EP0205626A1 - Sulfobetains of ammoniocarboxamides, and process for their preparation - Google Patents

Sulfobetains of ammoniocarboxamides, and process for their preparation Download PDF

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EP0205626A1
EP0205626A1 EP85106217A EP85106217A EP0205626A1 EP 0205626 A1 EP0205626 A1 EP 0205626A1 EP 85106217 A EP85106217 A EP 85106217A EP 85106217 A EP85106217 A EP 85106217A EP 0205626 A1 EP0205626 A1 EP 0205626A1
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formula
reaction
radicals
sulfobetaines
hydrogen
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EP0205626B1 (en
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Detlef Dr. Dipl.-Chem. Ballschuh
Roland Dr. Dipl.-Chem. Ohme
Jochen Dr. Dipl.-Chem. Rusche
Horst Dr. Dipl.-Chem. Seibt
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Akademie der Wissenschaften der DDR
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

  • the invention relates to new sulfobetaines and processes for the preparation of these sulfobetaines, which are derived from ammoniocarboxamides and are described by the general formula I.
  • R 1 and R 2 are hydrogen, straight-chain or branched alkyl radicals having up to 22 C atoms
  • R 3 and R 4 are identical or different short-chain alkyl radicals or hydroxyalkyl radicals having 1 to 4 C atoms or oxyethylene radicals
  • R 5 means hydrogen or alkylaminocarbonyl radicals or alkyl radicals with up to 22 carbon atoms and n numbers from 0 - 3.
  • Internal salts of the general formula I can generally be used to increase the conductivity, e.g. B. as an antistatic coating agent. If one of the substituents R 1 , R 2 or R 5 is long-chain (8 - 22 C atoms), these sulfobetaines also have valuable surfactant properties that enable them to be used as a component of detergents and cleaning agents, as flotation agents or as emulsifiers.
  • the invention has for its object to develop a process for the preparation of sulfobetaines of a new type which avoids the disadvantages mentioned and does not require unsymmetrical diamines as an intermediate product of the synthesis.
  • Sulfopropylated ammoniocarboxamides are to be prepared, the sulfo group being introduced by homogeneous catalytic hydrogen sulfite addition to allylammonium salts in accordance with DD-PS 154 443 and the use of propane sultone being avoided.
  • the application properties of the new sulfobetaines should reach or exceed those of the known products.
  • sulfobetaines of ammoniocarboxamides of the general formula I in which R 1 and R 2 are hydrogen, straight-chain or branched alkyl radicals with up to 22 C atoms, R 3 and R 4 are the same or different short-chain alkyl radicals with 1 to 4 C atoms or hydroxyalkyl radicals with 2 to 3 C atoms or oxyethylene radicals, R 5 is alkyl radicals having up to 22 carbon atoms or hydrogen or alkylaminocarbonyl radicals and n are integers from 0 to 3.
  • dialkylallylamines of the formula III quaternized with halocarboxylic acid esters of the formula IV and the resulting quaternary ammonium compounds V with ammonia or primary or secondary amines of the formula VIII and hydrogen sulfite implemented.
  • the reaction of the quaternary ammonium compounds can either first with hydrogen sulfite in the reactive intermediate of formula VII and then with amines of the formula VIII, and also first with an amine of the formula VIII via the intermediate of an amide of the formula VI and subsequent hydrogen sulfite addition can be carried out.
  • dialkylallylamines and halogen fatty acid esters, alkylamines and hydrogen sulfites which are easily accessible according to DD-PS 136 497 are used as synthesis building blocks.
  • intermediate V can also be obtained from alkyl N, N-dialkylamino esters, and intermediate VI from dialkylamino acid amides by reaction with allyl halides. It is possible without disadvantage to carry out the process steps up to the amide VI without solvent and without isolation of the intermediate stages, if appropriate also continuously.
  • sulfite anion radicals capable of addition can also be initiated with other oxidizing agents instead of the air oxygen / transition metal system;
  • oxidizing agents instead of the air oxygen / transition metal system
  • salts of peroxodisulfuric acid, alkyl peroxides, acyl peroxides or hydrogen peroxide are suitable.
  • the action of several oxidizing agents as free radical formers can also be advantageous.
  • the sulfobetaines I according to the invention show excellent surfactant properties. They outperform the previously known types of formula II in their lime soap dispersing capacity, in which the acid amide bond -CO-NH- is arranged in a different order. These unexpectedly favorable properties advantageously distinguish the new sulfobetaines from the known representatives of the compound class.
  • the process according to the invention can be carried out on a technical scale as a one-pot process, because the amine components III which were previously not technically available are now cheaply available according to DD-PS 136 497.
  • the subsequent synthesis steps surprisingly each proceed with quantitative yield; it is therefore possible to work without isolating intermediate stages, which is a valuable process effect compared to the known prior art.
  • Another advantage of the procedure according to the invention is that intermediate V makes a large number of sulfobetaines with carbonamide groups accessible without the carcinogenic propane sultone having to be used.
  • the slightly yellowish sulfobetaine solution also contains salts (NaCl, Na 2 S0 3 and Na2S04), from which the product can be separated by concentration and extraction with ethanol (melting point Z> 164 ° C).
  • N-Allyl-N, N-dimethyl-ammonio-malonic acid diethyl ester bromide 85 g (1 mol) of dimethylallylamine are dissolved in 200 ml of ethanol. 239.1 g (1 mol) of diethyl bromomalonate are added dropwise to this solution with stirring at 30 ° C. and the mixture is subsequently stirred at 80 ° C. for 2 hours.

