DE756185C - Process for the preparation of quaternary aliphatic ammonium chlorides - Google Patents

Description

Process for the preparation of quaternary aliphatic ammonium chlorides It is known that alkyl halides with tertiary amines to form quaternary Ammonium salts react.

The methods of preparation of quaternary ammonium salts given in the literature from tertiary aliphatic amines are mainly limited to use of alkyl iodides and alkyl broinides, and in very few cases are alkyl chlorides applied. This preference for iodides and bromides is due to the fact that that alkyl iodides very easily, alkyl bromides somewhat, less easily, alkyl chlorides on the other hand are very difficult to make to react. This occurs especially with alkyl halides with an alkyl radical containing at least 8 carbon atoms in appearance, because the reactivity of the alkyl halides decreases with the length of the alkyl group.

It has therefore been suggested that the reaction be carried out by applying higher To accelerate temperatures if necessary under pressure. These methods perform even with lower alkyl halides to the desired result, with higher alkyl halides, especially with chlorides, with at least 8 carbon atoms, on the other hand, the reaction works but so sluggish that, in spite of the increased temperature, it is only slightly Part expires. In order to eliminate these difficulties, one has to be more reactive Starting materials used, on the one hand heterocyclic Amines, such as pyridine, quinoline and their derivatives (French patent 7-13 973), on the other hand Alkyl esters e.g. B. of hydrohalic acids with at least 8 carbon atoms, their iscarbon chain interrupted by a foreign atom such as sulfur or nitrogen (Austrian Patent 152824). One of the last mentioned compounds is reactivity of the halogen atom is increased quite considerably, so that it is expedient to use solvents or diluents, like benzene, so as not to let the reaction go too stormy.

Very common, however, is the use of alkyl chlorides of those to the corresponding bromides and iodides. - Once the chlorides are cheaper, in addition, the solubility of the quaternary is particularly important in the higher members Ammonium chlorides larger than those of the bromides and iodides. It is also corrosive The effect of the quaternary ammonium chlorides on some metals is less than that of the bromides and iodides. It is true that the bromide and iodide can be converted into chlorides; but this is not only very expensive because it has to be done with silver chloride, but also because of the fact that the silver bromide or iodide is not in filterable form separates, very difficult to carry out technically.

It has now been found that you can Tetraalkylammoniumchloride with a can produce an alkyl radical containing at least 8 carbon atoms in good yield, by the mixture of an alkyl chloride with at least 8 carbon atoms and a tertiary aliphatic amine added to water and placed in a closed container heated to at least 80 °, preferably to over foo °. The reaction temperature is expediently chosen so that the reaction is complete within 20 to 40 hours. The amount of water should be 200/0 or more of the starting amount of amine and must be To obtain the most favorable yield, be determined on a case-by-case basis.

The addition of water significantly increases the yield, in such a way that z. B. in the implementation of primary n-dodecyl chloride with triethylamine with the addition of 36% water, a yield of 60% is achieved during the reaction takes place without the addition of water with only about 3% yield.

Example 1 204.5 r @ T prim.-n-1) odecyl chloride are placed in an enamelled autoclave, 121 g triethylamine and zoo g water. 1After you have locked it, heat with stirring or shaking for 24 hours at 150 °. thereafter nian sells it as a by-product resulting 1) odecene (i) and the triethylamine still present by distillation with water. 1.) The reaction product purified in this way is then applied in ethyl alcohol and tri-iitliyl-n-dodecylammonium chloride precipitated by adding ethyl ether. .1tis today: 641 / o.

Examples A mixture of 14.4 g of cetyl chloride and 1-4 g of primary n-octadecyl chloride is with 121 g of triethylamine and 250 g of water in an autoclave for .lo hours heated to 150 °. With the aid of ether or with the waterdanipf distillation used in example i can the octadecene (i) formed as a by-product and the triethylamine still present removed.

The yield of tetraalkylammonium chloride under these circumstances is 58%. while in the absence of water it is only 60 / n.

Example 3 28o g of primary n-dodecyl chloride are stirred with 720, -, an aqueous 40% Tritnetliv 1-amine solution in an autoclave with a stirring mechanism for 30 hours at a temperature of 80 °. The initially heterogeneous mixture becomes homogeneous in the course of the reaction. The excess trimethylamine and the by-products formed are removed by steam distillation. Yield of 'frimethvl-n-dodec_vlammoniuinclilorid 60%.

Claims (3)

PATENT CLAIM: Process for the production of quaternary aliphatic Ammonium chlorides by reacting tertiary aliphatic amines at elevated temperature in the presence of a solvent or diluent with an at least 8 C-atoms containing il #, alkyl radical having alkyl chloride, characterized in that that the reaction is calculated in the presence of at least 2o% water on the amine, at temperatures of at least 80 °, preferably hot temperatures above 100 °, below Printing. To differentiate the subject matter of the invention from the state of the art the following publications have been considered in the granting procedure: German Patent No. 63800.5; French patent specification no. 743973-. H ou he n, J., The method of the organ. Chemistry, 2nd ed., L.eilizi-g, 3. I3ci .. p.371. i