DD274332A3 - PROCESS FOR THE PREPARATION OF NEW SULFOBETAINES OF AMMONIOCARBONE ACID AMIDES - Google Patents

Abstract

The invention relates to a process for the preparation of sulfobetaines having a carbonamide group as an additional polar structural element. Synthesis building blocks for sulfobetaines of general formula I (R1 and R2H or alkyl, R3 and R4 are alkyl or hydroxyalkyl radicals, R5 is hydrogen, alkylaminocarbonyl radical or alkyl radical with n0 to 3) are dialkylallylamines, halocarboxylic acid esters, amines and hydrogen sulfites, which are partially variable in the process steps for Implementation be brought. Isolation of the intermediates is not required. The reactions are technologically simple to carry out, the yields are very high. Sulfobetaines of ammonium carboxylic acid amides are useful as conductive coating and antistatic materials. Long-chain substituted compounds of the class of compounds have valuable surfactant properties, which allow their use as a component of detergents and cleaners, as flotation or as emulsifiers.

Description

For this 2 pages formulas

Field of application of the invention

The invention relates to a process for the preparation of novel sulfobetaines, which are derived from Ammoniocarbonsäureamiden and are described by the general formula I.

In the general formula I, Fl _{1 is} hydrogen, straight-chain or branched alkyl radicals having up to 22C atoms, R _{2 is} hydrogen or short-chain alkyl radicals having up to 4C atoms, R ₃ and R _{4 are} identical or different short-chain alkyl radicals of the hydroxyalkyl radicals 1 to 4C atoms or oxyethylene radicals, Γ15 represents hydrogen or alkylaminocarbonyl radicals or alkyl radicals having up to 22 C atoms and η numbers from 0-3.

Internal salts of general formula I can generally be used to increase the conductivity, e.g. B. as an antistatic coating agent. If one of the substituents Ri and R _{6 is} long-chain (8-22 C-atoms), these sulfobetaines moreover have valuable surfactant properties.

Characteristic of the known technical solutions

There is already known a process for the preparation of sulfobetaines which contain a carboxamide group in a substituent of the quaternary N atom. In these known compounds, the carboxamide group is in the reverse order of -CO- and -NH-containing. They are derivatives of 1,2- or 1,3-diamines and have the general formula II, in which R _{6 is} alkyl, R ₇ and R _{8 are} methyl or hydroxyalkyl groups and η is 2 or 3. Te side of the general formula II have, for example, of the known compounds the best Kalkseifendispergiervermögen so far (VV.M. Linfield, J. Amer Oil Chem Soc 55 [1970] 87, FDSmith and WMLinfield, ibid 55 [1978] 741).

The said process for preparing the compounds of the general formula II has considerable disadvantages for industrial use: it requires asymmetrically dialkylated 1,2- or 1,3-diamines as starting materials and uses the highly carcinogenic propane sultone to build up the quaternary ammonium structure.

Object of the invention

It is the object of the present invention to develop a method which avoids the mentioned disadvantages. The use of the carcinogenic Propansultons as Syntheseesausein should be eliminated and the use of unsymmetrical aliphatic diamines avoided.

Presentation of the essence of invention

The object is achieved by a process for the preparation of new Sulfobetainen of Ammoniocarbonsäureamiden the general formula I, in which. R ₁ and R ^ are hydrogen, straight-chain or branched alkyl radicals having up to 22C atoms, R ₃ and R _{4 are} identical or different short-chain alkyl radicals having 1 to 4C atoms or hydroxyalkyl radicals having 2 to 3C atoms or

Oxyethylene, R ₅ alkyl radicals having up to 22 carbon atoms or hydrogen or Alkylaminocarbonreste and η gan * e numbers from 0 to 3, by quaternized ertindun & according to dialkylallylamines of the formula III with halocarboxylic esters of the formula IV and the resulting quaternary ammonium compounds V with amines of the formula VIII and hydrogen sulfite are reacted.

