DD224848A1 - PROCESS FOR PREPARING NEW 1- (3'-SULFO) PROPYL-3-SULFINATOMETHYL-4-SULFOMETHYL-PYRROLIDINIUM BEVERES - Google Patents

Abstract

The invention relates to a process for the preparation of sulfobetaines with an additional sulfinate group and a sulfonate group (I). Their synthesis is carried out by reacting triallyl ammonium salts with three times the molar amount of hydrogen sulfite, preferably in the p H value range of 4.0 to 5.5 in the presence of a catalytic amount of peroxodisulfate as an initiator. The reactive sulfinate group makes the new compounds versatile intermediates. Long-chain substituted representatives of the new substances are novel surfactants, which are effective in a wide p H value range. Formula I

Description

iitsl the invention

Process for the production of new ones

l- (3'-sulfo) propyl-3-sulfinatomethyl-4-sulfomethyl-pyrrolidiniumbetainen

Application scfe'bi et 'invention

The invention relates to a process for the preparation of novel 1- (3'-sulfo) propyl-3-sulfinatomethyl-4-sulfomethylpyrrolidinium betaines of general formula 1,

~ 0 _o 3 - CH ₀ - HC CH - CH ₀ - SG_ ~

^H 2 ^{C CH} 2 +

N I

R is CH ₂ - CH ₂ - CH ₂ - SO ₃

in which

R is hydrogen, a straight-chain or branched alkyl radical. in it 1 to 22 carbon atoms, which may also be interrupted by the groupings -CO-NH- or -NH-CO-, may be a hydroxyalkyl radical or Cxyalkylenrest and

M ^{+ is the} same or different karions, preferably Ma ^T ,: <", NH ^ ⁺ or H ~,

The new compounds I are sulfobetaines πι it two additional hydrophilic and polar groups; a sulfinate group which, because of its reactivity "(nucleophilic, aikyiisirbar,

i. υ 'J; -. SJv ^ i i υ O U 1

complexing, reducing) the new compounds to versatile intermediates makes, and a sulfonate group, which increases the polarity and solubility of the substances and in representatives with long-chain substituent R determines the surfactant properties of the substance group »

Characteristic of the known technical solutions

l- (3 ^f -Sulfo) propyl-3-sulfinatomethyl-4-sulfomethyl-pyrrolidiniumbetaine (SuIfobetain-sulfinate-sulfonate) of the general formula I are as a class of new · Technical solutions for making other SuIfobetain-sulfinate-sulfonates are also not known · From DD-WP 154 444 are only 3-methyl-4-sulfomethylpyrrolidiniumbetaine and DD-WP 200 739 thereof derivatives which carry an additional sulfopropyl group on the quaternary nitrogen, l- (3 * -SuIfο) propyl-3-methyl-4 -sulfo-methy1-pyrrolidinium betaines, known ·

These known substance series are obtained according to the aforementioned inventions in a homogeneous catalytic reaction in the pH range of 5 to 8 from Diallylammonium- or Triallylamraoniufflsalzen and hydrogen sulfites by dropping the reactants simultaneously to a submitted sulfite buffer solution. This synthetic route has the disadvantage that, in addition to low space-time yield, only sulfobetaines having only one additional sulfonate group are obtained, as a result of which these substances lack a reactive center for further reactions.

Object of the invention

It is the object of the invention, in the reaction of tri-allylammonium salts in one reaction step, to obtain high space-time yields of sulfoethenes with two additional anionic groups which are to be capable of further reactions *

Explanation of the essence of the invention

The object of the invention is to provide a multiple

functionalization of Triallylammoniumsalzen make new sulfobetaines with additional, capable of further reactions anionic groups; the sulfobetaines should be readily accessible in good yields

The object is achieved in that according to the invention solutions of triallylammonium salts of the general formula II,

II

HC N R CH = I CH ₂ χ " CH " = CH ^ CH ₂ - CH

in the

R has the abovementioned meaning and X ~ represents an anion, preferably chloride or bromide, with at least three times the molar amount of a hydrogen sulfite in the pH range from 2.5 to 6, preferably 4.0 to 5.5, in the presence catalytic amounts of a peroxodisulfate to l- (3'-sulfo) propyl-3-sulfinatomethyi-4-suifomethylpyrrolidiniumbetainen the general formula I in which R and M have the abovementioned meaning to be implemented ·

