DE1956626A1 - Process for the preparation of sulfitobetaines - Google Patents

Description

Badische Anilin- & Soda-Fabrik AG

Our reference: O.Z.26 476 ¥ B / Be

6700 Ludwigshafen, November 10, 1969 Process for the production of sulfitobetaines

The invention relates to a process for the preparation of sulfitobetaines by reacting thionamide compounds with 1,2-alkylene oxides.

It is known that sulfitobetaines can be prepared by reacting amines with mixtures of equimolar amounts of sulfur dioxide and alkylene oxides (DBP 1 150 095). This process has the technical part that under the catalytic influence of amines, the mixture of sulfur dioxide and alkylene oxide is very easily converted into polymeric glycol sulfite (Chim. Et Ind. §1_, 233 (1952); French patent specification 1 011 225), which the reaction products contaminates and makes special cleaning operations necessary.

It has now been found that sulfitobetaines of the general formula

R-. R-f R ^

R ₂ -IT CH CHOSO ₂ I,

R ₂ "

in which the individual residues R ,, R _? , R ^ can be the same or different and each mean an aliphatic, cycloaliphatic ^ araliphatic or aromatic radical, in addition the individual radicals R ₂ and / or R-, each also for a hydrogen atom, can stand for R ₁ and a radical R ₂ together with the adjacent nitrogen atom can also mean members of a heterocyclic ring, advantageously obtained when thionamide compounds in the form of thionamide acids of the general formula

405/69 ^ά ■. ■ - 2 -

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in which R ₁ and Rp have the aforementioned meaning, or of sulfites of the thionylamides of the general formula

R ₁ 0 R ₁ R ₀ -FSFR

2 y

III,

in which R ^ and Rp have the aforementioned meaning with 1,2-alkylene oxides the general formula

■ ρ r \ r \ "ρ · ΤΛΓ

Xl ₃ <- » \ ~> XW -LV,

⁵ HH ³

in which the individual radicals R _{3 have} the aforementioned meaning.

The reaction can be carried out in the case of using piperidyl thionamic acid or thionyl di (trimethylammonium) sulfite and Represent ethylene oxide by the following formulas:

H Jf-SO ₀ H + HoG

CX

H IrH-GH ₂ -CE ₂ C-SC ₂

CH, O CH,

• GH, - F - S - F - CH, 3 y ν 3

SO,

CH ₃ φ
2 GH ₃ -F-GH

-CH,

Compared to the known methods, the terrar delivers: according to the invention in a simple way before a large number. ..- fitobetainen in better yield and purity. Polymers of series not clearly formed.

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The thionamide compounds used as starting materials II or III can be prepared, for example, by reacting amines with sulfur dioxide (Houben-Weyl, Methods of Organic Chemistry, Volume 11/2, pages 731 ff; Zeitschrift für physik.Chemie (1937) Volume 178 A, pages 57 ff). If primary and secondary amines are used, the thionamic acids II are generally obtained, and the sulfites III in the case of tertiary amines. Preferred thionamide compounds II and III and correspondingly preferred end products I are those in whose formulas the individual radicals R ^ and Rp can be the same or different and in each case an alkyl radical with 1 to 34, in particular 1 to 12 carbon atoms, an alkenyl radical with 2 to 30, in particular 2 to 12 carbon atoms, a cycloalkyl radical or cycloalkenyl radical with 5 to 7 carbon atoms each, an aralkyl radical with 7 to 12 carbon atoms, a phenyl or naphthyl radical, in addition the individual radicals Rp can each also represent a hydrogen atom, R ₁ and a radical Rp together with the adjacent nitrogen atom can also mean members of a 3-, 5- or 6-membered heterocyclic ring which, in addition to the nitrogen atom, can also contain an oxygen atom or a further nitrogen atom. In the preferred alkyl and alkenyl radicals, the carbon chains can also be interrupted by groups which are inert under the reaction conditions, such as -CO-NH- or _q_q_. The aforementioned radicals and rings can also be replaced by groups and / or atoms which are inert under the reaction conditions, for example chlorine atoms, bromine atoms, hydroxyl, carbonamido, nitro groups; Carbalkoxy, alkyl, acyloxy, acylamido, alkoxy groups can be substituted with up to 7 carbon atoms each.