The substituents R ₁ to R ₅ and η always have the meaning given in formula I. The reaction of the quaternary ammonium compounds can be carried out both first with hydrogen sulfite and then with amines of the formula VIII and also first with an amine of the formula VIII and then a bisulfite addition.

There are always compounds of formula I.

The DD-PS 136497 readily accessible dialkylallylamines, halo fatty acid esters, alkylamines and hydrogen sulfites are used as synthesis building blocks.

In some cases, the intermediate V can also be obtained by quaternization of Ν, Ν-dialkylamino acid esters with allyl halide. Surprisingly, it is possible without any disadvantage to carry out the process steps up to the amide Vl without solvent and without isolation of the intermediates, optionally also continuously. As a possible reaction medium are mainly water, alcohols and water-alcohol mixtures used. The formation of quaternary ammonium salts usually requires reaction temperatures between 20 and 100 ⁰ C, the production of acid amide formation takes place in the same temperature range. Hydrogen sulfite addition to sulfobetaine occurs under the simultaneous catalytic action of atmospheric oxygen and transition metals, preferably ions of iron, copper or manganese in the pH range 4-8. The optimum reaction temperatures are in the range 20-50 ° C; however, the temperature can be increased if the solubility conditions require it.

The formation of addition-capable sulfite anion radicals can also be initiated with other oxidants instead of the system oxygen / transition metal; For example, salts of peroxodisulfuric acid, alkyl peroxides, acyl peroxides or hydrogen peroxide are suitable. The action of several oxidants as radical formers may also be advantageous.

The novel sulfobetaines I according to the invention exhibit excellent surfactant properties. Surprisingly, they surpass in their lime soap dispersibility the hitherto known type of formula II, in which the acid amide bond -CO-NH- is arranged in a different order. This arrangement also leads to excellent adhesion to plastic surfaces; this unexpected favorable property distinguishes the new sulfobetaines favorably from the known representatives of the class of compounds.

An advantage of the procedure according to the invention is to be considered that the intermediate V makes a variety of sulfobetaines accessible with carbonamide groups, without the carcinogenic propane sultone must be used.

embodiments

example 1

N- (3-sulfopropyl) -N, N-dimethy! -Ammonio-acetic acid-dodecyl-amide

N-Allyl-N, N-dimethyl-arr-.monio-acetic acid methyl ester chloride:

850 g (10 mol) of dimethylallylamine are placed in a reaction vessel. 1085 g (10 mol) of methyl chloroacetate are added dropwise thereto. During the dropping, the temperature rises slowly and is maintained between 60 and 70 ° C by occasional cooling. The reaction product is clearly transparent and viscous in terms of quantitative conversion achieved after about 30 minutes.

N-Allyl-N, N-dimethyl-ammonio-acetic acid dodecylamide chloride:

The resulting methyl ester chloride is added dropwise with 1853g (10 moles) of dodecylamine (cocoamine), such that the exothermic reaction of amide formation at a reaction temperature of 70 to 8O ⁰ C can be maintained. After about 30 minutes, the reaction is complete, and we obtain a highly viscous product in quantitative yield of pH 7.

3788g of dodecylamide chloride? are diluted with 11.36 kg of tap water to a 25% solution (solution I).

Then, 950 g (5 mol) of sodium metabisulfite Na ₂ S ₂ O ₅ and 126 g (1 mol) of sodium sulfite Na ₂ SO _{3 are dissolved} in 14.07 kg of tap water (solution II).

126 g of Na ₂ SO ₃ (1 mol) are dissolved in 5 liters of water and placed in a stirred vessel with an air inlet tube. At room temperature, the solutions are added dropwise with stirring and simultaneous introduction of air! and Il siinultan too. Since the reaction mixture is highly schiiumt, the foaming is moderated by the addition of about 1.5 liters of Isopropa.iol. After a dropping time of about 90 minutes, the temperature of the reaction mixture increases by 1O ⁰ C; the pH-who; During the reaction, it remains at 7. After the temperature has dropped, stirring is continued for 30 minutes under intensive aeration. The conversion of the dodecyl-amide chloride used is now quantitative. The weakly yellow sulfobetaine solution still contains salts (NaCl, Na ₂ SO ₃ and Na ₂ SO ^, of which can be separated by concentration and extraction of the product with ethanol (melting point