H ₀ C = HC CH = CH ₀ ² t! ²

R CH "- CH =

0 _o 5 - H ₀ C - HC - CH - CH ₀ - 30

\\ ^{Z 3}

w _v '2 = ° 8 ^{V + /}

pH 2.5 to -5 /

R is CH ₂ - CH ₂ - CH ₂ - SO ₃

This Trifunktionalisierung of Triallylammoniumsalzen to products with three oxygen-containing sulfur functions will be called SuIfocyclosulfinierung · The surprisingly triggered by this procedure exothermic implementation is fundamentally different from all previously performed on Triallylammoniumsalzen Hydrogensulfitadditionen i the simultaneous installation of a sulfinate and two sulfonate groups represents a new reaction. The speed of the reaction proceeding after a radical mechanism is also surprising; Sulfocyclosulfination requires at initiator concentrations <. 2 Mo 1% only minutes or at concentrations> 2 mol% even only seconds until practically complete conversion · This reaction is one of the fastest solution-free radical reactions known to organic chemistry ·

The initiation of the sulfocyclosulfination reaction is specifically linked to the presence of salts of the peroxydisulfuric acid, preferably sodium, potassium or ammonium peroxodisulfate; other per compounds, e.g. 3 »Hydrogen peroxide or perborates can not induce a comparable reaction, but simply oxidise sulphite to sulphate.

However, in special cases it is also possible to co-use peroxodisulfates and other oxidizing agents, for example oxygen or in particular air, in such a way that about 1 mol% or less of a peroxodisulfate is then added to initiate the reaction in the initial phase and the sulfoflocculphination is completed with simultaneous stirring or passage of air. However, extended reaction times must be accepted with this procedure, but the composition of the reaction products does not change.

The selectivity of the course of the reaction is highly dependent on the set starting pH. Thus, in the preferred pH range from 4.0 to 5.5, the new sulfobetaine sulfinate sulfonates I in a proportion of 50 to 70%

in addition to the still further sulfonated products l- (2'-3-sulfinato-3 ^t -sulfo) propyl-3-sulfinatomethyl-4-sulfomethyl-pyrrolidiniumbetainen III and the known (cf. DD-WP 200 793) 1- (3 * -SuIfο ) propyl-3-methyl-4-sulfomethyl-pyrrolidinium betaines IV.

O ₀ S - H ₀ C - HC CH - CH - SO ₀

* - I! <c j

^H 2 ^C _V. ^CH 2 III

R is CH ₀ - CH - CH - SO 30 ~

H ₀ C - HC CH - CH ₀ - 30 _o

3 j, d. 3

H ₀ C CH ₀

S \

R is CH ₂ - CH ₂ - CH ₂ - SO ₃

Lowering the starting pH below 4, the reaction product contains virtually no more IV, while at pH values above 5.5 practically no III is formed »The favorable for the implementation of the method pH range 4 , 0 to 5.5 is also already achieved by mixing the triallyl ammonium salts with technical bisulfite solution, optionally with the addition of small amounts of a base, ·.

To prepare the sulfonyl sulfinate sulfonate I is preferably carried out in aqueous solution at the highest possible concentrations of the reactants by mixing the crystalline triallyl ammonium salts or their solutions with saturated technical Hydrogensulfitlösung, the pH of the mixture, optionally with bases, preferably between 4 , 0 and 5.5 and adding the initiator as a solution or in crystalline form, wherein the progressive reaction by rapid heating of the

Reaction mixture can be seen. Cooling of the reaction mixture is usually not necessary because the released heat of reaction is not sufficient to heat it to boiling when starting the reaction at room temperature,

Long chain substituted triallyl ammonium salts give sulfonyl sulfonatesulfonates having valuable surfactant properties. In a suitable apparatus, the process according to the invention can also be carried out continuously if the reactants in the corresponding molar ratio and the initiator are combined at the beginning of a residence time segment.

embodiments

The C-MFiR spectrum reported in the following example was measured in DpO; as external standard TMSj served chemical shifts in ppm.

example 1

Dinatriu ?nl-mathyl-l- (3 ^f -sulfo) propyl-3-sulf ina tome thy1-4-sulfomethyl-pyrrolidinium betaine (R = CbU in the general formula I) by SuIfocyclosulfinierung of methyltriallylammonium chloride. ,

95.2 g (0.2 mol) of 39.43% strength aqueous methyltriallylammonium chloride solution and 152.8 g (0 ₉ moles) of 33 % ± aqueous technical sodium hydrogen sulfite solution having an iron content of. Were obtained in a mixing flask provided with stirrer, thermometer and glass electrode 3 mg / mol of solution are mixed together to give a homogeneous solution of pH 4.3. "1.9 g (4 mol%) of sodium peroxodisulfate are then added in one portion to the pale yellow starting solution while stirring, the peroxodisulfate dissolving immediately, the reactive mixture warms and turns orange.