For example, those obtained by reaction with sulfur dioxide can be used Thionamide compounds of the following tertiary amines as starting materials II and III are used: tridodecyl, tristearyl, tricyclohexyl, triphenyl, methyl-ethyl-dodecyl, diethylphenyl, Tri- (2,4-dinitrophenyl) -, tri- (ß-lauric acid amidoethyl) -, Stearyl-di- (ß-stearatoethyl) -, di- (ß-lauryl acid amidoethyl) -ßcarbbutoxyäthyl-, Dimethyl stearyl, methyl distearyl, trimethyl, Triethylamine, tributylamine, N-methyl-ethyleneimine, N-ethylpenta-methylenimine, N-methylmorpholine, N-methylpiperidine; Butylamine, dodecylamine, cetylamine, stearylamine, cyclohexylamine,

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Aniline, c6- or ß-] tfaphthylamine, benzylamine, allylamine pr.opargylamine, Ethylenimine, diethylamine, diethanolamine, 'dibutylamine · ■ Di- (2-ethylhexyl) amine, methylaniline, diallylamine.

Other starting materials are alkylene oxides, which in stoichiometric .scher Amount or in excess, preferably in a molar ratio of 1 to 1.5 moles per mole of starting material II or 2 to 3 moles each Mole of starting material III, are implemented. Preferred starting materials IY and correspondingly preferred end materials I are those in their formulas the individual radicals R, identical or different can be, and each for an alkyl radical with 1 to 7 carbon atoms, a phenyl group, a hydrogen atom, a carbalkoxy group with 2 to 6 carbon atoms, a carbonamido group. The mentioned residues can still be through the above indicated inert groups and / or atoms may be substituted. If the starting materials IY have more than one epoxy group, e.g. Butadiene diepoxide, corresponding di- or polybetaines are obtained.

E.g. the following alkylene oxides are used as starting materials IY are: ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, Styrene oxide, epichlorohydrin, glycidic acid amide, butadiene diepoxide, ß-methylglycidic acid ethyl ester, glycidomethyl ether.

The reaction is continuously or intermittently carried out usually at a temperature between O ⁰ C and 20O ⁰ C, preferably between 20 and 100 ⁰ C, under atmospheric or superatmospheric pressure. It is expedient to use organic solvents which are inert under the reaction conditions, such as chlorinated hydrocarbons, for example ethylene chloride, chloroform, trichlorethylene; Alcohols, for example ethanol; Ketones, for example acetone, methyl ethyl ketone; Ethers, for example dioxane, tetrahydrofuran, diethyl ether; aliphatic hydrocarbons, for example heptane, octane, petroleum ether, ligroin; cycloaliphatic hydrocarbons, for example cyclohexane; or their mixtures.

The reaction can be carried out as follows: A mixture of the Starting materials II or III and IV, optionally together with Solvent, is kept at the reaction temperature for 1 to 8 hours. Then the end product is made from the reaction

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mix in the usual way, e.g. through. Filtration or fractionated Distillation, separated.

The new "compounds which can be prepared by the process of the invention are valuable starting materials for the production of dyes, detergents, wetting agents, finishing agents, dishwashing detergents, hair shampoos, emulsifiers, dispersants, lotation auxiliaries, softeners and auxiliaries in the textile dyeing and printing industry, and pesticides. For example, with the reaction product of thionyl-di- (methyl-di- $ *, ^ * ¹ -s tear insäur e-amido-propyl-ammonium) sulfite and ethylene oxide in an amount of 1 to 20 grams per Liters of aqueous finishing liquor impregnate cotton or rayon fabrics, dry them and thus give the fabrics a soft, smooth and plump feel the remaining components can be any known detergent components. The following two mixtures serve as examples: ■

a) Dishwashing detergent (liquid, moderately foaming)

Composition;

5 parts by weight of alkylbenzenesulfonic acid (diethanolamine salt) 5 "nonyl phenol x 10 ethylene oxide 5 "end product I (example 18) N, N-dimethyl-N-ß-

laurato-isopropyl-N-O ^ -phenyl-ß-sulfito-ethyl-

ammonium betaine
5 "isopropanol
5 "tetrapotassium pyrophosphate 75" water

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"* b) Dishwashing liquid (liquid, high foaming) Composition:

10 parts by weight of alkylbenzenesulfonic acid (diethanolamine salt)

3 "nonyl phenol x 10 ethylene oxide

4 "fabric
1 "Trilon-B

3 "end product I (example 20) N, N-dimethyl-N-

('y-stearic acid-amido -) - propyl-N- (Λ-phenyl) » ß-sulfito-ethyl-ammonium-betain 79 "water

The parts mentioned in the examples are parts by weight.

