DD200739A1 - PROCESS FOR THE PREPARATION OF NEW SULFOBETAIN SULPHONATES - Google Patents

Abstract

The invention relates to a process for the preparation of sulfobetaine sulfonates of the formula II in which R & ind1! Hydrogen and alkyl having 1-22C atoms, of which the beta-C atom may be optionally substituted with a hydroxyl group, branched or straight chain, and R & ind2! 3'-sulfopropyl or R & ind1! and R & ind2! may be closed with the inclusion of the nitrogen atom to a 3-methyl-4-sulfomethyl-pyrrolidiniumring. To prepare the compounds, a reaction of triallyl or tetraalkylammonium salts takes place with thorough mixing under mild reaction conditions in the presence of catalytically active ions of the transition metals of the PSE and radical initiators at pH 2-9 with salts of the sulfuric acid. To carry out the process, technical chemicals can be used, the process is low in energy and technologically simple to carry out. In just one reaction step, the compounds are formed selectively and in almost quantitative yield. The sulfobetaine sulfonates with long-chain alkyl radicals (R) are valuable surfactants with partially amphoteric character, which are versatile. formula

Description

Title of the invention

Process for the preparation of novel sulfobetaine sulfonates

Field of application of the invention

The invention relates to a novel process for the preparation of Sulfobetainsulfonaten a new structural type »The compounds have by introducing a V / eiteren sulfo group better solubility in polar solvents than sulfobetaines and are surfactants, which are available due to their structure in a wide pH range *

Characteristic of the known technical solutions

Sulfobetaines having an additional sulfo group of the formula I are known,

CH ₀ - CH ₀ - CH ₀ - SO®

j dcd J

Alkyl J% -CH ₂ -CH ₂ -OH T

CH ₂ - CH ₂ - CH ₂ - SO®

(P. D _# Smith and W. M * Linfield, J. Amer. Oil Chemists' Soc. 55 (1978) 741). They are characterized by very good caustic soap dispersibility and are obtained by the action of 2 moles of propane sultone on the corresponding hydroxyethylamino compounds manufactured*

The disadvantage of this method is that propanesultone is one of the most dangerous carcinogens (Z.Cancer Research, 25 (1970) 69; Registry of Toxic Effects of Chemical Substances, National Institute for Occupational Safety and Health, Maryland, USA, 1975 edition, 826). and for technical syntheses only

can be used under particularly complex health protection measures.

Two processes for the preparation of sulfobutaines without additional sulfoalkyl group ( II ) mono- or diallylammonium compounds by a homogeneous catalytic free-radical bisulfite addition reaction are also known to give corresponding sulfobetaines (DD applications: WP C 07 C / 222 562 and WP C 07 D) / 222 563) * A disadvantage is that the sulfobetaines produced have a too low solubility for some applications.

It is known from polyfunctional allylammonium compounds under radical reaction conditions that polymers and crosslinked polymers coexist (J. Amer. Chem. Soc., 2§ (1954) 713 and J. Amer. Chem. Soc. 76 (1954) 2418).

Object of the invention

The aim of the invention is to develop a process for the preparation of new Sulfobetainsulfonate * The use of carcinogenic alkylating agents should be avoided. The process should be based on available starting materials, allow the use of technical chemicals and lead under mild reaction conditions in short reaction times with high selectivity to the highest possible quantitative conversion. By using approximately stoichiometric amounts of the reactants, the accumulation of by-products or by-products should be minimized.

Explanation of the essence of the invention

This object is achieved by a process for the preparation of novel sulfobetaine sulfonates of general formula II,

- CH - CH - CH ₀ - S0 ~

CH ₂ CH _{2 χτ}

in the R. hydrogen or alkyl having 1 to .22 C-atoms, of which the / 3-substituent may optionally be substituted by a hydroxyl group, branched or straight-chain, and R ^ 3-sulfopropyl or R ^ and Rp including the Nitrogen atom can be closed to a 3 * -methyl-4 "-sulfomethyl- or 3-sulfomethyl-4-methyl-pyrrolidinium ring by simultaneously salts according to the invention on alkylammonium salts with more than two allyl substituents in solution in the pH range from 2 to 9 sulfuric acid and an oxidizing agent

Suitable oxidizing agent is either aerated acid in the presence of traces of metal ions of the 1, 5 *, 7 * or 8 "transition group of the Periodic Table of the Elements or such oxidizing agents as peroxodisulfates, HpO ₂ , organic peroxides or hydroperoxides and Hitrate or nitrite" The reaction can in the temperature range from 5 to 100 ^° C., preferably at room temperature. "Water or water-alcohol mixtures are suitable as solvents." Good mixing of the components is advantageous during the reaction. "