Abstract

1. Sulfobetaines of ammoniocarboxylic acid amides of general formula I, see diagramm : EP0205626,P8,F4 where : R1 and R2 signify hydrogen or straight-chain or branched C1-22 -Alkyl, R3 and R4 signify identical or independent C1-4 -Alkyl or C2-3 -hydroxyalkyl, R5 signifies H, C1-22 -alkyl or alkylaminocarbonyl, and n signifies 0, 1, 2 ou 3, and at least one of the substituents R1 , R2 and R5 has 8 to 22 C atoms.

Description

Die Erfindung betrifft neue Sulfobetaine sowie Verfahren zur Herstellung dieser Sulfobetaine, welche sich von Ammoniocarbonsäureamiden ableiten und durch die allgemeine Formel I beschrieben werden.

Figure imgb0001
The invention relates to new sulfobetaines and processes for the preparation of these sulfobetaines, which are derived from ammoniocarboxamides and are described by the general formula I.
Figure imgb0001

In der allgemeinen Formel I bedeuten R1 und R2 Wasserstoff, geradkettige oder verzweigte Alkylreste mit bis zu 22 C-Atomen, R3 und R4 bedeuten gleiche oder verschiedene kurzkettige Alkylreste oder Hydroxyalkylreste mit 1 bis 4 C-Atomen oder Oxyethylenreste, R5 bedeutet Wasserstoff oder Alkylaminocarbonylreste oder Alkylreste mit bis zu 22 C-Atomen und n Zahlen von 0 - 3.In the general formula I, R 1 and R 2 are hydrogen, straight-chain or branched alkyl radicals having up to 22 C atoms, R 3 and R 4 are identical or different short-chain alkyl radicals or hydroxyalkyl radicals having 1 to 4 C atoms or oxyethylene radicals, R 5 means hydrogen or alkylaminocarbonyl radicals or alkyl radicals with up to 22 carbon atoms and n numbers from 0 - 3.

Innere Salze der allgemeinen Formel I können allgemein zur Erhöhung der Leitfähigkeit verwendet werden, z. B. als antistatische Beschichtungsmittel. Wenn einer der Substituenten R1, R2 oder R5 langkettig ist (8 - 22 C-Atome), so haben diese Sulfobetaine darüber hinaus wertvolle Tensideigenschaften, die ihre Anwendung als Bestandteil von Wasch- und Reinigungsmitteln, als Flotationsmittel oder als Emulgatoren ermöglichen.Internal salts of the general formula I can generally be used to increase the conductivity, e.g. B. as an antistatic coating agent. If one of the substituents R 1 , R 2 or R 5 is long-chain (8 - 22 C atoms), these sulfobetaines also have valuable surfactant properties that enable them to be used as a component of detergents and cleaning agents, as flotation agents or as emulsifiers.

Es ist bereits ein Verfahren zur Herstellung von Sulfobetainen bekannt, welche in einem Substituenten des quartären N-Atoms eine Carbonamidgruppe enthalten. In diesen bekannten Verbindungen ist die Carbonamidgruppe in umgekehrter Reihenfolge von -CO- und -NH- enthalten. Sie sind Derivate von 1,2- oder 1,3-Diaminen und haben die allgemeine Formel II,A process for the preparation of sulfobetaines which contain a carbonamide group in a substituent of the quaternary N atom is already known. In these known compounds, the carbonamide group is contained in the reverse order of -CO- and -NH-. They are derivatives of 1,2- or 1,3-diamines and have the general formula II,

Figure imgb0002
Figure imgb0002

in welcher R6 Alkylreste, R7 und R8 Methyl- oder Hydroxyalkylgruppen und n die Zahlen 2 oder 3 bedeuten. Tenside der allgemeinen Formel II haben z. B. von den bekannten Verbindungen das bisher beste Kalkseifendispergiervermögen (W. M. Linfield, J. Amer. Oil Chem. Soc. 55 (1978) 87; F. D. Smith und W. M. Linfield, ebenda 55 (1978) 741).in which R 6 is alkyl, R 7 and R 8 are methyl or hydroxyalkyl groups and n is 2 or 3. Surfactants of the general formula II have, for. B. of the known compounds the best lime soap dispersing capacity so far (WM Linfield, J. Amer. Oil Chem. Soc. 55 (1978) 87; FD Smith and WM Linfield, ibid. 55 (1978) 741).

Das genannte Verfahren zur Herstellung der Verbindungen der allgemeinen Formel II hat für den technischen Einsatz erhebliche Nachteile: es benötigt unsymmetrisch dialkylierte 1,2-oder 1,3-Diamine als Ausgangsstoffe und verwendet zum Aufbau der quartären Ammoniumstruktur das hochgradig cancerogene Propansulton.The process mentioned for the preparation of the compounds of the general formula II has considerable disadvantages for industrial use: it requires unsymmetrically dialkylated 1,2-or 1,3-diamines as starting materials and uses the highly carcinogenic propane sultone to build up the quaternary ammonium structure.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Sulfobetainen eines neuen Typs zu entwickeln, welches die genannten Nachteile vermeidet und keine unsymmetrischen Diamine als Zwischenprodukt der Synthese erfordert. Es sollen sulfopropylierte Ammoniocarbonsäureamide hergestellt werden, wobei die Einführung der Sulfogruppe durch homogenkatalytische Hydrogensulfitaddition an Allylammoniumsalze nach DD-PS 154 443 erfolgt und die Verwendung von Propansulton vermieden werden kann. Die Anwendungseigenschaften der neuartigen Sulfobetaine sollen die der bekannten Produkte erreichen oder übertreffen.The invention has for its object to develop a process for the preparation of sulfobetaines of a new type which avoids the disadvantages mentioned and does not require unsymmetrical diamines as an intermediate product of the synthesis. Sulfopropylated ammoniocarboxamides are to be prepared, the sulfo group being introduced by homogeneous catalytic hydrogen sulfite addition to allylammonium salts in accordance with DD-PS 154 443 and the use of propane sultone being avoided. The application properties of the new sulfobetaines should reach or exceed those of the known products.