example 1

a) 22 parts of sulfur dioxide are introduced into a solution of 90 parts of stearylamine in 400 parts of benzene at 40 to 50 ^{° C. with stirring.} After one hour of stirring Mach is cooled to 10 ⁰ C and filtered with suction, the crystal mass formed. This gives 85 parts (69.7 $> of theory) Stearylthionamidsäure.

b) To a solution of 80 parts of stearyl thionamidsäure in 200 parts of cyclohexane are slowly added at 25 to 30 ⁰ C, with stirring, 29 parts of styrene oxide. After seven hours of stirring the mixture at 75 ⁰ C, the solvent is distilled off. 104 parts (95.4 # of theory) of N-stearyl-N-oO-phenyl-β-sulfito-ethyl-ammonium-betaine are obtained. n ^ = 1.4983.

Example 2

a) 85 parts of piperidine, which are dissolved in 100 parts of acetone, are slowly added to a solution of 64 parts of sulfur dioxide in 200 parts of acetone at -5 ° C. with stirring. The formed crystalline. After stirring for two hours, the mass is filtered off with suction. This gives 145 part (97 1 * 5 'of theory) piperidyl thionamidsäure in the form of colorless crystals. Z ⁰ O (decomp.)

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b) 11 parts of ethylene oxide are introduced into a solution of 32 parts of piperidylthionamic acid in 150 parts of ethanol at 35 ° to 37 ° C. with stirring. After two hours of stirring of the mixture at 35 ⁰ C, the solvent is distilled off under reduced pressure. 33 parts (80.4% of theory) of β-sulfitoethyl-piperidinium-betaine are obtained in the form of a yellow oil. n ^ ° = 1.4679.

Example 3

a) 64 parts of sulfur dioxide are introduced ^{at 30 °} C. with stirring into a solution of 87 parts of morpholine in 150 parts of benzene. The mixture is stirred for two hours and the solvent is distilled off under reduced pressure. Parts (90.7% of theory) of morpholylthionamic acid are obtained in the form of colorless crystals. Mp. 118 to 120 ⁰ C.

b) In a solution of 60 parts morpholyl-thionamidsäure in 100 parts of ethanol are introduced 28 parts of ethylene oxide with stirring at 26 to 33 ⁰ C. After three hours of stirring the mixture at 40 ⁰ C, the solvent is distilled off under reduced pressure. 55 parts are obtained (70.5 i> of theory) of N-ß-sulfito-ethyl-morpholinium-betaine as a yellow oil. n ^ ° = 1.4918 / - .. ".

Example 4

a) To a solution of 64 parts of sulfur dioxide in 150 parts of acetone, a solution of 267 parts of oleyl amine in 400 parts of acetone was added slowly at 5 ⁰ C with stirring. After stirring the mixture for one hour, the resulting crystal slurry is filtered off with suction, washed with acetone and dried. 320 parts (96.6% of theory) of oleyl thionamic acid are obtained in the form of colorless crystals. Fp 78 to 80 ⁰ C.

b) In a solution of 100 parts of oleyl thionamidsäure in 200 parts of dioxane are introduced at 41 "to 45 ⁰ C, with stirring, 33 parts of ethylene oxide After two hours of stirring the mixture, the solvent is under reduced pressure.

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distilled off. 100 parts (88.5 ° fo of theory) oleyl-ß-sulfitoethyl-ammonium-betaine are obtained in the form of a yellow,

20th
water soluble paste, n ^ = 1.4838.

Example 5

a) To 64 parts of liquid sulfur dioxide are "30 parts of trimethylamine was added slowly at -30 ⁰ C under stirring. It separates a crystal slurry from which is filtered off with suction and washed with acetone. This gives 55 parts (88.9 ° i of theory) Thionyldi- (trimethylainmonium) sulfite colorless in the form of crystals. Pp 75.5 to 77.5 C ⁰

b). In a solution of 31 parts Thionyldi- (trimethyl-ammonium) sulphite in 50 parts of ethanol, 11 parts of ethylene oxide are introduced at 25 ⁰ C, with the temperature at 35 ° C increases. By adding 400 parts of acetone, the N-trimethyl-N-ßsulfitoäthyl-ammonium-betaine is precipitated as a hygroscopic mass. 17 parts (40.5% of theory) of N-trimethyl-IT-ß-sulfitoethyl-ammonium-betaine are obtained. n £ = 1.4957.

