DD224844A1 - PROCESS FOR PREPARING NEW 1,1-DIALKYL-3,4-DISULFOMETHYL-PYRROLIDINIUM BEVERES - Google Patents

Abstract

The invention relates to a process for the preparation of 1,1-dialkyl-3,4-disulfomethyl-pyrrolidinium betaines, a new type of sulfobetaine sulfonates. Compounds of this type can be used as valuable surfactants which retain their surfactant activity over a wide p H range when at least one of the substituents on the nitrogen is long chain. For the preparation of the compounds of the general formula I diallylammonium salts of the general formula II according to the invention are reacted with two molar equivalents of a Hyhdrogensulfits and one molar equivalent of a Peroxodisulfats, wherein a p H value range of 2 to 4 is observed. Instead of the peroxodisulfate alone, combinations of peroxodisulfates with customary oxidizing agents, eg. As hydrogen peroxide can be used. In reaction times of a few minutes, the compounds of general formula I can be prepared in quantitative yield. formula

Description

Title of the invention

Process for the preparation of new 1 _# 1-dialkyl-3,4-disulfomethyl-pyrrolidinium etaines

Field of application of the invention

The invention relates to a process for the preparation of novel 1, 1-glycyl-3,4-disulphomethylpyrrolidinium betaines of general formula I,

'CUS - CH ₀ - CH - CH - CH ₀ - SCL ο 2 t 3 .2

^H 2 ^C / ^H 2 M ⁺

N l ' ^V 2

in which

12 R and R independently represent hydrogen, straight-chain or branched alkyl radicals having 1 to 22 carbon atoms, never by the groups -CO-NH- or -MH-CO - can be och sn un C = rb.r, hydroxyalkyl or Cxyalkylenrests or Ring closed substituents can be and

M is a cation, preferably Na "" K, NH or H,

The compounds are sulfobetaines with an additional anionic group and, because of their charge-carrying groups, can be used as conductive salts, as dispersible coating agents or for the preparation of salts. Long-

Ί '-' - ^: i: - ·; "" J-J ü i ϊ. ^! Ϊ

Chain-substituted substituents of the new class of compounds have good surfactant properties. They retain their transiting effect in a wide pH range *

Characteristic of the known technical solutions

Compounds of structure I are new; Only 3-methyl-4-sulfomethyl-pyrrolidiniumbetaine (DD-VVP 154 444) and derivatives of this ring system with an additional sulfopropyl group as substituted on the nitrogen atom (DD- ¹ WP 200 739) are known. In these known Sulfobetainsulfonaten the introduction of an additional acid residue was carried out with the aim to improve the solubility of the underlying Sulfomethylpyrroli'diniumbetaine. This route, as well as the synthesis of another group of sulfobetaine sulfonates (0, Amer Oil Chemists * Soc 555: 741, 1978), has the disadvantage that the introduction of a further hydrophilic acid group takes place by sulfopropylation, ie with the acid group simultaneously a hydrocarbon radical must be introduced »

Zial of invention

It is the object of the invention to combine the sulfocyclization reaction of diallyl ammonium salts with the introduction of a second sulfonic acid group so as to obtain a new type of sulfobetaine sulfonates *

Presentation of the invention

The object of the invention is achieved by using, in accordance with the invention, solutions of dialkylammonium salts of the general formula II,

1 2 -

in the R and. R have the meanings and X is an anion, preferably bromide or chloride, ia pH range from 2 to a maximum of 4 with hydrogen sulfite and psroxodisulfate in a molar ratio 1: 2: 1 to 3, 4-Oisuifoiäthylpyrrolidiniurabetainen the general Formula 1 to be implemented »

= HC S 1 R * / CH = CH, - 2 f. I H ₀ C CH ₂ * "\ + N R ²

+ 2 HSO ₃

w'O - Πϋ - ΓΙ o "™ ^^ '-Π -' -"

3 2 j, 2

H ₂ C 3H 2 to ^ ^ *

₉ + 2 HSO /

R ~

T X

Triggered by this procedure, the reaction is fundamentally different in progress and final product is the corresponding 3-sulf ometny 1-py r rolidiniurnbe tainen (DD-WP 154 444} leading implementation with only i moi Hydrogenaulfit _/; 7 ol Diallylarnmoniunisa Iz and! Initiator.g with air oxygen / Q'oergangsme tali, who incorporation of a second sulfonic acid group under these conditions is surprising and has not been found in this form in other compound kassan yet *

The reaction "is sospecific ar, which is bound by peroxodisuifsten." Other per-compounds, for example, Vasse rs toffee roxid or ^ liolipe rbora te, solve a certain problem.