Diese Aufgabe wird gelöst durch neue Sulfobetaine von Ammoniocarbonsäureamiden der allgemeinen Formel I,

Figure imgb0003
in welcher R1 und R2 Wasserstoff, geradkettige oder verzweigte Alkylreste mit bis zu 22 C-Atomen, R3 und R4 gleiche oder verschiedene kurzkettige Alkylreste mit 1 bis 4 C-Atomen oder Hydroxyalkylreste mit 2 bis 3 C-Atomen oder Oxyethylenreste, R5 Alkylreste mit bis zu 22 C-Atomen oder Wasserstoff oder Alkylaminocarbonylreste und n ganze Zahlen von 0 bis 3 bedeuten.This object is achieved by new sulfobetaines of ammoniocarboxamides of the general formula I,
Figure imgb0003
 in which R 1 and R 2 are hydrogen, straight-chain or branched alkyl radicals with up to 22 C atoms, R 3 and R 4 are the same or different short-chain alkyl radicals with 1 to 4 C atoms or hydroxyalkyl radicals with 2 to 3 C atoms or oxyethylene radicals, R 5 is alkyl radicals having up to 22 carbon atoms or hydrogen or alkylaminocarbonyl radicals and n are integers from 0 to 3.

Erfindungsgemäß werden dazu Dialkylallylamine der Formel III

Figure imgb0004
mit Halogencarbonsäureestern der Formel IV quaternisiert
Figure imgb0005
und die entstehenden quartären Ammoniumverbindungen V
Figure imgb0006
mit Ammoniak oder primären oder sekundären Aminen der Formel VIII
Figure imgb0007
und Hydrogensulfit umgesetzt.According to the invention, dialkylallylamines of the formula III
Figure imgb0004
 quaternized with halocarboxylic acid esters of the formula IV
Figure imgb0005
 and the resulting quaternary ammonium compounds V
Figure imgb0006
 with ammonia or primary or secondary amines of the formula VIII
Figure imgb0007
 and hydrogen sulfite implemented.

Die Substituenten R1 bis R5 und n haben immer die Bedeutung, wie in Formel I angegeben.The substituents R 1 to R 5 and n always have the meaning as indicated in formula I.

Die Umsetzung der quartären Ammoniumverbindungen kann sowohl zuerst mit Hydrogensulfit in die reaktionsfähige Zwischenstufe der Formel VII

Figure imgb0008
und dann mit Aminen der Formel VIII erfolgen, als auch zuerst mit einem Amin der Formel VIII über die Zwischenstufe eines Amids der Formel VI
Figure imgb0009
und anschließende Hydrogensulfitaddition durchgeführt werden. Es entstehen stets Verbindungen der Formel I.The reaction of the quaternary ammonium compounds can either first with hydrogen sulfite in the reactive intermediate of formula VII
Figure imgb0008
 and then with amines of the formula VIII, and also first with an amine of the formula VIII via the intermediate of an amide of the formula VI
Figure imgb0009
 and subsequent hydrogen sulfite addition can be carried out. There are always compounds of the formula I.

Die nach DD-PS 136 497 leicht zugänglichen Dialkylallylamine und Halogenfettsäureester, Alkylamine und Hydrogensulfite werden als Synthesebausteine verwendet.The dialkylallylamines and halogen fatty acid esters, alkylamines and hydrogen sulfites which are easily accessible according to DD-PS 136 497 are used as synthesis building blocks.

Die Zwischenstufe V kann in Einzelfällen auch aus N, N-Dialkylaminosäurealkylestern, die Zwischenstufe VI aus Dialkylaminosäureamiden durch Umsetzung mit Allylhalogeniden erhalten werden. Es ist ohne Nachteil möglich, die Verfahrensschritte bis zum Amid VI ohne Lösungsmittel und ohne Isolierung der Zwischenstufen durchzuführen, ggf. auch kontinuierlich.In individual cases, intermediate V can also be obtained from alkyl N, N-dialkylamino esters, and intermediate VI from dialkylamino acid amides by reaction with allyl halides. It is possible without disadvantage to carry out the process steps up to the amide VI without solvent and without isolation of the intermediate stages, if appropriate also continuously.

Als mögliches Reaktionsmedium kommen vorwiegend Wasser, Alkohole und Wasser-Alkohol-Gemische zur Anwendung. Die Bildung der quartären Ammoniumsalze erfordert in der Regel Reaktionstemperaturen zwischen 20 und 100 °C, die Herstellung der Säureamidbindung erfolgt im gleichen Temperaturbereich. Die Hydrogensulfitaddition zum Sulfobetain erfolgt unter der gleichzeitigen katalytischen.Wirkung von Luftsauerstoff und Obergangsmetallen, vorzugsweise Ionen des Eisens, Kupfers oder Mangans im pH-Bereich 4 - 8. Die optimalen Reaktionstemperaturen liegen im Bereich 20 - 50 °C; die Temperatur kann jedoch erhöht werden, wenn die Löslichkeitsverhältnisse es erfordern.Water, alcohols and water-alcohol mixtures are predominantly used as the possible reaction medium. The formation of the quaternary ammonium salts usually requires Reaction temperatures between 20 and 100 ° C, the production of the acid amide bond takes place in the same temperature range. Hydrogen sulfite addition to sulfobetaine takes place 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 optimal reaction temperatures are in the range 20 - 50 ° C; however, the temperature can be increased if the solubility ratios so require.