The transfer of the proposed in DD application: WP G 07 C / 222 562 Sublimation on AlIyIammoniumsalze with more than two allyl radicals should be expected because of the multiple reaction possibilities mixtures of simple to often sulfopropylated compounds Since the reaction - in contrast to sulfoalkylation with propane sultone - free-radically initiated, polyfunctional allylammonium compounds should simultaneously contain polymers and crosslinked polymers such as those described by G.B. Butler and R # A "Johnson, JY Amer. Chem. Soc.,""C1954" 713 and G * B * Butler, et al R »L · Goette, J. Amer · Chem * Soc ·, 76i (1954) were 24I8 already observed result" It was therefore completely surprising that from Triallylalkylammoniumsalzen III under free radical conditions to the simultaneous action of bisulfites and oxidizing agents in a uniform reaction course exclusively the new sulfo-betainsulfonates IV are formed · In general formulas III and IV is R = hydrogen, straight-chain or

branched alkyl radicals having 1 to 22 carbon atoms which may be substituted by OH at the β-C atom optionally "X""can mean conventional anions, such as" B · halide, methods

OCLex

III

HSO "/

pH 5 - 8

Equally surprising was the finding that from the Tetraallylaarnioniumsalzen Y, where X ^{- has} the abovementioned meaning, with fourfold possibility of Radiicalangriffs Sulfobetaine sulfonates of the spiro structures YI and YII arise without crosslinked polymers can be detected as a byproduct »

HSO "/ O, j f

pH 5 - 8

CH ₂ - SOY

YI

CH ₀ -

YII

The process according to the invention is carried out in such a way that allylammonium salts having 3 or 4 olefin substituents are preferably reacted simultaneously in an aqueous solution in the pH range 2-9 with hydrogen sulfites and an oxidizing agent. In accordance with the aim of obtaining sulfobetaine sulfonates, hydrogen sulfites are present in twice the molar amount with possibly minor amounts It is advisable to adjust the pH range (preferably 5-8) by addition of neutral sulfite (ITa ₂ SOo). Since the reaction proceeds according to a radical chain mechanism, the requisite oxidant may be used in stoichiometric excess. As the oxidant for generating the starting radicals, aerated acid may preferably be used in the presence of transition metal ions. Other free-radical initiators may be used instead of oxygen, for example peroxodisulfates, perfluorocarboxylic acid, organic peroxides, hitrates, nitrites and the like.

If the solubility conditions so require, lower alcohols may also be used as solvents instead of water, preferably as water-alcohol mixtures. Isopropanols are particularly suitable. If the system is oxygen / transition metal

-4. 10 to 10 gram atoms / liter are sufficient for homogeneous catalysis. Suitable are ions of the metals of the Periodic Table 1, 5, 7 and 8, eg B, copper, vanadium, manganese, iron, cobalt and nickel, according to the invention is in the temperature range of 10 - 100 ⁰ G, preferably between 20 and 40 C, worked »The course of the reaction is exothermic *

The novel sulfobetainesulfonates IV with long-chain alkyl radicals are anionic surfactants with a partially amphoteric character. As a hydrophilic structural element, sulfobetaine sulfonates are particularly suitable for converting even very long-chain amines into sufficiently soluble surfactants. As a result of their both anionic and amphoteric character, the compounds are in a wide pH Range, so that this type of compound retains surfactant properties even under acidic conditions, which is of particular interest, for example, for use in hard surface cleaners.

The advantages of the method according to the invention are that

- no carcinogenic substances have to be used,

the reaction is carried out under mild conditions (preferably Dei ca, 20 ^° C.) and virtually quantitative yields are achieved,

- the resulting connections are new,

- The compounds have a good solubility due to the 2 'sulfo group in polar solvents, and

- to be used as surfactants within a wide pH range due to their amphoteric and acid character

Exemplary embodiments Example 1

Sulfocyclisierung of triallylamine for 1- ^(3> * sulfopropyl) -3-niethyl-4-sulf omethyl- "pyrrole idinium betaine

14.4 35.6 37.7 51.0 _A H-aC-CH-CH-CH ₂ -SO®

56, 3 ^X CH ₂ CH ₂ 58.1 ^X

^N Έ / ν 61.6 ^X 22.6 49.3 _ö

H ^XX CH ₂ - CH ₂ - CH ₂ - S0 ~

¹ ^ C-HMR spectrum (D ₂ O, external standard TMS):

The numbers on the C atom symbols in the structural formula correspond to the chemical shifts in ppm · χ: chemical shifts can be reversed »

Prepare the following solutions:

1 * 3.43 g (25 mmol) of triallylamine are converted into triallylamine hydrochloride with dilute hydrochloric acid and diluted with tap water containing per liter 10 gram atom of Fe ²⁺ and made up to 50 ml, the pH of the solution being determined 7 ·

4 υ y ι w y υ

2. Dissolve 4.75 g (25 mmol) of sodium metabisulfite and 3.15 g (25 mmol) of sodium sulfate in tap water and make up to 50 ml.