3 ^: ~ l ~ i: z \ i sulphate, It is "3 -" - similar, inacas 11a ~

Preferably, in accordance with the invention, the diallylammonium salts are mixed with 2 mol of hydrogen sulfite in aqueous solution, adjusted to pH 2 (up to nsax, 4) and the peroxodisulfate is introduced with stirring, with the progressing reaction being characterized by rapid heating of the Reaction mix reveals that can come to the boil,

Long chain substituents give Pyrrolidiniumbetainsulfonate with surfactant properties that precipitate in the described procedure from the Reaktionsgeraisch and can be easily isolated and recovered in pure form. In other cases, the worked-up sulfuric acid is neutralized before the work-up and the Setainsulfonat extractively separated from the inorganic salt fraction in case of need *

In a suitable apparatus, the process according to the invention can be carried out continuously if the components are combined in the stated molar ratio at the beginning of a residence time zone.

embodiments

The "" "C-NMR spectra shown in the following examples were measured in DpQ with TMS as external standard. The numbers given on the C atom symbols of the structural formulas correspond to the chemical shifts for the respective cis compounds with respect to the sulfomethy! groups in the 3,4-position in ppm.

Example 1

Sodium-l, l-dimethyl-3,4-disulfomethyl-pyrrolidiniurabetain

1 2 (R = R = CH ₃ in the general formula I) from dimethyldiallylammonium chloride

349.2 g (1 mol) of 46.3% technical dimethyl diallyl ammonium ammonium chloride solution, 533.6 g (2 mol) of 39 % strength technical sodium hydrogen sulfite solution with an iron content of 9 mg / m are provided in a mixing flask equipped with stirrer, reflux condenser, dropping funnel and thermometer. mol solution and 30 g of 37% hydrochloric acid mixed together to form a homogeneous solution of pH 2.1. To oer thus prepared pale yellow initial solution is added a 40% aqueous sodium peroxodisulfate solution consisting of 238.1 g (1 mol) of sodium peroxodisulfate and 357.15 g of water was prepared, added to the extent that the reacting solution in about, a Hinute , starting at room temperature, heated to boiling. During this time the solution had turned red. * The metered addition of the persulfate solution is continued rapidly so that the heat of reaction of the solution boiling from 103 C can be easily removed by evaporative cooling, which required a total of 5 minutes.

vpxqdi, After about three-quarters of the Pe'risulfatlösung had dosed, brightened up the Raaschelösung increasingly and

was at the end finally yellow-green. An H-NMR spectrum prepared from the solution confirmed the quantitative and selective conversion of the diallylammonium salt into the sulfobetaine sulfonate. After neutralization of the solution with 33 % caustic soda, ice salts flocculated as ferric hydroxide using technical chemicals contained therein and could be filtered off together with most of the sodium sulfate. A C-NMR spectrum prepared from the colorless filtrate showed that the sulfofetainesulfonate is present mainly in the cis configuration with low transubstantiality,

50.9 36.3 36.3 50.9.

0 _o S - CH "- CH CH - CH ₀ - SO-,"

^{3 2} Ί \ 2 3

χ H ₀ C CH ₀ x'Na *

^ ²

14 ³

ο H ₃ C CH ₃ ο

14 70.8; 70.7; 70.5, Signaling by N-quadrupole moment

56.1; 55.9; 55.7 / 54.5; 54.3; 54.1 '