The time course of the exothermic sulfocyclosulfination shows the following overview:

Time (s) 0 15 25 40 60 Temp. ( ⁰ C) 23 42 Sl 54 S3

After reaching the maximum temperature, the reaction is complete. The ^ H-NMR spectrum of the reaction solution exhibited the quantitative sulfocyclosulfination of the methyltriallylammonium chloride. The sulfonated sulfonate sulfonate I was in addition to the sulfofetamine-disulfinate-sulfonate II and the sulfofatty-sulfonate IV 50 to 60 % yield obtained *

To separate the free sulfonyl sulfonyl sulfonate I, the procedure is as follows:

After concentration of the above-obtained reaction solution under reduced pressure to dryness, the resulting salt residue with the sufficient amount of conc. Hydrochloric acid is added, worked through, filtered off from the insoluble sodium chloride and again concentrated under reduced pressure. "The addition of alcohol to the remaining oily residue may precipitate the sulfocyclosulfination product."

13 The C-tNMR spectrum of the hydrochloric acid residue shows that the chemical shifts (ppm) of individual signals of the carbon atoms have doublings, which proves the presence of the following structural isomers.

"0 _o 3 - CH ₀ >HC" CH 1 CH ₀ - SO- "

2 2 j, 2 3

HC CH

H ₃ C CH ₂ - CH ₂ - CH ₀ - 5O ₃

'O ₂ S - H ₂ C

CH 1

CH ₂ - SO ₃ '

^H 3 ^C

CH

- CH ₂ - CH ₂ - SO ₃

N - CH ₂ (ring N - CH "

CH ₂ - SO ₂ N - CH

3 Si

- SO,

CH ₂ --SO ₃

(Ring)

CH - CH ₀ - SO, CH - CH ₂ - SO ₂ ^- ChU

69.2; 69.5

63.5; 57, Ii

56.5 57.3

50.8i 53.1 51.1; 51.3 49.2

36.0; 36.8 33.0; 33.9 20.5; 21.1

A product obtained by sulfocyclosulfination of methyldiallyl-3-sulfopropyl-ammoniumammaine (see DD-PS 200 739) at pH 2.5 with two molar amounts of hydrogen sulfite and 4% by weight of psroxodisulfate according to the above procedure

13 showed an identical C NMR spectrum »

Example 2

The procedure according to Example 1 and mixed 0.2 mol Methyltriallylanimoniumchlorid, 0.6 mol sodium bisulfite solution and 14 g of 33% sodium hydroxide solution to a homogeneous mixture of pH 5.4 and then adds 4 Mo'2-% Kaiiumperoxodisulfat at once · The reaction product was about 2/3 of the sulfofatty sulfinate sulfonate I and about 1/3 of the sulfobetaine sulfonate IV *

Example 3

The procedure of Example 1 and mixed 0.2 mmol of methyltriallyl ammonium chloride solution, 0.7 mol Matriumhydrogensulfitlösung and 2.8 g 37 / eig ^e hydrochloric acid to a homogeneous solution and adds 4 mol% ammonium peroxodisulfate all at once »was the reaction product, the sulfonated sulphonate sulfonate I and the sulfobetaine disulfinate sulfonate III

to obtain about the same amount in addition to a small amount of about 5 % of the sulfofatty acid sulfonate IV *

Example 4

This example is intended to demonstrate the possibility that peroxodisulfate can also be used in conjunction with other oxidants, such as air, to initiate sulfonyl-sulfonation when less than about 1 mole of peroxodisulfate is used. Compared to example 1, the reaction time is increased until complete conversion considerably.