Example 2

N- (3-sulfopropyl) -N, N-dimethyl-a.Timonio-acetic acid heptylamid

O ₃ S-CH ₂ -CH ₂ -CH ₂ -N (CH 1 -CH ₇ -CO-NH-C ₇ H _1. ,

0.1 mol of N-AIIyI-N, N-dimethyl-ammonio-acetic acid methyl ester chloride prepared according to Example 1 are reacted in a corresponding procedure instead of cocoamine with 0.1 mol of n-heptylamine and then with bisulfite solution / sodium sulfite solution as described in Example 1 in the Converted sulfobetaine; Melting point Z> 178 ° C.

Example 3 N-IS-sulfopropyl-N, N-dimothyl-ammoniacic-acetic-n-hexylamide

-O ₃ S-CHj-CH ₂ -CH ₂ -N (CHj) ₂ -CH ₂ -CO-NH-C ₆ H ₁₃

0.1 mol of N-AIIyI-N, N-dimethyl-ammonio-acetic acid methyl ester chloride prepared according to Example 1 are reacted in a corresponding procedure instead of cocoamine with 0.1 mol of n-hexylamine and then with hydrogen sulfite / sodium sulfite solution as described in Example 1 in the Converted sulfobetaine; In this case, an addition of isopropanol is not required as a foam reducer; Melting point Z> 178 ° C.

Example 4

N- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid-n-butylamide

-O-S-CH ₂ -CH ₂ -CH ₂ -N (CH ₃ I ₂ -Ch ₂ -CO-NH-C ₄ H ₉

0.1 mol of Example 1 prepared, N-AIIyI-N, N-dimethylammonio-acetic acid methyl ester are reacted in a corresponding Arboilsweise instead of cocoamine with 0.1 mol of n-butylamine and then with hydrogen sulfite / sodium sulfite solution as described in Example 1 in the sulfobetaine converted, with an addition of isopropanol to avoid foam is not required; Melting point Z> 213 ° C.

Examples

N- (3-sulfopropyl-N, N dimethyl-ammonio-acetic acid-isopropyl-amide

"O ₃ S-CHr-CH ₂ -CH ₂ -N (CH ₃ J ₂ -CH ₂ -CO-NH-CH (CH ₃ I ₂

The procedure is as in Examples 1-4 beschriebeil using isopropylamine for the preparation of the amide with otherwise the same procedure. Sales are also quantitative here. Melting point Z> 237 ⁰ C. The melting point of the corresponding n-Propylderivats Z is> 18S ° C.

Examples

N- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetamide

¹³ C NMR spectrum

(D ₂ O, external standard TMS); the numbers on the atomic symbols correspond to the chemical shifts in

48.9 20.0 63.8 53.7 65.4 168.0 "O ₃ S-CH ₂ -CHi-CHz-NtCH ^ CHj-CO-NHj

Prepared in 0.1 mol of Example 1 N-AIIyI-N, N-dimethyl-amrnonio-acetic acid methyl ester chloride are introduced to prepare the Amiastufe at least 0.1 mole of ammonia. The resulting amide is converted into the sulfobetaine according to the procedure of Examples 1-4; Melting point Z> 268 ^° C.

Example 7

N- (3-sulfopropyl) -N, N-dimethy! -Arnmonio-acetic acid-n-hexadecyl-amide

-O ₃ S-CH ₂ -CH ₂ -CH ₂ -NICH ₃ I ₂ -CHr-CO-NH ^ C ₁₆ H ₃₃

10 moles of N-allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride are prepared as described in Example 1, and this is mixed in portions with solid n-hexadecylamine in the temperature range of 70 ° C.-90 ° C. over a period of 30 minutes with stirring syrup-containing opaques obtained Hexadecylamidchlorid is dissolved boi 45 ⁰ C in isopropanol-containing water and the solution according to the procedure of Example 1, but be 40 ^c C, further reacted to sulfobetaine, melting point 123ΧΙ 27 ⁰ C. The conversion is quantitative.