The N-CH groups are not equivalent; signal splitting

14 by N-quadrupole nucleotide

trans compound 70.2 (N-CH ₂ ); 53.7 (N-CH ₃ ); 40.2 (CH),

If the Sulfobetainsulfo.nat completely separated from its inorganic .Addition salts and the free 1,1-Oimethyl-3-sulfonic acid methyl-4-sulfoinethyl-pyrrolidiniumbetain be isolated, can measure as follows procedure: After concentration of the above-obtained Raaschelösung to dryness, is added The resulting salt residue with the sufficient amount of concentrated hydrochloric acid and worked through it, filtered from the undissolved sodium salts and the hydrochloric acid solution of sulfonated sulfonic acid under reduced pressure to dryness. Shortly thereafter, the sulfonic acid begins to crystallize; by the addition of ethanol dia complete crystallization may be accomplished * by suction of the ethanol and drying of the crystal slurry, the colorless crystalline SuIfobetainsulfonsäure _t which zarsetzt from 220 ⁰ C, are isolated. The C-NMR spectrum of this acid is completely identical to that of the corresponding sodium salt. By re-dissolving the suifonic acid in an equimolar amount of sodium hydroxide solution and concentrating the resulting solution, the sodium betaine sulfonate can be recovered pure and in crystalline form. By neutralization, sulfofatty acid with any bases If necessary, the respective salts can be obtained formula-pure *

Example 2

This example is intended to demonstrate the influence of the starting pH on the selectivity of the proceeding reaction.

The procedure is as described in detail in Example 1 and mixed 69.34 g (0.2 mol) of 45.3% Dimethyidialiylaaitnoniumchloridlösung with 105.7 g (0.2 mol) of 39% sodium bisulfite solution to a ho / nogenen solution whose pH Value was 4.1. Aqueous 119.05 g (0.2 mol) of a 40% sodium peroxodisulfate solution are added dropwise in the course of 4 minutes. After only 2 minutes, the reacting mixture boils, the heat surplus of which can easily be dissipated by evaporative cooling. The following overview shows the time course of the exothermic reaction during the dosing phase of the oxidizing agent,

Time, (min), 0 .... _: .1. 1 * 5. 2 3 4,.

Temperature 22 94 99 103 103 100 ( ⁰ C)

The cooled colorless reaction solution of pH 0.3 was neutralized with 33 % sodium hydroxide solution and filtered from the crystallized sodium sulfate and the precipitated iron-III hydroxide. The quantitative composition of the filirate was determined by comparing the intensities of appropriate signals by H NMR spectroscopy, and showed. daS next to 90 -; _Q 1, 1-dimethyl-3,4-disulfonyl-2-pyrrolidiniumbetaine contained 10 % 1,1,3-tri-methyl-4-sulfomethylpyrrolidinium betaine (see DD-WP 154 444).

Example 3

This and the following Seispiel 4 are intended to illustrate the suitability of combined oxidants.

The procedure according to Example 1 is followed and from dimethyldiallyl-ammonium chloride solution, sodium bisulfite solution and hydrochloric acid a homogeneous starting solution of pH 2.1 and forth first in about 1.5 minutes 10 mol ro of a 50.0 % lgsn ATT.Tioniuniperoxodisuliat solution and - then 90 mol%

Added hydrogen peroxide at such a rate that the exothermic reaction can be controlled by evaporative cooling * H-NMR spectroscopy showed that the Diallylaimnoniumsalz was selectively and quantitatively converted to Sulfobetainsulfonat the repetition of this experiment exclusively with hydrogen peroxide as an oxidant resulted in unchanged starting material and its polymer only to oxidation of the sulfite to sulfate,

Example 4

The procedure of Example 3 and is used instead of 90 mol% of hydrogen peroxide as the oxidant chlorine, in which the chlorine was introduced into the reacting mixture so that the heat of reaction could be well dissipated, H-NMR spectroscopy was only the Sulfobetainsulfonat The repetition of the experiment exclusively with chlorine as an oxidizing agent led sulfite oxidation to sulfite *

Example 5

Potassium l-methyl-3,4-disulfomethy1-pyrrolidinium betaine

_ 1 2 (κ = ^ H ₀ ; ^ ⁵ H in the general formula i) from methyldiallylammonium chloride

A homogeneous solution of pH 2.0 is prepared from 1 mol of methyldiallylamine, 1 mol of potassium metabisulphite (K ₀ S ₀ O.-) and 37 % hydrochloric acid and the procedure according to one of the examples described above .

