CS252363B1 - Process for preparing quaternary salts - Google Patents

Abstract

The solution concerns the preparation of quaternary salts of the formula 2 ®_C»;fC00R where X is Br, Cl or I and R is an alkyl, alkenyl, haloalkenyl and alkynyl group with up to 4 carbon atoms. The essence of the solution is that an excess of 2 to 25 moles of liquid haloacetate is treated with 1 mole of hexamethylenetetramine. The obtained products are suitable as bactericidal and fungicidal additives to coatings, latexes, adhesives, cutting oils and the like.

Description

The invention relates to a method for preparing quaternary salts by reacting hexamethylenetetramine with haloacetates, which are characterized by biological, especially bactericidal activity, whereby the preparation conditions are chosen so as to shorten the preparation time and increase the reaction yield.

Haloacetates react with hexamethylenetetramine in halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, perchloroethylene, etc. [US Pat. No. 3,624,253; N. Blaževič, D. Kolbach, B. Bělin, V. Šunjič, F. Kajfež: Synthesis, 1979 (3), 161—174] according to the scheme:

CH^COOR

h.ato&eaovan> _N _

KctteCOOM X®

where X is Br, Cl or I and R is an alkyl, alkenyl, haloalkenyl or alkynyl group.

The reaction takes place for 3 to 6 hours in a solution with constant stirring at room temperature or at a slight increase in temperature. The yield of the reaction, with respect to the quality of, for example, bromoacetates, ranges from 57 to 93%.

The disadvantages of the prior art are the relatively long reaction time, low reaction yield and problems with the large volume of contaminated halogenated hydrocarbons.

Some of the above shortcomings are addressed by the present invention, according to which a method for preparing quaternary salts of the formula:

/ >®_CH,-COOR X® where X is Br, Cl or I and R is alkyl, alkenyl, haloalkenyl and alkynyl with up to 4 carbon atoms, the reaction of hexamethylenetetramine with haloacetates is carried out by treating 2 to 25 moles, preferably 10 to 20 moles of liquid haloacetate, with 1 mole of hexamethylenetetramine and the quaternary salt formed is isolated.

This simple change in conditions according to the invention shortens the reaction time, increases the yield of the reaction and eliminates the problems of working with large volumes of halogenated hydrocarbons, etc.

The parameters that influence the amounts of haloacetates include their quality. Taking into account the above fact, the amount of haloacetate ranges from 2 to 25 moles per 1 mole of hexamethylenetetramine, only exceptionally is the above range exceeded.

The preparation of quaternary salts according to the invention is documented by the following examples, which, however, in no case exclude the possibility of variability in the preparation of the substances in question.

Example 1

167.0 g (1 mol) of ethyl bromoacetate are introduced into a 250 ml flask equipped with a stirrer. At a laboratory temperature of 23 °C, 14.0 g (0.1 mol) of crystalline hexamethylenetetramine, free from lumps, are gradually added with constant stirring. After 1 hour of stirring, the resulting suspension is filtered and the filter cake is washed three times with 10 ml of chloroform and dried in the open air. This results in 30.1 grams of quaternary salt, i.e. 98.05% of theory.

Using differential thermal analysis (DTA), working with a linear temperature rise rate of 5 3C. min ^-1 , a measuring range of 1 mV per scale scale and weighing 50 to 70 mg of sample, the beginning of exothermic decomposition in the solid state is found at 117.0 °C. Then the first exo-decomposition peak at 142.4 ^° C; endo-peak at 146.0 °C and the second exo-decomposition peak at 150.6 °C. The change in the nature of the decomposition occurs at a temperature

135.2 °C.

The determined melting point of the sample on the “Boetius” micro-heating stage is 142—143 degrees Celsius.

The product has in the IR spectrum a pair of ester bands at about 1740 and 1290 cm ^-1 and four "urotnopin" bands (with slight shifts). The bands between 3000—2800 cm ^-1 belong to the valence vibrations of CH vSzieb, the strongest of which are in the CHž _band at about 2920 cm ^-1 . In the region of deformation vibrations of CH bonds, the strongest is the ÓCH2 scissor band at about 1470 cm ^-1 and there is also a band of the so-called active CH2 groups at about 1410 cm ^-1 (active = leading groups with I effect). Example 2

The procedure is as in Example 1, except that the filtrate (150 g) obtained by the procedure of Example 1 is introduced, which is supplemented with fresh ethyl ester of the acid.

5 2 3 Β 3 bromoacetic acid (17 g) i.e. total 167.0 g (1 mol) of haloacetate is presented for bactericidal activity tests. The results are given in Table 1.

30.3 g of quaternary salt, that is 98.70% of theory.