Example 6

a) 29 parts of ΪΤ, Ν-dimethyl-F-hexylamine are dissolved in 25 parts of acetone. 15 parts of sulfur dioxide are passed in at 25 to 30 ^{° C. with stirring.} The yellow solution is concentrated, and 42 parts (95.6% of theory) thionyl di (dimethylhexyl ammonium) sulfite are obtained. n ^ = 1.4720.

b) In a solution of 42 parts Thionyldi- (dimethyl-hexylammonium) sulfite in 25 parts of acetone are introduced with stirring at 20 to 4O ⁰ C, 10 parts of ethylene oxide. After three hours ITachrühren the mixture at 3O ⁰ C, the solvent is distilled off under reduced pressure, obtaining 51.3 parts (97.0 $ of theory) ΙΤ, ΙΤ-Dimethyl-F-hexyl-N-ß-sulfitoäthyl-ammonium- betaine in the form of a red-brown oil. n | ° = 1.4621.

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Example 7

a) In a solution of 392 parts of Ν, Ν-dimethyl-N-octylamine in 200 parts of acetone are introduced at 10 to 3O ⁰ C in the course of 2 hours 200 parts of sulfur dioxide. After another 2 hours of stirring at 3O ⁰ C, the mixture is concentrated, and the residue obtained is 541 parts (98.3 i "of theory) Thionyldi- (dimethyl-octyl-ammonium) sulphite. n ^ = 1.4711.

b) In a solution of 541 parts Thionyldi- (dimethyl-octylammonium) sulfite in 200 parts of acetone are introduced with stirring at 10 to 25 ⁰ C, 110 parts of ethylene oxide, the temperature rising to 55 ⁰ C. The solvent is distilled off under reduced pressure. 543 parts (98.7% of theory) of NjN-dimethyl-N-octyl-N-ß-sulfito-ethylammonium-betaine are obtained in the form of a light brown paste. n ^ ° = 1.4775.

Example 8

a) In a solution of 68 parts of Ν, Ν-dimethyl-N-tridecyl-aniln in 40 parts of acetone, 20 parts of sulfur dioxide are introduced at 25 to 30 ⁰ C in 1/2 hour. After concentration, 79 parts are obtained (90.8 $> of theory) Thionyldi- (dimethyl-tridecyl-ammonium) sulphite. n ^ ° = 1.4716.

b) In 79 parts Thionyldi-idimethyl-tridecyl-ammoniumy sulfite are introduced at 25 to 30 ⁰ C, with stirring, 14 parts of ethylene oxide, the temperature rising to 80 ⁰ C. After four hours of stirring of the mixture, 90 parts are obtained (97.7 1 "of theory) Ν, Ν-dimethyl-N-trideeyl-N-ß-sulfitoäthyl-ammonium-betaine in the form of a yellow, water-soluble oil. n | ° = 1.4801

c) To 100 parts Thionyldi-Cdimethyl-tridecyl-ammonium) sulphite> 42 parts of styrene was added slowly and the mixture is stirred for 8 hours at 75 ⁰ C. 137 parts (96.4 $> of theory) are obtained Ν, Ν-dimethyl-N-tridecyl-N-oG-phenyl-ßsulfito-ethyl-ammonium-betaln in the form of a yellow oil. ni ° = 1.5090. 109821/2273 -.10-

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Example 9

a) In a solution of 283 parts of a mixture of F, H-dimethyl-F-hexadecyl-amine and F, F-dimethyl-1-M-octadecyl-amine in 300 parts of acetone are "at 25" to 40 ⁰ G 97 parts Sulfur dioxide initiated. After two hours of stirring, the solvent is distilled off under reduced pressure and 343 parts (98.8 % of theory) of the mixture of thionyl di (dimethyl hexadecyl ammonium) sulfite and thionyl di (dimethyl octadecyl ammonium) are obtained. sulfite in the form of a yellow paste. n ^ ° = 1.4594.

b) In 1041 parts of the mixture of Thionyldi- (dimethyl-hexadecyl-ammonium) sulphite and Thionyldi- (dimethyl-octadecylammonium) sulfite are introduced at 20 ⁰ C, 132 parts of ethylene oxide. Multiple times for four hours stirring the mixture at 30 ⁰ G obtained 1 170 (99.6 <fo of theory) of the mixture fjf-dimethyl-hexa-F / octa-decyl-F-ß-sulfito-'äthylammonium betaine in the form of a Paste, n £ = 1.5074.

c) 104 parts of the mixture of TMonyldi- (dimethyl-hexadecylammonium) sulfite and Thionyldi- (dimethy1-octadecyl-ammonium) sulphite are stirred with 36 parts of styrene oxide for four hours at 70 to 75 ⁰ C. This gives 138 parts (98.5 1 ° of theory) of the mixture of FJN-dimethyl-H-hexa-deeyl-N-fl ^ -phenyl-ßsulfito-ethyl-ammonium-betaine and F, F-H-Dimeth.yl -octadecyl-F-oO-phenyl-ß-sulfitoethyl-ammonium-betaine in the form of a yellow paste, n ^ = 1.4878.