The sulfobetaine sulfonate was obtained quantitatively and showed the following ^J C-NMR spectrum:

50.5 37.8 37.8 50.5

"O" S - CH ₀ - CH CH - CH ₀ - ₀ SO "

^{3 2} I f 2 ο ₊

60.2 "HC CH 50.2 ^K

N 43.8 H ₃ CH

If the free sulfonic acid is to be recovered, it can be separated and isolated from the inorganic salts by the procedure described in Example 1 * By neutralization of the sulfonic acid with one or two molar equivalents of any base so the respective salts of l-methyl-3 _# 4-disulfomethyl-pyrrolidinium betains or of l-methyl-3,4-disulfomethylpyrrolidine can be obtained in pure form ·

Example 6

1 2 sodium 3,4-disulfomethylpyrrolidinium bet3in (R = R = H in the general formula I)

A homogeneous solution of pH 2.0 is prepared from 1 mol of oiallylamine, 2 mol of sodium hydrogensulfite and hydrochloric acid and the procedure according to one of the examples described above. The sulfobetainesulfonate was quantitatively

13 yielded and showed the following C-NMR spectrum (cis configuration):

50.1 38.4 38.4 50.1

G _O S - CH ₀ - CH CH - CH ₀ - S0 "

^{J 2} j 1 2 3 50.1 H ₂ C CH ₀ 50.1

V /

While the chemical shifts for the cis-compound of the groups N-CH and CH _n coincide ₀ -SO ₃ "50.1 ppm, which is trans-3 Varbincung shows expected signals: 40.4 ppm (CH); 51.0 ppm (CH -S0- _o ""); 53 ppm S (NOU)

If the free sulfonic acid is to be obtained 'can be separated them according to the procedure described in 3eispiel one operation from the inorganic salts and insulate

 By neutralizing the Sulfobetainsulfonsäure with one or two molar equivalents of any base so the respective salts of 3,4-Disulfomethyl-pyrrolidiniumbetains or 3,4-Qisulfomethyl-pyrrolidine can be obtained formula pure,

C-NMR spectrum of cis-disodium-3,4-disulfomethyl-pyrrole

lidins:

50.8 39.2 39.2 50.8

NaQ ₀ S - CH ₀ - CH CH - CH ₀ - SO ₀ Na

51 HC CH ₀ 51

 N

trans configuration: 42.1 ppm (CH); §2 ppm (CH SO ₃ Na); 55 ppm (M - CH ₂ ),

Example 7

Na t-criterion 1 - benzy 1-1-met hyl-3, 4-OMe disu If thy iumbetain -pyrrolidine (R = CH _3; R = CH ₂ -C ₅ H ₅ aer in general formula I) of! Senzylnsethyldiallylammoniumchlorid

A homogeneous solution of pH 2.0 is prepared from 1% by 50% benzylmethyldiallylammonium chloride solution, 2% from matriurabydrogensulfite and hydrochloric acid, and the procedure according to one of the examples described above is followed.

Suifobetainsulfor.at was obtained in quantitative yield.

13 and showed the following C-NMR spectrum:

Sl, 2 35 , 3 35.3 51 2 ^S0 3 ~ N / A - CH ₂ • χ - CH Γ T S ♦ Ζ " ² CH χ 2 50.2 ^H 3 ^C ' N XSx CH ₂ 0 5 ^Η 5

χ: 68.3; 68.6; 70.2;

ο: 129.5 130.9; 132.3; 134

If necessary, the free sulfobetaine sulfonic acid can be obtained according to the procedure described in Seispiel 1,

Example 8

Sodium l-propyl-l-methyl-S, 4-disulfometnyl-pyro-rolidide in

· ^Λ '2 betaine ( "= R' ^ 2 ^{''? 1 = =} ~ ^H '? ^H * ^""^ ^{H 3 c' he} ^^ ^a ^ 9 ^{eüiQ nan} formula I):

The procedure of Example 1 is mixed with 23.4 g (0.1 mol) of propylisethyldiallylammonium bromide, 53.4 g (0.2 mmol) of 39% strength sodium hydrogensulfite solution, 4.5 g of 37% strength hydrochloric acid and 47 g of water to give a homogeneous solution whose pH was 2.0. To this solution is added in the course of 7 minutes. finely powdered crystalline Kaliumperoxodisuifat added in portions. The initially reddish reaction solution discolored completely towards the end of Persulfatzugabe * Oer exothermic reaction course during Oer Zudosierungsphase the oxidizing agent is as follows overlooks refer to:

Time (min) 0 12 3 5 5 7

Temperature 21 32 48 51 88 92 94 ·

The H-NhR spectrum of the neutralized colorless filtrate showed that the sulfofetate sulfonate was obtained in quantitative yield,

C-NhR-3 Spectrum: 35.0 36.0

51.3 35.3 36.9 51 "3 ~ 0 ^ S - CH ₀ - CH CH - CH - SO ₀ "

² sf ² -

59.0 / 69.5 H ^ C CH, 53.0 / 69.5

53.5 / 54.2 H "C CH ₂ - CH _O - CH,

57.2 13.4 12.5 19.0

The doubling of the signals in the chemical shifts of single carbon atoms indicates that the sulfobutylene suifonate represents a mixture of products of the possible cis isomers with respect to the sulfomethyl groups in the 3,4-position,

Seizes 9 to 13

Sodium-l-alkyl-l-methyl-3,4-disulfomethy1-pyrrolidinium

12

betain (R - CH; R = alkyl in the alkylation of alkylarynyldiallyl ammonium salts

12

betaine (R - CH; R = alkyl in the general formula I)

0 "S - GH ₀ - CH - CH - CH ₀ - SO - 3 2, j 2 3

CH

^d na

HC alkyl

The procedure according to one of the examples described above and provides a homogeneous solution of pH 2.0 to 2.5 from 1 mol Alkylmethyldiallylammoniujnsalz, 2 moles of a hydrogen sulfite, hydrochloric acid and water nerve In the case of the longer-chain alkylmethyldiallylammonium (Alkyl ^ C) must the initial suspension to about 40 C are heated, so that a homogeneous starting solution and too much dilution was avoided * After successful implementation with 1 mol of a peroxodisulfate or a peroxodisulfate-oxidizing agent combination especially the longer-chain reaction products (alkyl> C ₁ ") already during the reaction or of the cooling solution from "De on whether dis Reaktionsmischunc was neutralized before, could be separated either the free Su-lfo · betainsulfonsaure or the corresponding SuIfobetainsuifonate.

In? In the case of the shorter-chain sulphonyl sulphonates, these are separated from the inorganic salts either by the method described in Example 1 or by extraction of the residue with ethanol / water (ratio 70:30), after evaporation of the solution.

Table 1: Sodium l-alkyl-l-methyl-3,4-disulfomethyl-pyrrolidinium groups

Example R {n-alkyl) decomposition point (C)

9 C ₁₀ H ₂₁ 225

10 C ₁₂ H ₂₅ 215

11 C ₁₄ H ₂₉ 261 *>

12 C._H _QQ 220

13 C ₁₈ H ₃₇ 228

x) free sulfonic acid; it begins to decompose in part from 228 ⁰ C; at 261 ⁰ C it melts with complete decomposition.

Example 14

Na triuronic-1-butyl-aryl-carbonyl-methyl-1-methyl-3,4-disulphomethylpyrrolidinium betaine (R ¹ = CH ₃ ; R = CH-CO-NH-C ₄ H ₉ in the general formula I)

0 "S - CH ₀ - CH CH - CH ^ - SO"

j 2 j j 2 3

HC CH ₀ Na ⁺

² ₊ / ²

The procedure according to Example 3 is repeated and the homogeneous solution of pH 2.0 to 2.5 is prepared from 1 mol of n-butylaminocarbonylmethyl-methyldiallylanimonium chloride prepared from methyldiailylamine, methyl chloroacetate and n-butylamine, 2 moles of sodium bisulfite, hydrochloric acid and water Init ^ mmoniumperoxodisulf at / hydrogen peroxide using external cooling so that a reaction temperature of not more than 50 C is not exceeded * After the reaction is immediately neutralized with sodium hydroxide to avoid the hydrolysis car acid amide function,

However, if it is desired to react only with peroxodisulfate analogously to Example 1, after approximately 10 mol% of the peroxodisulfate solution has been added to the diallylammonium salt, at least the two molar amount of sodium hydroxide solution with the remaining amount of peroxodisulfate solution should be maintained while maintaining a temperature not higher than 50 C should be added.