In a according to Example 1 additionally equipped with a gas inlet tube sulfonation flask, the starting solution described in this example the pH value of 4.3 x 0.2 moi Methyltriailylammoniumchloridiösung and Ό / 31 m'ol 'NatriumHydrogen'sulfitlösung Herges was polishes and "pre- With vigorous stirring, a weak stream of air is now passed through the solution in such a way that air bubbles are constantly dispersed therein, and at the same time 333 mg (0.7 mol%) of sodium peroxodisulfate, which was previously dissolved in 2 g of water, are added at once. Immediately after the peroxodisuitrate addition, the initially pale yellow solution turns bright orange, but after 3 minutes, its original color had returned to its original color., 16 minutes after the start of the reaction, the reacting mixture warms from 25 to 50.5C , the maximum temperature, in order to gradually cool down with continued stirring *

The entire time course of the exothermic sulfocyclosulfonation with the oxidizing agent mixture shows, the following overlooks:

Zsit (min) O 1 1.5 2 5 il IS 20 80 140 Tempv (°) 25 40 43 45 43 50 50.5 50 37 30

At the time of the maximum temperature, however, no complete conversion was reached, only about 4 hours later could H-NMR spectroscopy no more triallylammonium salt be detected. The pH of the reaction solution had increased to 5.2 at the end of the reaction. "The composition of the product mixture corresponded to that of Example 1.

Example 5

Qinatrumum-1-tetradecyl-1-CS'-suifojprcpyi-S-sulfinato-di-ethyl-4-sulfomethylpyrrolidinium betaine (R = C ₁ H - in the general formula I) by sulfocyclosulfination of tetradecyltriallylammonium bromide

The procedure according to Example 1 is repeated and the homogeneous solution of the pH 4.5 aus'0.1 times Tetradecyltriallylammoniumbromid and 0.3 mol sodium hydrogen sulfite with 4 mol% potassium peroxodisulfate us. The neutralized, clear reaction solution can either be used for further reactions or, if necessary, concentrated to dryness to separate by extraction with ethanol / water (2: 1) the sulfonation product of the inorganic salts. "The recrystallized from ethanol / vVaser extraction product decomposed at a Temperature above 270 ^° C. *

Example S

D ina t riu m-1-dodecyl / te t rad ecyi-a mi noc ar bonyiiae thy 1-1- (3 '' - sulfo) propy 1-3-si-fi- nylmethy1-4-sulfomethylpyrrolidinium batain (R = QH- CO-NH-C ^ ₂ H. ^ / C ^^ H ₂ in the general formula I) by sulfocyclosulfination of dodecyl / tatradacylaminocarbonylmethyl-triallylammoniumchiorid

The procedure of Example 4 is followed and dodecyl / tetradecylaminocarbonylmethyl-1-riallylammonium chloride, which had been prepared from triallylamine, methyl chloroacetate and dodecyl / tetradecylarain (cocosamine, component ratio 1: 1), is added to the 3-sulfobetaine-sulfinate-sulfonate mixture.

The extracted with ethanol / water (2: 1) of the evaporated reaction solution extraction product, which is recrystallized from ethanol / water, melted at 212 ⁰ C with decomposition,

Claims (3)

invention claim 1 » Process for the preparation of novel 1- (3'-sulfo) propyl-3-sulfinatomethyl-4-sulfomethylpyrrolidinium betaines of general formula I, "CUS - CH ₀ --HC CH - CH ₀ - SO 2. The method of item 1, characterized in that the M ⁺ cations Na ^+, K ^+, NH ₄ ⁺ or H ⁺ means. 2 ^d I \ H ₂ C CH ₂ R is CH ₂ - CH ₂ - CH ₂ - SO ₃ in which R is hydrogen, a straight-chain or branched alkyl radical having 1 to 22 carbon atoms, which may also be interrupted by the groupings -CO-NH- or -NH-CO- "may be a hydroxyalkyl radical or Oxyalkylanrest and M ^{+ means the} same or different cations, characterized in that triallylamonium salt of general formula II, H ₀ C = HC CH = CH ₀
² II ²
H "C CH ₉ N
S \ R is CH ₂ - CH in the R has the meaning given above and X ~ is an anion, with the threefold molar amount of a hydrogen sulfite under the action of catalytic amounts of a peroxodisulfate or the action of peroxodisulfate and simultaneous or subsequent exposure to atmospheric oxygen in the pH range from 2.5 to 5, preferably 4.0 to 5.5 reacted become" Process according to item 1, characterized in that the anion X.sup.-1 of the triallylammonium salts used is chloride, broride, methosulphate or equivalent sulphate.