Die Bildung additionsfähiger Sulfitanionradikale kann anstelle des Systems luftsauerstoff/Obergangsmetall auch mit anderen Oxydationsmitteln eingeleitet werden; beispielsweise sind Salze der Peroxodischwefelsäure, Alkylperoxide, Acylperoxide oder Wasserstoffperoxid geeignet. Auch die Einwirkung mehrerer Oxydationsmittel als Radikalbildner kann vorteilhaft sein.The formation of sulfite anion radicals capable of addition can also be initiated with other oxidizing agents instead of the air oxygen / transition metal system; For example, salts of peroxodisulfuric acid, alkyl peroxides, acyl peroxides or hydrogen peroxide are suitable. The action of several oxidizing agents as free radical formers can also be advantageous.

Die erfindungsgemäßen Sulfobetaine I zeigen hervorragende Tensideigenschaften. Sie übertreffen in ihrem Kalkseifendispergiervermögen die bisher bekannten Typen der Formel II, in welchen die Säureamidbindung -CO-NH- in anderer Reihenfolge angeordnet ist. Diese unerwartet günstigen Eigenschaften unterscheiden die neuen Sulfobetaine vorteilhaft von den bekannten Vertretern der Verbindungsklasse.The sulfobetaines I according to the invention show excellent surfactant properties. They outperform the previously known types of formula II in their lime soap dispersing capacity, in which the acid amide bond -CO-NH- is arranged in a different order. These unexpectedly favorable properties advantageously distinguish the new sulfobetaines from the known representatives of the compound class.

Das erfindungsgemäße Verfahren ist in technischem Maßstab als Eintopfverfahren durchführbar, weil die bisher nicht technisch verfügbaren Aminkomponenten III jetzt nach DD-PS 136 497 wohlfeil zur Verfügung stehen. Die nachfolgenden Syntheseschritte verlaufen überraschenderweise jeweils mit quantitativer Ausbeute; deshalb kann ohne Isolierung von Zwischenstufen gearbeitet werden, was gegenüber dem bekannten Stand der Technik einen wertvollen Verfahrenseffekt darstellt.The process according to the invention can be carried out on a technical scale as a one-pot process, because the amine components III which were previously not technically available are now cheaply available according to DD-PS 136 497. The subsequent synthesis steps surprisingly each proceed with quantitative yield; it is therefore possible to work without isolating intermediate stages, which is a valuable process effect compared to the known prior art.

Als weiterer Vorteil der erfindungsgemäßen Verfahrensweise ist anzusehen, daß die Zwischenstufe V eine Vielzahl von Sulfobetainen mit Carbonamidgruppen zugänglich macht, ohne daß das cancerogene Propansulton eingesetzt werden muß.Another advantage of the procedure according to the invention is that intermediate V makes a large number of sulfobetaines with carbonamide groups accessible without the carcinogenic propane sultone having to be used.

Im folgenden wird die Erfindung anhand von Ausführungsbeispielen näher erläutert.The invention is explained in more detail below on the basis of exemplary embodiments.

Beispiel 1example 1 N-(3-Sulfopropyl)-N,N-dimethyl-ammonio-essigsäure-dodecyl-amidN- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid-dodecyl-amide

N-Allyl-N,N-dimethyl-ammonio-essigsäuremethylester-chlorid: 850 g (10 Mol) Dimethylallylamin werden in einem Reaktionsgefäß vorgelegt. Dazu tropft man unter Rühren zunächst bei Raumtemperatur 1085 g (10 Mol) Chloressigsäuremethylester (frei von Chloressigsäure). Während des Zutropfens steigt die Temperatur langsam an, die reagierende Mischung trübt sich und beginnt ständig das Quarternierungsprodukt als dickes viskoses Öl auszuscheiden. Durch gelegentliches Kühlen wird die Reaktionstemperatur im Bereich zwischen 60 und 70 °C gehalten, so daß nach etwa 30 min der Chloressigsäuremethylester zugesetzt ist.N-Allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride: 850 g (10 mol) of dimethylallylamine are placed in a reaction vessel. 1085 g (10 mol) of methyl chloroacetate (free of chloroacetic acid) are first added dropwise with stirring at room temperature. During the dropping, the temperature rises slowly, the reacting mixture becomes cloudy and the quaternization product begins to excrete as a thick viscous oil. The reaction temperature is kept in the range between 60 and 70 ° C. by occasional cooling, so that the methyl chloroacetate is added after about 30 minutes.

Man läßt kurzzeitig in diesem Temperaturbereich nachreagieren, bis der pH-Wert des Reaktionsproduktes auf 7 abfällt. Der Umsatz ist zu diesem Zeitpunkt quantitativ, da H-NMR-spektroskopisch nur noch das Zielprodukt nachweisbar ist, welches als homogene, klar durchsichtige Flüssigkeit anfällt.The reaction is allowed to continue for a short time in this temperature range until the pH of the reaction product drops to 7. The conversion at this point in time is quantitative, since only the target product can be detected by H-NMR spectroscopy, which is obtained as a homogeneous, clearly transparent liquid.