Example 10

a) 22 parts of sulfur dioxide are introduced into 97 parts of a mixture of F-methyl-H-benzyl-IT-hexadecylamine and F-methyl-F-benzyl-F-octadecyl-aiain with stirring at room temperature. If the mixture is stirred for one hour, 112 parts (97.4 $> of theory) of a mixture of thionyldi- (methylbenzylhexadecylammonium) sulfite and 3hionyldl- (methylbenzyl-oetadecylammonium) sulfite are obtained in the form of a yellow , water-soluble oil. nl ° = 1.5031.

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1956625

b) In 100 parts of a mixture of Thionyldi- (methyl-benzylhexadecyl-ammonium) sulphite and Thionyldi- (methyl-benzyloctadecyl-ammonium) -sulfi-fc are introduced "at 23" to 28 ⁰ G with stirring 105 parts of ethylene oxide. After stirring the mixture for three hours at 35 ° G, 105 parts (95% of theory) of the mixture of IT ^ -Bimethyl-IT-hexadecyl-IT-B-sulfitoethyl-ammonium-betaine and !!, K-M-methyl -iT-octadecyl-N-ß-sulfitoethyl-ammonium-betaine in the form of a water-soluble, yellow oil that slowly crystallizes, n ^ = 1.4924.

Example 11

a) 143 parts of sulfur dioxide are introduced into 197 parts of F-octylpiperidine at 25 to 30 ^{° C. with stirring.} After six hours of stirring of the mixture at 40 ⁰ C, the excess sulfur is removed under reduced pressure. 248 parts (95.0 # of theory) thionyldi-octylpiperidinium are obtained -

50 sulfite in the form of a red-brown 01s. n ^ = 1.4848.

b) To 105 parts Thionyldi- (octyl-piperidinium) sulfite are added at 25 to 30 ° C, 35 parts glycidamide and stirred for three hours at 45 to 55 ⁰ C. This gives 135 parts (96.1 1 ° of theory) H-Oetyl-H "- (" i "-carbonai3iido-ß-sulfito) -äthylpiperidinium betaine in the form of a viscous, brown, water-soluble oil n _D = 1. 5019

Example 12

a) 51 parts of sulfur dioxide are introduced into 202 parts of N-dodecylpiperidine at room temperature with stirring, the temperature rising to 48.degree. Each three hours of stirring of the mixture at 25 to 30 ⁰ C 251 parts is obtained (99.2 ° i of theory) Thionyldi- (dodecyl-piperidinium) sulfite in the form of a red-brown oil. n ^ = 1.4882.

b) 30 parts of epichlorohydrin are slowly added to 101 parts of thionyldi-CdodecylpiperidiniumJ-sulfite at room temperature. Times four hours Nachrührett of the mixture at 60 ⁰ C 125 parts are obtained (96.2 $> of theory) F-Do.decyl-N- (OC

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chloromethyl-ß-sulfito-äthyli-piperidinium-betaine in the form of a red oil. n ^ ° = 1.4879.

Example 13

a) In 159 parts of N-octyl morpholine are introduced with stirring at room temperature "91 parts of sulfur, with the temperature at 43 ⁰ G increases. After two hours of stirring of the mixture at 35 ⁰ C, the excess sulfur dioxide under reduced pressure is removed. This gives 200 parts (95j3 i ° of theory) Thionyldi- (octyl-morpholinium) sulfite in the form of a yellow oil. n ^ = 1.4828.

b) 22 parts of ethylene oxide are introduced into 131 parts of thionyl di (octyl morpholinium) sulfite. After stirring for four hours at 45 to. 5O ⁰ C 143 parts (93.5 $ of theory) of N-octyl-N-ß-sulfitäthyl-morpholiniuin betaine in the form of a yellow oil. nj- ⁰ = 1.4922.