Table 1

End- Pseudomonas Escherichia coli Staphytoooccus Candida albicans tracia aoi uginosa aureus (%) (gram-j (gram-) (gram-) (yeast)

100 very effective same 2 effective effective 1 effective effective 0.5 effective effective (less) (less)

Example 3

33.1 g (0.2 mol) of ethyl bromoacetate are introduced into a 100 ml flask equipped with a stirrer. At a temperature of 50 °C, 14.0 g (0.1 mol) of crystalline hexamethylenetetramine, free from lumps, are gradually added with constant stirring. After 1 hour of stirring, the resulting suspension is filtered and the filter cake is washed three times with 10 ml of chloroform and dried in the open air. This gives 30.4 g of quaternary salt, which is 99.1% of theory.

Example 4

417.5 g (2.5 mol) of ethyl bromoacetate are introduced into a 1000 ml flask equipped with a stirrer. At a temperature of 98 °C, 14.0 g (0.1 mol) of crystalline ^1- hexamethylenetetramine are gradually added with constant stirring. After stirring for 1 hour and cooling to room temperature, the resulting suspension is filtered and the filter cake is washed three times with 10 ml of chloroform and dried in the open air. This gives 28.7 g of quaternary salt, which is 93.5% of theory.

Example 5

The procedure is as in Example 1, except that esters with different R are used. The results are summarized in Table 2.

Table 2

Attempt No. R Yield (%) Melting point (°C) 1. methyl 99.2 146 2. 2-propiinyl 99.0 140 3. 2-bromoallyl 99.1 141 4. allyl 85.4 149 5. 2-Chloroallyl 99.6 144

Under similar conditions, quaternary salts with esters in which R is 2,3-dichloroallyl, n-butyl, or isobutyl, respectively, for X = Cl or I, are formed with the same effect.

The products obtained by the process according to the invention are suitable as bactericidal and fungicidal additives to coatings, latexes, adhesives, cutting oils, etc.

SUBJECT

Claims (2)

2 5 2 3 Β 3 bromoacetic [17 g] i.e., celcoin is tested for bactericidal activity represented by 167.0 g (1 mol) of haloacetate. Table 1 results. 30.3 g of quaternary salt, i.e. 98.70% over theory. Table 1 End-of-Pseudomonas Escherichia coli Staphylococcus Candida albicans tract aoi uginosa aureus (%) (gram- (gram-) (gram-) (yeast) 100 very effective dtto 2 effective 1 effective 0.5 effective (less) (less) EXAMPLE 1 and 3) 33.1 g (0.2 mol) of bromoacetate are introduced into a flask containing 100 ml of caustic agitator. At a temperature of 50 ° C with stirring, 14.0 g (0.1 mol) of lump-free crystalline hexamethylenetetramine are successively metered in. After stirring for 1 hour, the resulting suspension is filtered and the filter cake is washed three times with 10 ml of chloroform and dried in air. 30.4 g of quaternary salt result, i.e. 99.1% of theory. EXAMPLE 4 417.5 g (2.5 mol) of bromoacetic acid ethyl ester were introduced into a 1000 ml flask equipped with this effective, inactive, effective inactive (less) stirrer. 14.0 g (0.1 mol) of crystalline hexamethylenetetramine are successively metered in at 98 DEG C. with stirring. After stirring for 1 hour and cooling to room temperature, the resulting suspension is filtered and the filter cake is washed three times with 10 ml of chloroform and dried in the air. 28.7 g of quaternary salt is obtained, i.e. 93.5% of the oprotitor. EXAMPLE 5 The procedure of Example 1 is followed, except that esters with rhodium R are used. The results are summarized in Table 2. Table 2 Experiment No. R Yield (%) Melting point (° C) 1. Methyl 99.2 146 2. 2-Propynyl 99,0 140 3. 2-Bromoallyl 99,1 141 4. Allyl 85,4 149 5. 2-Chlorallyl 99,6 144 Under similar conditions, quaternary salts with esters are formed. R is 2,3-dichloroallyl, n-butyl, isobutyl, X = Cl or I. The products of the invention are useful as bactericidal and fungicidal additives in coatings, latexes, adhesives, thinners. oils and the like. OBJECT A method for preparing quaternary salt forms INVENTION nyl, haloalkenyl and alkynyl with up to 4 carbon atoms, by reaction with hexamethylenetetramine with haloacetates, characterized in that the woman has 2 to 25 moles, preferably 10 to 20 moles of liquid haloacetate, with 1 mole of hexamethylene tetramine and the formed quaternary sol1 is isolated. 2. Process according to claim 1, characterized in that at least a portion of the haloacetate is used from the step after isolating the quaternary salt. wherein X is Br, Cl or I and R is alkyl, alkenyl-