N-Allyl-N,N-dimethyl-ammonio-essigsäure-dodecylamid-chlorid:

  • Das so erhaltene Methylester-chlorid wird durch Zutropfen mit 1853 g (10 Mol) Dodecylamin (Cocosamin) versetzt, derart, daß die exotherme Reaktion der Amidbildung bei einer Reaktionstemperatur von 70 bis 80 °C gehalten werden kann. Nach ca. 30 min ist die Reaktion beendet und man erhält ein hochviskoses Produkt in quantitativer Ausbeute vom pH-Wert 7. 3788 g des Dodecylamidchlorids werden mit 11,36 kg Leitungswasser zu einer 25 %igen Lösung verdünnt (Lösung I).
N-allyl-N, N-dimethyl-ammonio-acetic acid-dodecylamide chloride:
  • The methyl ester chloride thus obtained is added dropwise with 1853 g (10 mol) of dodecylamine (cocosamine) in such a way that the exothermic reaction of the amide formation can be kept at a reaction temperature of 70 to 80 ° C. The reaction is complete after approx. 30 min and a highly viscous product is obtained in quantitative yield with pH 7. 3788 g of the dodecylamide chloride are diluted with 11.36 kg of tap water to a 25% solution (solution I).

Dann werden 950 g (5 Mol) Natriummetabisulfit Na2S2O5 und 126 g (1 Mol) Natriumsulfit Na2S03 in 14,07 kg Leitungswasser gelöst (Lösung II). 126 g Na2S03 (1 Mol) werden in 5 Liter Wasser gelöst und in einem Rührgefäß mit Lufteinleitungsrohr vorgelegt. Bei Zimmertemperatur tropft man nun unter Rühren und gleichzeitigem Lufteinleiten die Lösungen I und II simultan zu. Da das Reaktionsgemisch hierbei stark schäumt, wird die Schaumbildung durch Zusatz von ca. 1,5 Liter Isopropanol gemäßigt. Nach einer Zutropfzeit von ca. 90 min erhöht sich die Temperatur des Reaktionsgemisches um 10 °; der pH-Wert hält sich während der Umsetzung um 7. Nach Abfallen der Temperatur wird noch etwa 30 min unter intensivem Belüften stark gerührt. Der Umsatz des eingesetzten Dodecyl-amid-chlorids ist nun quantitativ. Die schwach gelbliche Sulfobetainlösung enthält noch Salze (NaCl, Na2S03 und Na2S04), von denen durch Einengen und Extraktion des Produktes mit Ethanol getrennt werden kann (Schmelzpunkt Z > 164 °C).Then 950 g (5 mol) sodium metabisulfite Na 2 S 2 O 5 and 126 g (1 mol) sodium sulfite Na 2 S0 3 are dissolved in 14.07 kg tap water (solution II). 126 g Na 2 S0 3 (1 mol) are dissolved in 5 liters of water and placed in a stirred vessel with an air inlet tube. At room temperature, solutions I and II are simultaneously added dropwise with stirring and simultaneous introduction of air. Since the reaction mixture foams strongly, the foam formation is moderated by adding about 1.5 liters of isopropanol. After a dropping time of approx. 90 min, the temperature of the reaction mixture increases by 10 °; the pH remains around 7 during the reaction. After the temperature has dropped, the mixture is stirred vigorously for about 30 minutes with vigorous ventilation. The conversion of the dodecyl amide chloride used is now quantitative. The slightly yellowish sulfobetaine solution also contains salts (NaCl, Na 2 S0 3 and Na2S04), from which the product can be separated by concentration and extraction with ethanol (melting point Z> 164 ° C).

Beispiel 2Example 2 N-(3-Sulfopropyl)-N,N-dimethyl-ammonio-essigsäure-heptylamidN- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid heptylamide

Figure imgb0010
Figure imgb0010

0,1 Mol nach Beispiel 1 bereitetes N-Allyl-N,N-dimethyl- ammonio-essigsäuremethylesterchlorid werden in entsprechender Arbeitsweise anstelle von Cocosamin mit o,1 Mol n-Heptylamin umgesetzt und anschließend mit Hydrogensulfitlösung/Natriumsulfitlösung wie in Beispiel 1 beschrieben in das Sulfobetain übergeführt; Schmelzpunkt Z> 178 °C.0.1 mol of N-allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride prepared according to Example 1 are reacted in a corresponding manner instead of cocosamine with 0.1 mol of n-heptylamine and then with hydrogen sulfite solution / sodium sulfite solution as described in Example 1 in the Converted to sulfobetaine; Melting point Z> 178 ° C.

Beispiel 3Example 3 N-(3-Sulfopropyl-N,N-dimethyl-ammonio-essigsäure-n-hexylamidN- (3-Sulfopropyl-N, N-dimethyl-ammonio-acetic acid-n-hexylamide

Figure imgb0011
Figure imgb0011

0,1 Mol nach Beispiel 1 bereitetes N-Allyl-N,N-dimethyl- ammonio-essigsäuremethylesterchlorid werden in entsprechender Arbeitsweise anstelle von Cocosamin mit 0,1 Mol n-Hexylamin umgesetzt und anschließend mit Hydrogensulfitlösung/Natriumsulfitlösung wie in Beispiel 1 beschrieben in das Sulfobetain übergeführt; hierbei ist ein Zusatz von Isopropanol als Schaumminderer nicht erforderlich; Schmelzpunkt Z> 178 °C.0.1 mol of N-allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride prepared according to Example 1 are reacted in a corresponding manner instead of cocosamine with 0.1 mol of n-hexylamine and then with hydrogen sulfite solution / sodium sulfite solution as described in Example 1 in the Converted to sulfobetaine; it is not necessary to add isopropanol as a foam reducer; Melting point Z> 178 ° C.

