DE1768407C3 - Process for the production of sulfitobetaines - Google Patents

Description

Γ R ₂ R ₃ 'R ₃ Ί ^θ

IT T

R ₁ -N-CH-CHOSO ₂ J

R ₁ -NR ₂

(Π)

20th

characterized in that one primary, secondary or tertiary amines of formula 25

R ₂ -N

R ₁

with 1,2-glycol sulfites of the formula

(HI)

implements.

\ / S.
H ^R * / I. Il
O I. CH-
1 -CH
ι I.
O I.
O

35

(IV)

45

The subject of the invention is the method defined in the claim.

The claimed implementation can be used for case 50 the use of triethanolamine and 1,2-glycol • sulfite represented by the following formulas:

HIGH ₂ - CH ₂

CH, - CH,

HIGH ₂ - CH ₂ - N + O HIGH ₇ -CH,

Il ο

HIGH ₂ -CH ₂

- -> HIGH ₂ - CH ₂ - ^Θ Ν - CH ₂ - CH ₂ OSOf

HIGH ₂ -CH ₂ 65

The method according to the invention surprisingly delivers a large number of sulfitöbetaineni starting from simple starting materials, in good yield and purity

The amines used as starting materials of Formula III can be primary, secondary or tertiary. Preferred starting materials III and correspondingly preferred end materials I are those in whose formulas the individual radicals Ri and R _{2 can be the} same or different and in each case an alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl or aryl radical with up to 22, preferably mean up to 18 carbon atoms, in addition the individual radicals R _{2 can} each also stand for a hydrogen atom. The radicals mentioned can also be substituted by groups and / or atoms which are inert under the reaction conditions, for example hydroxyl groups, alkyl groups with up to 4 carbon atoms, chlorine atoms, bromine atoms, sulfo groups, nitro groups, cyano groups. If you work with mixtures of starting materials III, for example the palm kernel fatty amine powder obtained by reacting dimethylamine with lauryl chloride, consisting essentially of amines with 12 to 14 carbon atoms, corresponding mixtures of sulfite betaines are obtained.

For example, the following amines can be used as starting materials III: butylamine, dodecylamine, Cetylamine, styrylamine, cyclohexylamine, aniline, «- or / i-naphthylamine, benzylamine, allylamine, propargylamine, Ethylenimine, diethylamine, diethanolamine, dibutylamine, di- (2-ethxylhexyl) amine, methylaniline, Diallylamine, methylbenzylamine, trimethylamine, triethylamine, Tributylamine, dimethyldodecylamine, dimethylstearylamine, Distearylmethylamine, dimethylaniline. Dimethylcyclohexylamine, triethanolarine, tniso-propanolamine.

The starting materials! are made with 1,2-glycol sulfites of formula IV, generally implemented in stoichiometric amounts. One can use the starting amine III, especially in the case of primary amines, also in excess, e.g. B. in an up to 2-fold excess, based on starting material IV. The starting materials IV can, for. B. through implementation of ethylene oxide with sulfur dioxide by the method described in DT-OS 12 5 i 769 will.

It is also possible to use compounds which form 1,2-glycol sulfites during the reaction for the reaction, e.g. B. poly-1,2-glycol sulfite. The polyglycol sulfite is obtained, for. B. by reacting ethylene oxide with sulfur dioxide at O ⁰ C.

Preferred starting materials IV and correspondingly preferred end materials I are those in whose formulas the individual radicals R _{3 can be} identical or different and each represent a hydrogen atom, an alkyl, cycloalkyl, aralkyl or aryl radical with up to 7 carbon atoms. It can e.g. B. the following 1,2-glycol sulfites are used as starting materials! V: 1,2-glycol sulfite, 1- methyl, 2-phenyl, 1-cyclohexyl, 2-benzyl, l ^ -dimethyl-l ^ -glycolsulphite .

Those made by the process of the invention Sulfobetaines I can be during the reaction or when working up the reaction mixture in convert their salts of general formula II. As a rule, in the case of using tertiary amines sulfitobetaine I as end products, in the case of the use of secondary amines the End products I or Π or their mixtures, e.g. B. in the ratio of 1 mole of end product I to 1 mole of end product II, in the case

the use of primary amines as a rule end productsII after working up the reaction mixture.
The implementation is usually carried out at a

"Temperature between -10 and -4-200" Q preferably

, between 20 and 150 ^Q C, under atmospheric or linier pressure continuously or intermittently carried out, advantageously inert solvent such as water is used under the Reaktionsbgdingungen; Alcohols e.g. B methanol, butanol, cyclohexanol; aromatic: o hydrocarbons, e.g. B. benzene, toluene; Xylene, nitrobenzene, chlorobenzene; Ketones, for example acetone; Chlorinated hydrocarbons, e.g. B. chloroform, ethylene chloride, or their mixtures.