3 x 0.63 g (5 mmol) of sodium sulfite are dissolved in 150 ml of tap water

In one with stirrer, dropping funnel, gas inlet tube and thermometer sulfonation flask provided the solution is "presented" 3 consists of two dropping funnels, one now simultaneously dropwise Solutions 1 · and 2. in the course of 30 minutes, starting at a starting temperature of 21 ⁰ C *

During the dropwise addition, air is introduced while being stirred vigorously to achieve the finest possible distribution of the air bubbles, which is an essential prerequisite for a rapid conversion * over the entire dropping time, the temperature rises to 27 ⁰ C; Five minutes later, the temperature of 28 C is passed through. The reaction is allowed to continue for a further 15 minutes. The pH value remains constant for 7 minutes during the entire reaction time.

The Ξ-HMR spectroscopically determined conversion was quantitative at this point, as can be seen easily from the disappearance of the allyl proton signals.

If the reaction solution is concentrated to dryness, a colorless mixture of the betaine is obtained in addition to sodium chloride, sodium sulfate and residual sodium sulphite, from which the betaine can be separated from the accompanying salts by ion exchange.

Example 2 '.

1,3-Dimethyl-1 ~ (3'-sulfopropyl) -4-sulfomethylpyrrolidinium betaine

14.4 33.9 35.9 51.2 _ß

HoC - CH - CH - CH ₀ - SO ^ 3 / I ^

66.4 ^ CH _{9 Ä} CH ₀ 69,

H ₃ C CH ₂ - CH ₂ - CH ₂ - SOJ 71.8 63.7 ^X 21.0 49.0

¹³ C-HMR spectrum (D ₂ O, external standard TMS):

The numbers on the C atom symbols of the structural formula correspond to the chemical shifts in ppm * x: chemical shifts may be reversed «

a) by sulfocyclization of methyl "aiallyl-3-sulfopropyl ammonium-b et ain

Methyldiallyl-3-sulfopropylammonium betaine is prepared by reacting methyldiallylamine with propanesultone. won * The betaine

13 shows the following C-MR spectrum (see figures):

130.6 125.6 65.1 @ 48.6 60.6 19.3 48.9 = CH '- CH ₂ ) ₂ Έ · (CH ₃ ),

The sulfocyclization is carried out according to the procedure described in Example 1:

You first prepare three solutions. As solution 1, use 25 ml of a solution which is prepared by dissolving 11.66 g (50 mmol) of methyldiallyl-3-sulfopropylammonium betaine in tap water. Compared with Example 1, the solution 2 instead of 50 ml only to 25 ml or »solution 3» replenished to 50 ml instead of to I50 ml · during the 30 minutes Zutropfzeit the solutions 1 * and 2 »to 3» increased the temperature of the reaction solution from 24 ⁰ C to 38.5 ⁰ C; 5 minutes later, the temperature had already dropped to 38 ⁰ C again. The pH remained at 7 »throughout the reaction.

H-HMR spectroscopy no more allyl proton signals were detectable at this time

One of the concentrated reaction product (colorless, crystalline

1 3

Mass) produced ^ C ~ MR spectrum showed chemical shifts, as they can be seen from the above structural formula - numbers on the C atomic symbols - *

b) by sulfocyclization; of methyl triallyl ammonium bromide d

Methyl triallyl ammonium bromide (colorless crystals) was prepared by quaternization of methyldiallylamine and allyl bromide. The procedure is as described in Example 1 and the following solutions are prepared with tap water:

υ υ-1 ** υ u

1 »50 ml solution - through. Dissolve 11.6 g (50 mmol) of methyl

triallylammonium bromide · 2 »50 ml solution - by dissolving 50 mmol of sodium metabisulfite

or · 50 mmol of sodium sulphite * 3 «100 ml of solution - by dissolving 10 mmol of sodium sulphate«

The reaction mixture warmed from 23 ⁰ C to 39 ⁰ C during 50 'minutes of dropping and held this temperature for five minutes, then gradually drop again * The pH was maintained throughout the reaction time The colorless reaction solution was concentrated to dryness; a colorless crystal mass containing sodium bromide, sodium sulphate, and sodium sulphite in addition to the betaine was obtained. "A salt-blended _H | TMR spectrum showed no allyl proton signals."

The ^ C-MR spectrum of the raw betaine proved to be completely identical to the product obtained under a) *

Example 3

SuIfocyclisierung. of Tetraallylammoniumbromid to the isomeric mixture of bis-cyclos-pirosulfobetainsulfonate VI and VII

HC-CH CH-CH ₀ -SO? H ^ C-CH -CH-CH ₀ -SO?