The sulfobetainesulfonate (decomposition point> 238 C) was separated from its inorganic accompanying salts by extraction of the residue obtained after evaporating the reaction solution with aqueous ethanol (SO 2)

Example 15

Sodium r-1-dicyclohexylaminocarbonylmethyl-1-methyl-S, 4-

disulfomethylpyrrolidinium betaine (R = CH-;

R = CH ₀ -CO-N (C ₁ -H. _Λ J ₀ in the general formula I)

"0-3 - CH ₀ - CH CH - CH ₀ - SO ₀ "

H ₀ C CH ₂ Na ⁺

H ₃ C

The procedure of Example 14 is followed and the amount of oicyclohexylaminocarbonylmethyl-methyldiallylammonium chloride prepared from methyldiallylamine, methyl chloroacetate and dicyclohexylamine is quantitatively converted to suifobetainesulfonate (decomposition point> 270 ° C.).

Seispiel IS

Natriusa-1-dodecyl / tetradecylaminocarbonyl-methyl-1-ethyl

umbetaine (R = CU , in general formula I)

3,4-disulfomethylpyrrolidinium betaine (R = di -;

OS - CH ₀ - CH CH - CH, -

³²

-CH- N "N 1 • CH f H-C CH /

N / A

The procedure of Example 14 and sets dodecyl / tet radecylaminocarbonylmetnyl-methyldiallylammoniumchlorid, which is from methyldiallylamine, methyl chloroacetate and dodecyl / tetradecylamine mixture (cocosamine, component ratio about 1: 1) produces, quantitatively to Sulfobetaine sulfonate (decomposition point> 246 C).

Seismic Example 17

Sodium l- / di (dodecyl / tetradecylaminocarbonyl) / methyl-1-methyl-3,4-disulfoniethyl-pyrrolidinium betaine (-R = CH; R ² = CH (CO-NH-C ₁₂ H ₂₅ ZC ₁₄ H _g ) ₂ in the general formula I)

₀ S - CH ₀ - CH CH - CH ₀ -. SO,

3 2, j 2 3

Na ⁺

The procedure according to Seispiel 13 and sets Di "{dodecyl / tet radecylaminocarbonyi) methyl-ethyldiallyla! I) moniumbromid, one from Methyldiallyiamin, 3rommalonsäurediethylester and dodecyl / tet radecylamin mixture (cocoamine, component ratio 1: 1) herstallt, at a reaction temperature of 40 ⁰ C Ziirn 5ulfobeta.insulfonat (melting point 139-148 C, to crystallization from. ethanol) in order.

Claims (4)

invention claim 1, Process for the preparation of novel 1, l-dialkyi-3,4-disulfomethyi-pyrroiidiniumbetainen of the general formula I, 0 "S - CH ₀ - HC CH - CH _n - SO.-, ² Ii 23 HC CH M ⁺ in which 12
R and R independently of one another are hydrogen, straight-chain or branched alkyl radicals having 1 to 22 carbon atoms which may also be interrupted by the groupings -CO-NH- or -NH-CO-, hydroxyalkyl radicals or cycloalkylene radicals or ring-closed substituents, and M means a cation characterized in that the dia llylaromonxumsaIze the general formula II » H ₀ C = HC CH β CH ₀ 2, Method according to item 1, characterized in that the cation M ⁺ Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ means » ² 1! ² H ₀ C CH ₀ C s. j> d. - > j. / Λ R ¹ ' ^N R ^{2 X1} in the 12
R * and R "have the o * .g. Meanings and X represents an anion, in the presence of twice the molar amount of a hydrogen sulfite with peroxodisulfate alone or peroxodisulfates, and other oxidizing agents at pH values of 2 to 4, such that per diamino diallyl ammonium salt is 1 mol peroxodisulfate or, in the presence of other oxidizing agents, 2 oxidation valents are available. 3, process according to item 1, characterized in that the diallyl ammonium salts used are chlorides, bromides,
Methosulfates or sulfates are, 4, Method according to item 1, characterized in that the oxidizing agent used in the mixture with peroxodisulfate chlorine or chlorine-releasing substances, chlorates, aroma te or hydrogen peroxide.