DE1275053B - Process for the production of ethionic esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

German class:

Number:
File number:
Registration date:
Display day:

C07c

12 ο-23/03

12 ο-19/03
12 ο-25

P 12 75 053.7-42 (F 37299)

July 12, 1962

August 14, 1968

It has been found that ethionic acid esters of the general formula

RO ₃ O CJrI ₂ CrI ₂ Ο0Ο3ΓΤ

in which R is an optionally inertly substituted aliphatic, is cycloaliphatic or araliphatic hydrocarbon radical, as well as producing salts thereof can, if you carbyl sulfate with an optionally inertly substituted monovalent aliphatic, cycloaliphatic or araliphatic alcohol and the reaction product, if appropriate treated in the usual way with acid-binding agents with salt formation.

This reaction can be represented schematically by the following equation:

R-OH + CH ₂
O
SO ₂ -

CH ₂
SO ₂
O

> R - O ₃ S -.CH ₂ CH ₂ OSO ₃ H

Here, R has the meaning given above. The monohydroxy compounds are primary, secondary and tertiary aliphatic or cycloaliphatic, straight-chain or branched alcohols in Consideration, which may optionally also contain substituents, which under the reaction conditions used are indifferent to carbyl sulfate. Examples of such substituents are called: halogen atoms, nitro, carboxyl or sulfonic acid groups. Of hydroxy compounds be z. B. Mentioned: methanol, ethanol, n-propanol, iso-propanol, n-butanol, i-butanols, decanol-1, 1-dodecanol, 1-octadecanol, cyclohexanol, allyl alcohol, Propargyl alcohol, mixtures of long-chain alcohols based on natural fats; furthermore oxo alcohols, as prepared by the oxo reaction with branched olefins, e.g. B. heptanol based on dipropylene, nonyl alcohol based on diisobutylene, decyl alcohol based on tripropylene, tridecyl alcohol based on tetramerpropene or triiso-butylene. Substituted alcohols that may be mentioned are: Chloroethyl alcohol, l, 3-dichloropropanol-2,2,3-epoxypropanol-1, Glycolic acid, oxyethanesulfonic acid, 2-oxypropanesulfonic acid-l. Also by aromatic Residues of substituted aliphatic alcohols, such as benzyl alcohol, / f-phenylethyl alcohol, can be used. the Aliphatic hydroxy compounds usable for the reaction can also be obtained by hetero-method for the production of ethionic acid esters

Applicant:

Farbwerke Hoechst Aktiengesellschaft
formerly Master Lucius & Brüning,
6000 Frankfurt

Named as inventor:

Dr. Rudolf Kühne, 6000 Frankfurt;

Dr. Helmut Diery, 6230 Frankfurt-Höchst;

Dr. Bernhard Kiefer, 6000 Frankfurt-Sindlmgen

atoms that are indifferent to the carbyl sulfate ring may be interrupted in the chain. Be here called: glycol monomethyl ether, products such as those produced by the reaction of alcohols, phenols and Carboxylic acids are obtained with ethylene oxide or propylene oxide, for example oxyethylation (oxypropylation) products of methanol, butanol, 1-dodecanol, tridecanol (oxidation product based on tetrapropylene), Stearyl alcohol, phenol, tri-iso-butylphenol, nonylphenol, dinonylphenol, acetic acid, Coconut fatty acid, stearic acid and naphthenic acid.

The implementation of the aliphatic, araliphatic and cycloaliphatic Hydroxy compounds with carbyl sulfate can be carried out in organic solvents. as Organic solvents are preferably chlorinated, low molecular weight aliphatic hydrocarbons or solvents with a high dipole moment are used. Examples include: methylene chloride, Ethylene chloride, perchlorethylene, methyl chloroform, dichlorobenzene, acetonitrile and nitrobenzene. Man the carbyl sulfate can be added in solid or dissolved form to the solution of the hydroxy compound in the organic Add solvent; however, the reverse is also possible. One can but also the alcohol used for the reaction itself as a solvent, if with one Excess of alcohol is worked.

The ethionic acid esters are treated with acid-binding agents, expediently in Presence of water, in the corresponding salts

JM 590/471

convicted. The salt form of the esters mentioned can be obtained up to a pH of about 8 to 9 will.

Even if this is the limit up to which salts of the ethionic acid esters can still be obtained, in general is at pH values of about 8 to 9, it must be said that this pH value depends on the Reaction brought reaction components and the reaction conditions, for. B .. temperature and residence time, is dependent; thus shifts can occur upwards or downwards.

Examples of acid-binding agents that may be mentioned are: alkali hydroxides, such as sodium or potassium hydroxide, Alkali carbonates or bicarbonates, such as sodium carbonate, sodium bicarbonate, potassium carbonate, Potassium bicarbonate, alkali phosphates, such as sodium phosphate, alkali silicates, alkali acetates, alkaline earth hydroxides, such as magnesium hydroxide, calcium hydroxide and alkaline earth bicarbonates.