-3 jj 2 3 3 j I. ²

CH ₀ CH ₀ CHp CHp

CH ₀ * CH ₀ , 2, 2

MD ₃ S-CH ₂ -CH CH-CH ₃ H ₃ C-CH CH-CH ₂ -SOJ

VI VII

¹³ C-NMR spectrum (DpO, external standard TMS) The numbers correspond to the chemical shifts in

-CH ₃ : 14.4; 14.6 -CH ₂ -SO ₃ : 51.4

-CH-: 34.5; 36.5 _ _GH _ +. 69.8; 70.0; 70.2;

" ² * 71.8; 72.1; 72.7;

Signal splitting by% quadrupole moment

Tetraallylamine monombromide (colorless crystals) was prepared by quaternization of triallylamine with allyl bromide. The procedure is as described in Example 1, and prepares 50 ml of solution 1. by dissolving 12.91 g (50 mmol) Tetraallylammoniumbromid in tap water forth »The solutions 2» and 3 * prepared according to Example 2b »

The reaction mixture warmed from '26 ⁰ G to 42 ⁰ C for 50 minutes and kept this temperature for 10 minutes, then gradually dropped again.' The pH remained 7 throughout the dropping time 7 'The colorless reaction solution became dry'evaporated; a colorless crystal mass was obtained which, in addition to the betaine mixture, also contained sodium bromide, sodium sulfate and sodium sulfate,

1 °>

A ^ C NMR spectrum prepared from this Krfetallmasse rejected the above-mentioned chemical shifts »

Comparison of the ^ G-ITMR spectrum with that of the DD application: WP C 07 D / 222 5β3. prepared 1,1,3-trimethyl-4-sulfo-methyl-pyrrole idiniumb et a shows that the chemical shifts are virtually identical. The 1,1,3-trimethyl-4-sulfomethyl-pyrrolidinium-betaine can be considered as a model substance.

Example 4

3-methyl-iT-tetradecyl-1- (3 ⁱ sulfopropyl) -4-sulfomethyl-1 pyrrolysine idinium-b et ain.

n-Tetradecyl-triallylammonium bromide was prepared by reacting n-tetradecyl-diallylamine with allyl bromide. 1.26 g (0.01 mol) of ITa ₂ SO- are dissolved in 300 ml of tap water in a boiling flask with stirrer, thermometer and air inlet tube. A solution of 6.3 g (0.05 mol) of Ha is simultaneously added dropwise to this solution ₂ SO ₃ and 29.4 g (0.1 mol) of 35.54% NaHSO ,, - solution with tap water made up to 200 ml and a solution of 20.73 g (0.05 mol) of n-tetra-decyl triallylammonium bromide, dissolved in tap water, to 200 ml solution. During the dropwise addition, air is introduced and stirred vigorously to obtain as fine a distribution of the oxygen as possible.

Palls the reaction mixture here foams too much, you can foam formation by addition of z. B · isopropanol moderate · In the dropping time of approximately _c 1.5 hours, the temperature increases by about 10 * ⁰ Co

It is evaporated and extracted from the solid reaction residue, the Sulfobetainsulfonat with ethanol.

Recrystallization of the crude product from ethanol gives colorless crystals

Mp: 248 - 253 ⁰ G; from 190 ^° C. slow decomposition Yield: 90%

Claims (6)

Erfindungsanspriiche 1 · A process for the preparation of novel SuIfobetainsulfonaten d-2r Ξ. "'~ * ^0" ΘΠΙ2ΪΏ.5' Ij ^{η 1} * QT ¹⁰ '"TI I ₃ - CH - CH - CH ₂ --SO " 2. Method according to item 1, characterized in that aerated acid is used as the oxidizing agent in the presence of traces of metal ions of the 1 ", 5 *" T * or 8 "lifting group of the Periodic Table of the Elements" 2 ^WXA 2 CH ₂ CH TD * D R ₁ R ₂ in which R 1 is hydrogen or alkyl having 1 to 22 C atoms, of which the C 2 -substituted atom may optionally be substituted by one hydroxyl group, branched or straight-chain, and R p is 3'-sulfopropyl or R-. and R ₂ including the nitrogen atom to a 3-methyl ~ 4-sulfomethyl or 3 ~ 8ulfomethyl-4-niethyl-pyrrolidinium ring may be closed, characterized in that one on Allylainmoniumsalze with more than two allyl substituents in solution in the pH range of 2 to 9 at the same time salts of sulfurous acid and an oxidizing agent act. 3 * Process according to item 1, characterized in that peroxodisulfates, hydrogen peroxide, organic peroxides or hydroperoxides, hitrates or nitrites are used as the oxidizing agent * 4. Process according to point 1-3 »characterized in that the reaction takes place in the temperature range of 5 - 100 ⁰ C, 5 »method according to item 1-4, characterized in that the solvent used is water or water-alcohol mixtures become· 6 * Procedure according to point 1-5 »characterized in that during the implementation of a good mixing *