Beispiel 4Example 4 N-(3-Sulfopropyl)-N,N-dimethyl-ammonio-essigsäure-n-butylamidN- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid-n-butylamide

Figure imgb0012
Figure imgb0012

0,1 Mol nach Beispiel 1 bereitetes N-Allyl-N,N-dimethyl- ammonio-essigsäuremethylesterchlorid werden in entsprechender Arbeitsweise anstelle von Cocosamin mit 0,1 Mol n-Butylamin umgesetzt und anschließend mit Hydrogensulfitlösung/Natriumsulfitlösung wie in Beispiel 1 beschrieben in das Sulfobetain übergeführt, wobei ein Zusatz von Isopropanol zur Schaumvermeidung nicht erforderlich ist; Schmelzpunkt Z>213 °C0.1 mol of N-allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride prepared according to Example 1 are reacted in a corresponding manner instead of cocosamine with 0.1 mol of n-butylamine and then with hydrogen sulfite solution / sodium sulfite solution as described in Example 1 Converted sulfobetaine, with the addition of isopropanol is not necessary to avoid foam; Melting point Z> 213 ° C

Beispiel 5Example 5 N-(3-Sulfopropyl-N,N-Dimethyl-ammonio-essigsäure-isopropyl- amidN- (3-sulfopropyl-N, N-dimethyl-ammonio-acetic acid-isopropyl-amide

Figure imgb0013
Figure imgb0013

Man verfährt wie in den Beispielen 1 - 4 beschrieben unter Einsatz von Isopropylamin zur Herstellung des Amids bei sonst gleicher Verfahrensweise. Der Umsatz ist auch hier quantitativ. Schmelzpunkt Z>237 °C.The procedure is as described in Examples 1-4 using isopropylamine to prepare the amide using the same procedure. Here, too, the turnover is quantitative. Melting point Z> 237 ° C.

Der Schmelzpunkt des entsprechenden n-Propylderivats beträgt Z > 189 °C.The melting point of the corresponding n-propyl derivative is Z> 189 ° C.

Beispiel 6Example 6 N-(3-Sulfopropyl)-N,N-dimethyl-ammonio-essigsäureamidN- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid amide

13C-NMR-Spektrum 13 C NMR spectrum

(D20, externer Standard TMS); die Zahlenangaben an den Atomsymbolen entsprechen den chemischen Verschiebungen in ppm:(D 2 0, external standard TMS); the numbers on the atomic symbols correspond to the chemical shifts in ppm:

Figure imgb0014
Figure imgb0014

In o,1 Mol nach Beispiel 1 bereiteten N-Allyl-N,N-dimethyl- ammonio-essigsäuremethylesterchlorid werden zur Herstellung der Amidstufe mindestens 0,1 Mol Ammoniak eingeleitet. Das erhaltene Amid wird nach der Verfahrensweise der Beispiele 1 - 4 in das Sulfobetain übergeführt; Schmelzpunkt Z>268 °C.In 0.1 mol of N-allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride prepared according to Example 1, at least 0.1 mol of ammonia is introduced to produce the amide stage. The amide obtained is converted into the sulfobetaine according to the procedure of Examples 1-4; Melting point Z> 268 ° C.

Beispiel 7Example 7 N-(3-Sulfopropyl)-N,N-dimethyl-ammonio-essigsäure-n-hexadecyl-amidN- (3-sulfopropyl) -N, N-dimethyl-ammonio-acetic acid-n-hexadecyl amide

Figure imgb0015
Figure imgb0015

Man stellt wie in Beispiel 1 beschrieben 10 Mol N-Allyl-N,N-dimethyl-ammonio-essigsäuremethylesterchlorid her und versetzt dieses im Teperaturbereich von 70° - 80° im Verlaufe von 30 min unter Rühren portionsweise mit festem n-Hexadecylamin. Das erhaltene sirupöse opake Hexadecylamidchlorid wird bei 45 °C in isopropanolhaltigem Wasser gelöst und die Lösung entsprechend der Verfahrensweise des Beispiels 1, jedoch bei 40 °C, weiter zum Sulfobetain umgesetzt; Schmelzpunkt 123° - 127 °C. Der Umsatz ist quantitativ.10 moles of N-allyl-N, N-dimethyl-ammonio-acetic acid methyl ester chloride are prepared as described in Example 1, and solid n-hexadecylamine is added in portions in the temperature range from 70 ° to 80 ° over the course of 30 minutes with stirring. The syrupy opaque hexadecylamide chloride obtained is dissolved in water containing isopropanol at 45 ° C. and the solution is further converted into sulfobetaine in accordance with the procedure of Example 1, but at 40 ° C.; Melting point 123 ° - 127 ° C. The turnover is quantitative.

Bei der Herstellung des analogen Produktes aus C16/C18-Fett- amingemisch verfährt man ganz entsprechend. Schmelzpunkt dieses Sulfobetaingemisches: 81° - 86 °C.The procedure for producing the analogue product from C 16 / C 18 -fatty amine mixture is very similar. Melting point of this sulfobetaine mixture: 81 ° - 86 ° C.

Beispiel 8Example 8 N-(3-Sulfopropyl)-N,N-dimethyl-ammonio-malonsäure-di-n-dodecylamidN- (3-sulfopropyl) -N, N-dimethyl-ammonio-malonic acid-di-n-dodecylamide

Figure imgb0016
Figure imgb0016

N-Allyl-N,N-dimethyl-ammonio-malonsäure-diethylester-bromid: 85 g (1 Mol) Dimethylallylamin werden in 200 ml Ethanol gelöst. Zu dieser Lösung tropft man unter Rühren bei 30 °C 239,1 g (1 Mol) Brommalonsäurediethylester und rührt noch 2 Stunden bei 80 °C nach.N-Allyl-N, N-dimethyl-ammonio-malonic acid diethyl ester bromide: 85 g (1 mol) of dimethylallylamine are dissolved in 200 ml of ethanol. 239.1 g (1 mol) of diethyl bromomalonate are added dropwise to this solution with stirring at 30 ° C. and the mixture is subsequently stirred at 80 ° C. for 2 hours.