, The transferable by the method of the invention new compounds are valuable starting materials for the production of dyes, detergents, • Netting, equipment and aids in the textile mill and textile printing area as well as from Pesticides. For example, with the reaction products of Ν, Ν-distearyl-N-methylamine and glycol sulfite in an amount of 10 to 40 g per liter of aqueous finishing liquor or cotton Impregnate and dry cellular wool tissue, giving the tissue a soft, smooth and full-bodied appearance Give grip.

The parts mentioned in the examples are parts by weight.

example 1

A solution of 99 parts of cyclohexylamine and 20 parts of water in 150 parts of methanol is slowly added to 54 parts of 1,2-glycol sulfite. After brief stirring, the mixture employs a highly exothermic reaction, by cooling the temperature to 8O ⁰ C. The precipitated colorless solid is filtered off with suction and crystallized from alcohol. 150 parts (corresponds to 98.0% of theory) of N-cyclohexyl-N-ethyl - ^ - sulfito-cyclohexyl-ammonium-betaine with a melting point of 305 ° C. (decomp.) Are obtained. .

Analysis for C ₁₄ H ₃₀ O ₃ N ₂ S (M = 306):

Calculated:

C55, O, H 9.8, O15.7, N9.2, S 10.3%;
found:

C 54.2, H 10.2, O 15.6, N 9.9, S 10.1%.

Example 2

A mixture of 121 parts of N-methylbenzylamine and 54 parts of 1,2-glycosulfite is heated to 8 (TC! After 5 hours, 11 parts (corresponds to 96.0% of theory) N-methylbenzyl-N-ethyl / i-sulfito • methyl-beazyl-ainmonium-betaine in the form of a water-soluble yellow oil. π f = 1.5534.

^{Analysis for} C ₁₈ H ₂₆ O ₃ N ₂ S (M = 350).
Calculated:

C61.7, H 7.45, O 13.7, N8.0, S9.15%;
found:

C 61.4, H 7.7, O 14.2, N 6.8, S 9.5%.

.
Example 3

A mixture of 74.5 parts triethan oil amine and 54 parts of glycol sulfite are stirred at 70 ° C. for 5 hours.

119 parts (corresponds to 93.0% of theory) of N - tris - / i - hydroxyethyl - fi - sulfito - ethyl - betaine are obtained. n ¥ - 1.5211.

3rd analysis door C ₈ H ₁₉ U ₅ Nb (M -

Calculated:

C 37.4, H 7.4, O 37.4, N 5.4, S 12.45%;
found:

C 38.0, H 7.9, O 38.6, N 5.3, S 11.7%.

Example 4

A stream of nitrogen 53 parts of dimethyl palmkemfettamin be (prepared by reacting 205 parts of lauryl chloride with 45 parts of dimethylamine) and 27 parts Polyglykolsulfit with stirring to 130 ⁰ C heated After one hour, the mixture was further stirred for 4 hours at 90 ⁰ C to obtain a clear water-soluble, yellow paste is obtained. 75 parts (corresponds to 94.0% of theory) of the sulfito-betaine of palm kernel fatty amine are obtained.

Analysis door C ₁₆ H ₃₅ O ₃ NS (M = 321):

Calculated:

C60.0, H 11.9, O15.0, N4.3, S9.9%;
found:

C 58.9, H 11.0, O 17.1, N 3.8, S 9.0%.

Claims (1)

'-i claim :: £ ^; Il Viajiahren zuc production- of sulphitobetauien; j the formula : '^ " ' .. ·;>;. ■. '■ · ■' ■. i> Ä; ■ '■,;. 3ρ>&;;, ψ '■ ■; "■■ -5; EvJa R ₂ J ^ j-CH-CHOSp? (I) J. 10 in which R ₁ , R ₂ , R _{3 can be} identical or different and each represent an aliphatic, cycloaliphatic, araliphatic "or aromatic radical, R ₂ " and / or R _{3 can} also stand for a hydrogen atom and / or salts 15 of the formula