Example 14

a) In 162 parts of a mixture of N-hexa-decyl-morpholine and N-octa-decyl-morpholin with stirring at room temperature 65 parts of sulfur are introduced. the temperature rising to 40 ° C. After removing the excess sulfur dioxide under reduced pressure, 164 parts of the mixture (84.5 i ° of theory) thionyldi- (octadecylmorpholinium) sulfite and thionyldi- (hexadecylmorpholinium) sulfite are obtained in the form of a yellow oil, which after a few days crystallized out. Ip 88 to 89 ⁰ C.

b) In a solution of 97.5 parts of the mixture of Thionyldi- (hexadecyl-morpholinium) sulfite and Thionyldi- (octadecylmorpholinium) sulfite in 100 parts of acetone are introduced at 25 to 30 ⁰ C, 15 parts of ethylene oxide. After three hours of stirring of the mixture at 35 to 4O ⁰ C, the solvent is distilled off under reduced pressure to give 105 parts (96.7 1 ° of theory) of a mixture of N-hexadecyl-N-ß-sulfitoäthyl-morpholinium-betaine, and N-octadecyl -N-ß-sulfitoethyl-

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Morpholinium betaine obtained in the form of colorless crystals

50
be, n ^ = 1.4694.

Example 15

a) 155 parts of sulfur dioxide are introduced into 578 parts of N-methyl-N-tridecyl-aniline with stirring at room temperature. After stirring the mixture for two hours at 35 ° C., the excess sulfur dioxide is removed under reduced pressure. 690 parts (97.8 <fo of theory) of thionyldi (methylphenyltridecylammonium) sulfite are obtained in the form of a red oil. n ^ ° = 1.5113.

b) In 353 parts Thionyldi- (methyl-phenyl-tridecyl-ammonium) sulphite be initiated at 25 to 30 ⁰ C, 50 parts of ethylene oxide. After stirring the mixture for three hours, 392 parts (98.7 $> of theory) K-Methy1-N-tridecyl-N-

20 phenyl-N-ß-sulfito-ethyl-anmionium-betaine. n ^. = 1.5091.

Example 16

a) In 254 parts of N-dimethyl-cyclohexylamine are introduced with stirring 179 parts of sulfur dioxide, maintaining the temperature at 7O ⁰ C increases. After stirring the mixture for a further two hours, the excess sulfur dioxide is removed under reduced pressure. 374 parts (97.8% of theory) thionyldi-idimethyl-cyclohexyl-ammonium sulfite are obtained as a yellow, crystallized oil. Is is recrystallized with acetone. Pp 132 to 134 ⁰ C

b) In 115 parts Thionyldi-idimethyl-cyclohexyl-ammonium) sulphite are introduced 27 parts of ethylene oxide, wherein the temperature to 92 ⁰ C increases. After stirring the mixture for two hours, a crystalline precipitate is obtained, which is treated with acetone and filtered off with suction. Yield: 117 parts (80.9 $ of theory) of N-dimethyl-N-cyclohexyl-N ^ ß-sulfitoethyl-ammonium-betaine. Mp 84 to 86 ⁰ C..

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Example 17

a) In a solution of 157 parts ϊΤ, ΪΓ-Dimethylamino-ethyl-inethacrylat in 100 parts of acetone at 1O ⁰ C 64 parts of sulfur are introduced. After the solvent has been distilled off, 215 parts (97.2% of theory) thionyldi- (dimethyl-β-methacrylato-ethyl-ammonium) sulfite are obtained in the form of hygroscopic crystals. n ^ ° = 4989.

b) In a solution of 221 parts of Thionyldi- (dimethyl-beta-methacrylato-ethyl-ammonium) sulphite in 100 parts of acetone are introduced 44 parts of ethylene oxide at ⁰ ° C and stirred for three hours at 30 ⁰ C. 256 parts (96.6% of theory) of ΪΤ-dimethyl-N- (ß-methacrylate) -ethyl-F-ß-sulfito-ethyl-ammonium-betaine are obtained as a yellow, viscous oil which crystallizes. n ^ ° = 1.5088. ■

Example 18

a) In 285 parts of N, N-dimethyl-N- (beta-laurato) -isopropylamine be initiated at room temperature, with stirring, 125 parts of sulfur dioxide, while the temperature rises to 40 ⁰ C. The mixture is kept for 2 hours with stirring at 40 ^° C. and the excess sulfur dioxide is separated off under reduced pressure. 314 parts (98.8% of theory) of thionyldi- (dimethyl-ßlaurato-isopropyl-ammonium) sulfite are obtained in the form of a red-brown oil. n ^ ° = 1.4622.

b) A mixture of 122 parts Thionyldi- (dimethyl-beta-lauratoisopropyl-ammonium) sulphite and 42 parts of styrene are kept under stirring for 4 hours at 65 ⁰ C. This gives 160 parts (98.5 1 ° of theory) Ν, ΙΤ-dimethyl-lT-beta-laurato-isopropyl-LT (oo-phenyl-ß-sulfito) ethyl-ammonium-betaine as a red oil. n £ ° = 1.4980.