N-Allyl-N,N-dimethyl-ammonio-malonsäure-di-n-doecyl-amid- bromid:

  • Die vorstehend erhaltene Ethylesterbromid-Lösung wird mit 370,6 g (2 Mol) n-Dodecylamin (Cocosamin) wie in Beispiel 7 beschrieben bei 700 - 80 °C umgesetzt, wobei zur Vervollständigung des Umsatzes noch 2 Stunden bei dieser Temperatur gerührt wird. Die homogenkatalysierte Hydrogensulfit-Addition wird zur Verbesserung der Löslichkeit in Gegenwart von n-Butanol bei 50° - 60 °C vorgenommen.
  • Nach Abkühlen des Reaktionsgemisches fällt das Sulfobetain aus und kann aus Ethanol umkristallisiert werden; Schmelzpunkt: 108° - 114 °C.
N-allyl-N, N-dimethyl-ammonio-malonic acid-di-n-doecyl-amide bromide:
  • The above-obtained solution is Ethylesterbromid with 370.6 g (2 mol) of n-dodecylamine (cocoamine) as described in Example 7 at 70 0 to 80 ° C reacted with stirring at this temperature to complete the reaction a further 2 hours. The homogeneously catalyzed hydrogen sulfite addition is carried out in the presence of n-butanol at 50 ° -60 ° C. to improve the solubility.
  • After the reaction mixture has cooled, the sulfobetaine precipitates and can be recrystallized from ethanol; Melting point: 108 ° - 114 ° C.

Beispiel 9Example 9 Vergleichende Bestimmung des KalkseifendispergiervermögensComparative determination of lime soap dispersing capacity

Die Bestimmung erfolgt nach DDR-Standard TGL 22254 Blatt 1 (Gruppe 482) von Juli 1967 (Determination of Lime-Soap Dispersing Property). Das Kalkseifendispergiervermögen ist die Fähigkeit, das Ausflocken oder Zusammenballen von Kalkseife zu verhindern und diese für eine bestimmte Zeit in so feiner Dispersion zu halten, daß sie sich nicht auf textilen oder anderen Oberflächen niederschlägt. Die Grenze der Beständigkeit von Seifenlösungen gegen hartes Wasser wird durch Zugabe von variierenden Mengen des zu prüfenden Produktes festgestellt. Zur Berechnung ist die gefundene Menge des zu prüfenden Produktes zugrunde zu legen. Die Angabe des Kalkseifendispergiervermögens K erfolgt in % Produkt, bezogen auf das als Standardbezugssubstanz eingesetzte Natrium-Oleat.

Figure imgb0017
daß heißt, niedrige Prozentwerte weisen ein gegenüber Natrium-Oleat gutes Kalkseifendispergiervermögen aus.The determination is made according to the DDR standard TGL 22254 sheet 1 (group 482) from July 1967 (Determination of Lime-Soap Dispersing Property). The lime soap dispersing ability is the ability to prevent flocculation or agglomeration of lime soap and to keep it in such a fine dispersion for a certain time that it does not deposit on textile or other surfaces. The limit of the resistance of soap solutions to hard water is determined by adding varying amounts of the test Product detected. The quantity found for the product to be tested must be used as the basis for the calculation. The lime soap dispersing capacity K is stated in% of product, based on the sodium oleate used as the standard reference substance.
Figure imgb0017
 that is, low percentages have a good lime soap dispersing capacity compared to sodium oleate.

Die Bestimmung erfolgte bei einer Wasserhärte von 30° dH.

Figure imgb0018
The determination was made at a water hardness of 30 ° dH.
Figure imgb0018

Claims (7)