In the preparation of the analogous product of C ₁₆ / C ₁₈ -Feltamingemisch veifährt one completely. Melting point of this sulfobetaene mixture: 81 "C-86 ^e C.

Example 8 N-O-sulfopropyl-N, N-dimethyl-ammonio-malonic acid di-n-dodecylamide

N-AlII.-N, N-dimethyl-ammonio-malonic acid diethyl ester bromide:

85 g (1 mol) of dimethylallylamine are dissolved in 200 ml of ethanol. To this solution is added dropwise with stirring at 30 ^c C 239.1 g I'i mol) of diethyl bromomalonate and stirred for a further 2 hours at 80 ° C according to. N-Allyl-N, N-dimethyl-ammonio-malonic acid di-n-dodecyl-amide-bromide:

The ethyl ester bromide solution obtained above is washed with 370.6 g (2 moles) of r. Oodecylamine (cocoamine) as described in Example 7 at 70 ° C-80 ^c C reacted to complete the reaction for 2 hours at this temperature is stirred The homogeneously catalyzed bisulfite addition to improve the solubility in the presence of n-butanol at 50 ° C-60 ° C made.

After cooling the reaction mixture, the sulfobetaine precipitates and can be recrystallized from ethanol; Melting point: 108 ^° C-IM ⁰ C.

Example 9

N- (3-Sulfopropy!) - N, N-dimethyl-ammonio-acetic acid-n-propylamide

-O ₃ S- (CH ₂ ) TN (CH ₃ I ₂ -CH ₂ -CO-Nh-C ₃ H ₇

The procedure is as described in Examples 1-4 using n-propylamine for the preparation of the amide with otherwise the same procedure. Sales are also almost quantitative. Melting point: Z> 230 ° C.

Examples 10-14

N- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid alkylamides or dialkylamides

-O ₃ S- (CH ₂ ) JN (CH ₃ Ir-CH ₂ -CO-NR ₁ R ₂

Prepare N-Allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloro as described in Example 1 and, at a suitable temperature, add this with dom alkyl or dialkylamine to the corresponding N-allyl-N, N-dimethyl- Ammonioessigsäureamid chloride to

 The synthesis of the sulfobetaines is carried out according to the examples given in Table 1.

Table 1:

example R rj manufacturing melting point after example "C. 10 H C ₁ SH ₃₃ ZC ₁ BH ₃ ? 7 81-86 11 H C ₁ BH ₃₇ 7 135 12 C _1B H ₃₇ C ₁₈ H ₃₇ 7 142 13 H C ₆ H) ₁ 1 .83 14 C ₆ H ₁₁ C ₆ H ₁₁ 1 16 /

Example 15 N-.beta.-sulfopropyl-N, N-diethyl-ammonio-acetic acid-n-tetradecylamide

-O ₃ S- (CH ₂ ) JN (C ₂ H ₆ I ₂ -CH ₂ -CO-NH-C ₁₄ H ₂₁ ,

11.4 g (0.1 mol) of allyl diethylamine are dissolved in 50 ml of ethanol. 1C, 85 g (0.1 mol) of methyl chloroacetate are added dropwise to this solution while stirring, and stirring is continued for 2 hours in AO'C . The resulting methyl ester chloride is mixed with 21.3 g (0.1 mol) of tetradecylamine and stirred for a further 2 hours. After completion of the reaction, the ethanol is i. Vak. and the residue - the N-allyl-N, N-diethyl-ammonio-acetic acid-n-tetradecylamide - is reacted in a molar ratio to the corresponding sulfobetaine as described in Example 1. After completion of the reaction, work-up and recrystallization from ethanol to obtain a compound which melts at> 160 ° C with decomposition.