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Example 19

a) In a solution of 712 parts of N ^ -Mmethyl-N - ^ - olsaureamido) -propyl-amine in 250 parts of acetone are introduced at 10 to 30 ⁰ C in 2 hours 198 parts of sulfur dioxide, After distilling off the solvent, 828 parts (96.5 io of theory) thionyldi- (dimethyl-oleic acid amidopropyl-ammonium) sulfite as a yellow oil. np = 1.4904.

b) In 86 parts Thionyldi- [dimethyl - (^ - ölsäureamido) -propylammonium] sulfite are introduced 12 parts of propylene oxide at 25 to 30 ⁰ G and stirred for 4 hours at 25 ° C. 92 parts (93.8% of theory) of N, N-dimethyl-N-oleic acid amido-propyl-N-oG-methyl-ß-sulfitoethyl-ammonium-betaine are obtained as a yellow oil. n ^ ° = 1.4860.

Example 20

a) 188 parts of sulfur dioxide are introduced into a solution of 736 parts of N, N-dimethyl-N - (^ - stearic acid amido-propyl) amine in 500 parts of acetone at 50 to 55 ^° C. in the course of 21/2 hours. After distilling off the solvent, 850 parts (98.5 % of theory) thionyldi- [dimethyl (^ - stearic acid amido) propylammonium] sulfite are obtained as colorless crystals.

Pp = 164 to 166 ⁰ C.

b) A solution of 86 parts Thionyldi- [dimethyl- (j ^ -stearinsäureamido) -propyl-ammonium] sulfite and 24 parts of styrene in 200 parts of cyclohexane is held for 8 hours at 75 ⁰ C. After the solvent has been distilled off under reduced pressure, 102 parts of N, N-dimethyl-N- (γ-stearic acid-amido) -propyl-N- (oC-phenyl-β-sulfito) -ethyl-ammonium-betaine are obtained in the form of a water-soluble , yellow paste. n5 = 1.5006.

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Example 21

a) 90 parts of sulfur dioxide are introduced into a solution of 102 parts of N-methyl-N-di - ^^ '- stearic acid amido) propyl-amine in 350 parts of ligroin at 35 "to 38 ⁰ C and the mixture for 3 hours at 30 ⁰ G stirred specialist distilling off the solvent under reduced pressure, 105 parts are obtained (93.7 $> of theory) Thionyldi- [methyl-di -. (<r, T ¹ -stearinsäureamido) propyl ammoniumJ sulphite in the form of crystals. Mp 100 to 102 ⁰ C. ■

b) In a solution of 222 parts of Thionyldi- [methyl-di (f, f ¹ - * stearic acid-amido) -propyl-a.mmonium] sulfite in 500 parts of ligroin are introduced at 60 to 65 ⁰ C, 13 parts of ethylene oxide and stirred for 4 hours. If the solvent is distilled off, 230 parts (97.8 % of theory) of F-methyl-N-di - ((T, T ¹ -stearic acid-amido) -propyl-N-β-sulf itoethyl-ammonium-betaine. Pp 80 to 83 ⁰ C

Example 22

a) In a solution of 426 parts of Ν, Ν-dimethyl-lT-dodecylamine in 250 parts of acetone at 25 to 30 ⁰ C, 206 parts of pivoting are introduced dioxide. After the solvent has been distilled off under reduced pressure, 520 parts (94.1% of theory) thionyldi (dimethyldodecylammonium) sulfite are obtained as a yellow oil. n ^ ° = 1.4707.

b) 24.5 parts of butadiene monoxide are slowly added to 97 parts of thionyl di (dimethyl dodecyl ammonium) sulfite with stirring. After four hours of stirring at 40 ⁰ C to obtain 117 parts (96.3 & theory) of N, N-dimethyl-N-dodecyl-N- (OEC vinyl-.beta.-sulfito) ethyl-ammonium-betaine in the form of a red, water soluble oil. n ^ ° = 1.4798.