1. Neue Sulfobetaine von Ammoniocarbonsäureamiden der allgemeinen Formel I,
Figure imgb0019
worin R1 und R2 Wasserstoff, geradkettige oder verzweigte Alkylreste mit bis zu 22 C-Atomen, R3 und R4 gleiche oder verschiedene kurzkettige Alkylreste mit 1 bis 4 C-Atomen oder Hydroxyalkylreste mit 2 bis 3 C-Atomen oder Oxyethylenreste, R5 Alkylreste mit bis zu 22 C-Atomen oder Wasserstoff oder Alkylaminocarbonylreste und n ganze Zahlen von 0 bis 3 bedeuten.1. New sulfobetaines of ammoniocarboxamides of the general formula I,
Figure imgb0019
 wherein R 1 and R 2 are hydrogen, straight-chain or branched alkyl radicals with up to 22 C atoms, R 3 and R 4 are identical or different short-chain alkyl radicals with 1 to 4 C atoms or hydroxyalkyl radicals with 2 to 3 C atoms or oxyethylene radicals, R 5 alkyl radicals with up to 22 carbon atoms or hydrogen or alkylaminocarbonyl radicals and n are integers from 0 to 3. 2. Verfahren zur Herstellung neuer Sulfobetaine von Ammoniocarbonsäureamiden nach Anspruch 1, dadurch gekennzeichnet, daß Dialkylallylamine der Formel III
Figure imgb0020
mit Halogencarbonsäureestern der Formel IV
Figure imgb0021
quaternisiert und die entstehenden quartären Ammoniumverbindungen der Formel V
Figure imgb0022
mit Aminen der Formel VIII
Figure imgb0023
und Hydrogensulfit umgesetzt werden, wobei die Substituenten R1 bis R5 und n in den Formeln die obengenannte Bedeutung besitzen.2. A process for the preparation of new sulfobetaines of ammoniocarboxamides according to claim 1, characterized in that dialkylallylamines of the formula III
Figure imgb0020
 with halocarboxylic acid esters of the formula IV
Figure imgb0021
 quaternized and the resulting quaternary ammonium compounds of formula V
Figure imgb0022
 with amines of formula VIII
Figure imgb0023
 and hydrogen sulfite are reacted, the substituents R 1 to R 5 and n in the formulas having the abovementioned meaning. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Reaktionen bei einer Temperatur von 20 bis 100 °C durchgeführt werden.3. The method according to claim 2, characterized in that the reactions are carried out at a temperature of 20 to 100 ° C. 4. Verfahren nach Anspruch 2 und 3, dadurch gekennzeichnet, daß die Hydrogensulfitaddition im pII-Bereich von 4 bis 8 vorgenommen wird.4. The method according to claim 2 and 3, characterized in that the hydrogen sulfite addition is carried out in the pII range from 4 to 8. 5. Verfahren nach Anspruch 2 bis 4, dadurch gekennzeichnet, daß nach der Quaternisierung zuerst die Hydrogensulfitaddition und anschließend die Umsetzung mit Aminen der Formel VIII erfolgt.5. The method according to claim 2 to 4, characterized in that after the quaternization, first the hydrogen sulfite addition and then the reaction with amines of the formula VIII. 6. Verfahren nach Anspruch 2 bis 4, dadurch gekennzeichnet, daß nach der Quaternisierung die Umsetzung mit Aminen der Formel VIII durchgeführt und anschließend die Reaktion mit Hydrogensulfit vorgenommen wird. .6. The method according to claim 2 to 4, characterized in that after the quaternization, the reaction with amines of the formula VIII is carried out and then the reaction is carried out with hydrogen sulfite. . 7. Verwendung der Sulfobetaine der Formel I nach Anspruch 1 als Tensidbestandteile von Wasch- und Reinigungsmitteln, als Flotationsmittel sowie als Emulgatoren.7. Use of the sulfobetaines of formula I according to claim 1 as surfactant components of detergents and cleaning agents, as flotation agents and as emulsifiers.
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US5336445A (en) * 1990-03-27 1994-08-09 The Procter & Gamble Company Liquid hard surface detergent compositions containing beta-aminoalkanols
US5342549A (en) * 1990-01-29 1994-08-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine
US5454983A (en) * 1992-01-23 1995-10-03 The Procter & Gamble Company Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US5536451A (en) * 1992-10-26 1996-07-16 The Procter & Gamble Company Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant
US5536450A (en) * 1993-11-12 1996-07-16 The Procter & Gamble Comany Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume
US5540864A (en) * 1990-12-21 1996-07-30 The Procter & Gamble Company Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
US5540865A (en) * 1990-01-29 1996-07-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine
WO2017048555A1 (en) * 2015-09-17 2017-03-23 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic alkyl-alkanoylamides and/or alkyl alkanoates
US9822073B2 (en) 2014-10-20 2017-11-21 Eastman Chemical Company Heterocyclic amphoteric compounds
US9877904B2 (en) 2014-10-20 2018-01-30 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic ester ammonioalkanoates containing a heterocyclic group
US9943816B2 (en) 2014-10-20 2018-04-17 Eastman Chemical Company Amphoteric ester sulfonates
CN109072061A (en) * 2016-04-08 2018-12-21 罗地亚经营管理公司 Zwitterionic surfactant suitable for intensified oil reduction
US11414380B2 (en) 2015-09-17 2022-08-16 Eastman Chemical Company Amphoteric compounds

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US5342549A (en) * 1990-01-29 1994-08-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine
US5540865A (en) * 1990-01-29 1996-07-30 The Procter & Gamble Company Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine
US5336445A (en) * 1990-03-27 1994-08-09 The Procter & Gamble Company Liquid hard surface detergent compositions containing beta-aminoalkanols
US5540864A (en) * 1990-12-21 1996-07-30 The Procter & Gamble Company Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
US5454983A (en) * 1992-01-23 1995-10-03 The Procter & Gamble Company Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol
US5536451A (en) * 1992-10-26 1996-07-16 The Procter & Gamble Company Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant
US5536450A (en) * 1993-11-12 1996-07-16 The Procter & Gamble Comany Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume
US5531933A (en) * 1993-12-30 1996-07-02 The Procter & Gamble Company Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US9822073B2 (en) 2014-10-20 2017-11-21 Eastman Chemical Company Heterocyclic amphoteric compounds
US9877904B2 (en) 2014-10-20 2018-01-30 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic ester ammonioalkanoates containing a heterocyclic group
US9943816B2 (en) 2014-10-20 2018-04-17 Eastman Chemical Company Amphoteric ester sulfonates
US11000816B2 (en) 2014-10-20 2021-05-11 Eastman Chemical Company Amphoteric ester sulfonates
WO2017048555A1 (en) * 2015-09-17 2017-03-23 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic alkyl-alkanoylamides and/or alkyl alkanoates
CN108024935A (en) * 2015-09-17 2018-05-11 强生消费者公司 Composition comprising amphion alkyl-alkanol-amide and/or alkyl alkanoate
KR20180051636A (en) * 2015-09-17 2018-05-16 존슨 앤드 존슨 컨수머 인코포레이티드 Compositions comprising zwitterionic alkyl-alkanoyl amides and / or alkyl alkanoates
US9993408B2 (en) 2015-09-17 2018-06-12 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic alkyl-alkanoylamides and/or alkyl alkanoates
US11414380B2 (en) 2015-09-17 2022-08-16 Eastman Chemical Company Amphoteric compounds
CN109072061A (en) * 2016-04-08 2018-12-21 罗地亚经营管理公司 Zwitterionic surfactant suitable for intensified oil reduction
CN109072061B (en) * 2016-04-08 2021-10-08 罗地亚经营管理公司 Zwitterionic surfactants suitable for enhanced oil recovery

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