Example 16

a-lN-O-SulfopropyD-N.N-dimethyl-ammonio-lpropansäure-n-tetradecylamid

-O ₃ S- (CH ₂ ) j N (CH ₃ ) ₂ -CH (CH ₃ hCO-NH-C ₁₄ H ₂₉

The preparation of this compound is carried out analogously to that of Example 7. Instead of the chloroacetic methyl ester, the α-Brompropionsäuremethvlester is used. The reaction takes place in equal molar ratios, as described in Example 7. The resulting compound melts after recrystallization from ethanol at> 156 ⁰ C with decomposition.

Example 17 u. 18

NO-sulfopropyl- ^1- N, N-dimothyl-ammonio-n-anilo-di-n-alkylai-nide

-O ₃ S- (CH ₂ ) ₃ -N (CH ₃ ) ₂ -CH ₂ - (CO-NHR _I ) ₂

The synthesis of Examples 17 u. 18 is carried out as described in Example 8. Instead of n-dodecylamine n-tetradecylamine or n-hexadecylamine is used.

Table 2:

Example R ₁ melting point ( ⁰ C)

17 C ₁₄ H ₂₉ 126-132

18 C ₁₆ H ₃₃ 130-140

Example 19 and 20

N- (3-sulfopropyl) -N, N-dimethyl-arnmonio-succinic acid-mono-n-alkyl-amide sodium salt

COONa

N-allyl-N, N-diniethyl-ammonio-succinate chloride

8.5 g (0.1 mol) of dimethylallylamine are dissolved in 50 ml of ethanol. 20.8 g (0.1 mol) of diethyl chlorosuccinate are added dropwise with stirring at 50 ° C., followed by stirring at 80 ° C. for a further 4 hours.

N-allyl-N, N-dimethyl-ammonio-succinic acid-mono-n-alkylamide chloride

The ethyl ester chloride solution obtained above is treated with 0.1 mol of n-decylamine (Example 19) or 0.1 mol of n-hexadecyl / n-octadecylamine mixture (molar ratio 1: 1) (Example 20) as described in Example 7 at 70 ° C-80 ° C umgeseiz · ge is stirred to complete the conversion for 3 hours at this temperature.

The homogeneously catalyzed bisulfite addition is carried out to improve the solubility, especially in Example 20, in the presence of n-butanol at 40 ° C.

After the reaction has ended, the pH of the solution is adjusted to 10 with industrial sodium hydroxide solution, and the mixture is heated with stirring to 70 ° C.-80 ° C. for 2 hours. The Roak ^f io isgemisch evaporated to dryness, the residue extracted with 80% aqueous, boiling ethanol. After filtration of the insoluble inorganic radical, the abovementioned compound crystallizes on cooling.

labeile 3: Ri Melting point ("C) example C "Ä" > 160 (Z)> 178 (Z) 19 20

Example 21 N- (3-sulfopropyl) -N, N-dimethyl-ammonio-succinic-di-n-decylamide

-O ₃ S- (CH ₂ ) JN (CH ₃ J ₁ -CH-CH ₂ -Co-NHC ₁ OH ₂₁ CO-NHc ₁₀ H ₂₁

The preparation of diethyl N-allyl-N, N-dimethyl-ammonio-succinic acid chloride is carried out as described in Example 19. The egg-containing ester chloride solution (0.1 mol) is reacted further with 0.2 mol of n-decylamine; the reaction conditions correspond to those described in Example 19.

The homogenkEtalysierte bisulfite addition is carried out in the presence of n-butanol at 4O ⁰ C. The reaction mixture is evaporated to dryness, extracted with boiling ethanol and recrystallized from ethanol. The resulting compound melts with decomposition at 162 ° C.

Example 22 a-IN-O-Sulfopropyl-N, N-dimethyl-ammonio-ladipic acid mono-n-tetradecylamine sodium

-O ₃ S- (CH ₂ ) _r -N (CH ₃ ) ₂ -CH- (CH ₂ ) ₃ -CO-NHC _M ! -I ₂₉ COONa

The preparation is carried out by reacting 8.5 g {0.1 mol) of dimethylallylamine and 25.3 g (0.1 mol) of a-Bromadipinsäuredimethyleiter in 50 ml Ethanoi and further reaction and work-up as in Example 19 u. 20 described. Melting point:> 146 ^° C. (Z).

