO ₂ M or SO ₃ M, M can be hydrogen or an alkali metal such as sodium or potassium, or NH ₄ ⁺ ;
¹ and R ² are each independently hydrogen, an alkyl residue having 1 to 3 carbon atoms, a hydroxyalkyl residue, an oxyalkylene residue having up to 10 ethylene oxide units, or a closed ring-forming substituent. R ³ represents hydrogen or an alkyl residue having 1 to 22 carbon atoms, which may contain —NH—CO— or —CONH— in the chain).
-Sulfopropyl-ammonium betaine. 2. A new formula I with a substitution at the new 2 position. (Wherein R represents hydrogen or a methyl group, X represents SO ₂ M or So ₃ M, M can be hydrogen or an alkali metal such as sodium or potassium, or NH ₄ ⁺ , R
¹ and R ² are each independently hydrogen, an alkyl residue having 1 to 3 carbon atoms, a hydroxyalkyl residue, an oxyalkylene residue having up to 10 ethylene oxide units, or a closed ring-forming substituent. R ³ represents hydrogen or an alkyl residue having 1 to 22 carbon atoms, which may contain —NH—CO— or —CONH— in the chain) 3-sulfopropyl- In the method for producing ammonium betaine, the general formula II (Wherein R, R ¹ , R ² and R ³ are as defined above and Y ⁻ represents an anion, preferably chloride or bromide), an allyl ammonium salt or a methallyl ammonium salt of which a PH value of 2.0 to 4.0 is obtained. Range, the presence of peroxodisulfate, optionally in combination with other oxidants, and the chemical conversion with at least twice the molar amount of bisulfite in aqueous solution. 3. A process according to claim 2, characterized in that the peroxodisulfate is added in a catalytic amount. 4. Peroxodisulfate is added singly in a molar amount or in combination with other oxidants so that a dioxidation equivalent of the allylammonium salt or methallyl ammonium salt used can be used. The method according to claim 2. 5. The oxidant used in combination with peroxodisulfate is chlorine or a chlorine-generating substance, chlorate, bromate, hydrogen peroxide or air. The method according to either item 2 or item 4.