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a) In 596 parts of triethanolamine are 326 parts sulfur dioxide introduced at room temperature with stirring, whereupon the temperature rises to 55 ⁰ C. After three hours of stirring of the mixture at 45 ⁰ C, the excess sulfur is removed under reduced pressure and to obtain 850 parts (99> 8 io of theory) of a yellow, viscous oil. The oil is taken up in methanol. On cooling, the TMonyldi- (tris-hydroxy-ethyl-ammonium) sulfite crystallizes out in the form of colorless crystals. Pp 46 to 48 C.

b) 100 parts of ethylene oxide are introduced into 426 parts of thionyl di (tris-hydroxy-ethyl-ammonium) sulfite in 500 parts of methanol. After three hours of stirring the mixture at 35 ⁰ C is cooled to give 316 parts (67.2 $ of theory) of N-tris-hydroxy-ethyl-N-ß-sulfito-ethyl-ammonium-betaine in the form of colorless crystals. Fp 44 to 46 ⁰ C.

Example 24

a) In 468 parts Ν, Ν-diethyl-ethanolamine under stirring at room temperature 326 parts of sulfur are introduced, in which the temperature rises to 40 ⁰ C. After three hours of stirring at 35 ⁰ C, the excess sulfur is removed under reduced pressure and to obtain 708 parts (97.8 $ of theory) Thionyldi- (diethyl-.beta.-hydroxy-ethyl-ammonium) sulphite as a reddish brown oil. n ^ ° = 1.5075.

b) In a solution of 306 parts Thionyldi- (diethyl-.beta.-hydroxyethyl-ammonium) sulphite at 35 to 40 ⁰ C, 85 parts of ethylene oxide are introduced. After stirring the mixture for two hours at 45 ° C, the solvent is distilled off under reduced pressure and 372 parts (97.7 $ of the theory) of Ν, Ν-diethyl-N-ß-hydroxy-ethyl-N-ß-sulfito- ethylammonium betaine as a viscous oil. n ^ = 1.5126,

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Example 25,

a) In 332 parts of diethanolamine are introduced at 25 ⁰ C with stirring, 200 parts of sulfur dioxide, the temperature rises to 65 ° C. If the mixture is stirred for three hours, 505 parts (95.8% of theory) of bis-β, β'-hydroxyethylthionamic acid are obtained as a colorless, viscous oil. n ^ = 1.5285.

b) 132 parts of ethylene oxide are introduced into 524 parts of bis-ß, ß ^{f -hydroxyethyl thionamic acid with stirring.} If the mixture is stirred for three hours, 621 parts (94.6% of theory) FjF-bis-hydroxy-ethyl-F-β-sulfito-ethyl-

? o ammonium betaine as a colorless, viscous 01. nt = 1.5299.

Example 26

a) In a solution of 275 parts of monoethanolamine in 200 parts of methanol are introduced at 25 ⁰ C with stirring, 288 parts of sulfur dioxide, · wherein the temperature rises to 55 ⁰ C. After stirring the mixture for three hours, the solvent is distilled off under reduced pressure and 548 parts (97.4% of theory) of hydroxyethylthionamic acid are obtained as colorless crystals. Mp 140 to 142 ⁰ C (dec.).

b> 132 parts of ethylene oxide are introduced with stirring at room temperature into a solution of 375 parts of hydroxyethyl thionamic acid in 200 parts of methanol. After three hours of professional stirring, the solvent is distilled off under reduced pressure, and 492 parts (96.9 % of theory) of F-β-hydroxyethyl-F-β-sulfito-ethyl-ammonium-betaine are obtained as a colorless oil. n ~ ° = 1.5204.

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Claims (2)

Patent claim. Process for the preparation of sulfitobetaines of the general formula .GH — CHOSO, in which the individual radicals R ₁ , R ₂ , R, can be identical or different and each represent an aliphatic, eycloaliphatic, araliphatic or aromatic radical, and the individual radicals R ₂ and / or R, each also for a hydrogen atom can stand, R-, and a radical R ₂ together with the "adjacent nitrogen atom can also mean members of a heterocyclic ring, characterized in that thionamide compounds in the form of thionamide acids of the general formula R. R ₂ N-S-0H II, in which R ₁ and R _{2 have} the aforementioned meaning, or of sulfites of the thionylamides of the general formula * D 1T \ Ό TL ϊ Ϊ1 Ro— Ή —S— Ή —R, 2.,
R, III, in which R ₁ and R _{2 have} the aforementioned meaning, with 1,2-alkylene oxides of the general formula IV, in which the individual radicals R ^ have the aforementioned meaning, implements. Badische Anilin- & Soda-Fabrik AG 109821/2273 ORIGINAL INSPECTED