Example 23 u. 24 2- [N- (3'-sulfopropyl) -N, N-din) ethyl-ammonio) piOpan-tricarboxylic acid mono-n-alkylemide-di-sodium salt

COONa

-O ₃ S- (CHj) ₃ -N (CH ₃ I ₂ -C-CH ₂ -CO-NHR ₁ CH ₂

COONa

The preparation is carried out by reacting 8.5 g (0.1 mol) of dimethylallylamine and 29.5 g (0.1 mol) of 2-chloro-propanetricarboxylic triethylestor-1,2,3 in 50 ml of ethanol and further reaction and workup much in Example 19 and 20 described.

Table 4: CioHji C16H33 / CUH37 Melting point CC) example 140 (Z) 120 (Z) 23 24

Example 25 2- [N- (3'-Su fopropyl!) -N, N-dimethyl-ammonio] -propane-tri ^r: 3rbonsäure-tridecyl

O-NHC ₁₀ H ₂ ,

H ₂ O-NHC "Hj,

Tue? This compound is prepared analogously to that of Example 21. Here, however, 0.3 mol of n-decylamine are used. Melting point: 156 ⁰ C (Z).

Example 26

Comparative determination of the lime-soap dispensing power The incorporation is carried out in accordance with GDR standard TGL 22254 Part 1 (Group 482) of July 1967 (Determination of oil-soap-dispersing property). Callus soap dispersibility is the ability to prevent lime soap from flocculating or agglomerating and to keep it in such fine dispersion for a certain period of time that it does not precipitate on textiles or other surfaces.The limit to the resistance of soap solutions to hard water is The amount of the product to be tested is taken as the basis for calculation.The lime soap dispersibility K is stated in% of product, based on the sodium oleate used as the standard fatty substance.

.. _o amount of product used ing ing ·

Amount of sodium oleate used

that is, low percentages indicate good lime soap dispersancy over sodium oleate. The determination was made at a water hardness of 30 ° dH.

100%

Sodium oleate

(Standard reference substance) C ₁₆ H ₃₁ CONH (CH ₂ ) JN (CH ₂ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ comparative substance according to Linfieii et al., J. Amer. Oil Chem. Soc.

55 (1978) 8?; 55 (197) 741 55.2%

Table 5 lists the values for the calcubability dispersibility of Examples 1-25 described. Table 5:

^1V

? + Ϊ3

H - 0 - (CH ₀₎ - ClIRp; - II - (CH ₂ ) ₃ - SO ₃

eilJi <- J ->

η ^ ^U 2 C ₁₂ H ₂₆ ¹ R ₃ R4 Rt η Kalkseifendispergier- example R C ₂ H ₁ S assets (K) -% C ₆ H ₁₃ CH ₃ CH ₃ H 0 60 1. H CH ₉ CH ₃ CH ₃ H 0 80 Second H i C ₃ H, CH ₃ CH ₃ H 0 110 * Third H H CH ₃ CH ₃ H 0 120 * 4th H CeH ₃₃ CH ₃ CH ₃ H 0 160 * 5th H C ₂ H ₂₅ CH ₃ CH ₃ H 0 ? 20 * L. H C ₃ H ₇ CH ₃ CH ₃ H 0 30 7th H C ₁₆ H ₃₃ ZC ₁₈ H ₃ , CH ₃ CH ₃ C ₁₂ H ₂₆ NHCO 0 16 8th. H C ₁₈ H ₃ I CH ₃ CH ₃ H 0 150 * 9th H C ₁₈ H ₃₇ CH ₃ CH ₃ H 0 30 :O. H CtH ₁₁ CH, CH ₃ H 0 36 11 Il CH ₃ CH ₃ H 0 26 12th C ₁ RHj; CH ₃ CH ₃ H 0 100 * 12th H