Because of the great sensitivity of carbyl sulfate to moisture, it must be considered extraordinary Surprisingly it can be said that the method according to the present invention, i.e. H. the reaction of the hydroxy compounds mentioned with carbyl sulfate, even in the presence of water can be carried out. Because it is known that the carbyl sulfate by the action of water is converted into ethionic acid. It was not foreseeable that alcoholysis would occur in spite of the possibility the hydrolysis takes place with good yields, so that, depending on the pH set, the Ethionic acid esters can be obtained.

A preferred procedure is to work in the two-phase system, in addition to the aqueous phase a different solvent is used, for example aliphatic or aromatic hydrocarbons, Halogenated hydrocarbons, such as methylene chloride or ethylene chloride, ethers, such as diethyl ether, Ketones, such as methyl ethyl ketone.

The acid-binding agents used can be in solid form, in aqueous solution or suspension added before the reaction or proportionately to maintain the desired pH be added during the reaction. When reacting in the presence of water, the carbyl sulfate introduced as such or in dissolved form. You can implement carbyl sulfate with aliphatic Hydroxy compounds also perform in the absence of any solvents. to for this purpose, for example, in the initially charged molar amount of the aliphatic hydroxy compound the carbyl sulfate entered in small proportions. The reaction mixture obtained is worked up in the usual way.

The reaction temperatures of the claimed method are preferably between -5 and +30 ⁰ C, but it may be advantageous for specific purposes, carry out the reaction even at higher temperatures, the resistance of the Carbylsulfats or of the reaction products formed if allowed it.

The ethionic acid esters or salts thereof obtainable by the process of the present invention are valuable products for the production of textile auxiliaries, plastics, dyes or Pesticides. The products of the process can, for. B. by alkalizing with cleavage of the sulfuric acid ester can be converted into the corresponding vinyl sulfonic acid ester.

The parts mentioned in the examples below are parts by weight.

example 1

In a mixture of 750 parts of ethylene chloride and 208 parts of carbyl sulfate is allowed dropwise 75 parts of n-butanol at 0 ⁰ C. After stirring for 2 hours at room temperature, the contents of the flask are added dropwise to a solution of 170 parts of potassium bicarbonate in 400 parts of water. After stirring for 2 hours at 10 to 15 ° C., the precipitated potassium salt of n-butyl ethionate can be isolated by suction in a yield of 36%. Further proportions are in the aqueous phase. The compound can be recrystallized from methanol, mp 173 ° C.

Example 2

187 parts of n-dodecanol are added dropwise to a suspension of 208 parts of carbyl sulfate in 1250 parts of ethylene chloride. After stirring for 2 hours at 10 to 2O ⁰ C and the flask contents into a solution of 210 parts of potassium bicarbonate in 700 parts of water is added dropwise at about 15 ° C. After half an hour, the precipitated potassium salt of the n-dodecyl ethionate is filtered off with suction and dried. The yield is over 80% of theory (based on n-dodecanol). The substance can be recrystallized from a large amount of methanol. The new substance melts with decomposition at around 200 ^° C.

Example 3

In a mixture of 625 parts of ethylene chloride, 300 parts of water, 10 parts of potassium bicarbonate and 111 parts of n-butanol, ^{94 parts of carbyl sulfate are introduced in small portions at 8 to 10 °} C. with vigorous stirring over the course of one hour. After 1 hour of stirring at 5 to 1O ⁰ C ⁰ C is cooled to O and the precipitated potassium salt of the Äthionsäure-n-butyl ester (relative to carbyl sulphate) in a yield of 61% was isolated by suction. The compound can be recrystallized from methanol, mp 173 ° C.

Example 4

In a solution of 324 parts of stearyl alcohol in 3750 parts of ethylene chloride, 188 g of carbyl sulfate are added in small portions at 10 ° C. After stirring for 1 hour, the contents of the flask are added dropwise to a solution of 220 parts of potassium bicarbonate in 1000 parts of water. After half an hour, the precipitated potassium salt of the stearyl ethionate is filtered off with suction and dried. The crude yield is over 80% of theory (based on carbyl sulfate). The substance can be recrystallized from a lot of ethanol, F. 19O ⁰ C (decomposition).

Example 5

In a mixture of 625 parts of ethylene chloride, 300 parts of water, 110 parts of potassium bicarbonate and 122 parts of 2-phenylethanol-1, 104.5 parts of carbyl sulfate (about 90%) are added in portions over the course of one hour at 5 to 10 ° C. After stirring for 1 hour, the mixture is ^{cooled to 0} ° C. and filtered off with suction. The precipitated potassium salt of the ethionic acid ester of 2-phenylethanol can be converted from a mixture of 500 parts by volume of ethanol and 60 parts of water, melting point 150 to 155 ° C.

Claims (2)

Patent claims: 1. Process for the preparation of ethionic acid esters of the general formula RO ₃ S - CH ₂ - CH ₂ - OSO ₃ H in which R is an optionally inertly substituted aliphatic, cycloaliphatic or araliphatic Is a hydrocarbon radical, and salts thereof, characterized in that carbyl sulfate is reacted with a corresponding monohydric alcohol and the reaction product, if appropriate, in a customary manner acid-binding agents treated under 'salt formation. 2. The method according to claim 1, characterized in that the reaction is carried out in the presence of water. ίο Publications considered: German patent specification No. 842 198.