example

Lime soap dispersibility (Κ) - °, Ό

14th C ₆ H ₁₁ C ₆ H ₁₁ CH ₃ CH ₃ H 0 70 15th H C ₁₄ H ₂₉ C ₂ H ₆ C ₂ H ₅ H 0 40 16th H C ₁₄ H ₂₉ CH ₃ CH ₃ CH ₃ 0 40 17th H C ₁₄ H ₂₉ CH ₃ CH ₃ C ₁₄ H ₂₉ NHCO 0 10 18th H C ₁₆ H ₃₃ CH ₃ CH ₃ C ₁₆ H ₃₃ NHCO 0 8th 19th H C ₁₀ H ₂₁ CH ₃ CH ₃ COONa 1 60 20th H C ₁₆ H ₃₃ ZC ₁₈ H ₃₇ CH ₃ CH ₃ COONa 1 3 2 \. H C ₁₀ H ₂₁ CH ₃ CH ₃ C ₁₀ H ₂₁ NHCO 1 30 22nd H C ₁₄ H ₂₉ CH ₃ CH ₃ COONa 3 40

II

ti

KaOOC GII ₃

GII ₉ - C - ' ^h il - (GlL) ₇ - SO./ GH ₀ GIu COONa

70

0 Hn 0OG ul - U I I t G - CIL. -C- ^r IT I Glu CI

GOOHa

^1V N - G - ClI ₂ -

- ^{1 year} -

ι ι

ClL, CiI

- SO ₃

20

The calcium carbonate dispersibility is used as a detergent for surfactants. These examples are compounds which, due to their structure (no hydrophobic or short hydrophobic hydrocarbon oil in the molecule) have no or hardly any surfactant character. Nevertheless, these types of compounds show lime soap dispersibility that was unexpected in terms of their molecular structure.

27 H 3 3-2 2

OR ₅ # 3

Il II _φ θ

N - C - (CW ₂ J _n - CH - _N - (CH ₂ ) - SO ₃

R

NH- [CH ₂ ) _n -

so:

> N- CHL-CH = CH ₂

Alkyl-O ^

^ C- (CHL) -CH-HaI O

?H

Akyl-0

ι ι

// - (CH ₂ ) _n - CH-N-CH ₂ -CH = CH ₂ Hal

for K H

CH-N-CH ₂ -CH = CH ₂ Hal

R

Alkyl-O

N - CH ₂ --CH ₁ --CH ₂ - SO ₃

rr

NH

Claims (6)

1. A process for the preparation of new Sulfobetainen of Ammoniocarbonsäureamiden of general formula I ₁ in which R ₁ and R _{2 is} hydrogen, straight or branched alkyl radicals having up to 22 carbon atoms, R ₃ and R _{4 are the} same or different short-chain alkyl radicals with 1 to 4C atoms or hydroxyalkyl radicals having 2 to 3C atoms or oxyethylene radicals, R _{5 is} alkyl radicals having up to 22 carbon atoms or hydrogen or alkylaminocarbonyl radicals and η is integers from 0 to 3, characterized in that dialkylallylamines of the formula III are reacted with halocarboxylic acid esters of the formula IV quaternized and dia resulting quaternary ammonium compounds V are reacted with amines of formula VIII and hydrogen sulfite, wherein the substituents R ₁ to R ₅ and η in the formulas have the abovementioned meaning. 2. Method nacn item 1, characterized in that after the quaternization first carried the Hydrogensulfitadditon and then the reaction with amines of the formula VIII. 3. The method according to item 1, characterized in that carried out after the quaternization, the reaction with amines dor formula VIII and then the reaction is carried out with hydrogen sulfite. 4. The method according to item 1-3, characterized in that the reaction at 20-100 ⁰ C is performed. 5. The method according to item 1-4, characterized in that the Hydrogensulfitaddition in the pH range of 4 to 8 is made. 6. The method according to item 1-5, characterized in that serve as a solvent, water, alcohols or water-alcohol mixtures.