CS210368B1 - A method of preparing alkyicin chlorides - Google Patents

Abstract

The invention falls within the field of organic technology. It provides a method for preparing alkyltin chlorides by alkyl chlorides from n- or isoalkyl chlorides in the presence of a catalyst, which is 2.0 to 3.0 of 2-alkoxymercaptoacetate or 2-alkoxyethyl-3-mercaptopropionate with 1 to 4 carbon atoms in the alkoxy group or 0.1 to 0.3 moles of a mixture consisting of 1 part of these substances with 1 part of a tertiary amine with 2 to 6 carbon atoms in the alkyl, 6 to 8 carbon atoms in the aryl, 6 to 10 carbon atoms in the cyclic or alkyl groups. Furthermore, the reactions require the presence of an activator, which is 0.05 to 0.1 alkyl iodide with 3 to 8 carbon atoms in the molecule or a lithium halide, where the halogen is chlorine, bromine or iodine, with the amounts of catalyst and activator being related to 1 gram atom of tin and the reaction taking place in a closed space under a stirrer at a speed of 800 to 1000 rpm.

Description

The present invention relates to a process for the preparation of alkyl tin chlorides by alkylation of tin metal and alkyl chlorides, and to the use of each of these compounds. 2-alkoxyethyl mercaptoacetates or 2-alkoxyethyl-3-mercaptopropionates, or the coupling of these compounds with tertiary amines and in the presence of activators from the group of alkyl iodides or lithium halides.

Disclosed is the alkylation of tin metal with alkyl chlorides of formula R-Cl, wherein R is an alkyl of 3 to 8 under tertiary amine catalysis using iodine-containing tin activators, resulting in a reaction product containing a mixture of alkyl tin chlorides of formula R Sn-Cl where mz 1 to 3 and n to 1 to 3, where m + nz 4. mn

The reaction is carried out in a pressure apparatus with good stirring, where at reaction temperatures of 60-130 ° C and longer reaction time, the predominantly in the mixture of alkyl tin chlorides is trialkyl tin chloride, at reaction temperatures 80-160 ° C and shorter reaction time the most desirable dialkyl chloride is predominant.

Its content is also favorably influenced by the addition of cocatalyst from the group of 2-alkoxy esters of mercaptoacetic acid or 3-mercaptoacetic acid. Alkyltin chlorides, which are present in the reaction mixture as adducts with amines, are released from the reaction mixture with aqueous hydrochloric acid solution, extracted and the individual alkyl chloride chlorides are usually separated by vacuum distillation. At a temperature above ^R 1 J C, a considerable amount of the appropriate 1-butene. A disadvantage of this procedure is that unreacted tin is unreactive for further alkylation.

This drawback is overcome by the invention describing a process for preparing alkyl tin chlorides of the general formula R Sn-Cl. wherein R is an alkyl of 3 to 8 carbon atoms, m is 1 to 3 mn to 3 m + n m of 4 by alkylation of tin with alkyl chlorides in the presence of a catalyst and an activator characterized in that 2.0 to 3.0 moles of n- or isoalkyl chloride 3 to 8 carbon atoms give 1 grammome of tin in the presence of 0.1 to 0.3 moles of a catalyst consisting of 2-alkoxyethylmercaptoacetin or 2-alkoxyethyl-3-mercaptopropionate with 1 to 4 carbon atoms in each alkoxy group relative to 1 grammome or the presence of 0.1 to 0.3 moles of a catalyst consisting of 1 part of 2-alkoxyethyl mercaptoacetate or 2-alkoxyethyl-3-mercaptopropionate each having 1 to 4 carbon atoms in the alkoxy group and 1 part of a tertiary amine having 2 to 6 carbon atoms in alkyl, 6 to 6 carbon atoms in the aryl and 6 to 8 carbon atoms in the cycloalkyl of the tertiary amine, and further in the presence of 0.05 to 0.1 mol of an activator consisting of an alkyl iodide of 3 to 8 carbons atoms in the molecule based on 1 gram gram of tin or 0.05 to 0.3 mol of a lithium halide activator, wherein the halogen is chlorine, bromine, iodine based on 1 gram gram of tin in an enclosure equipped with an agitator of 800 to

000.min at temperatures of 130 to 180 ° C for 2 to 8 hours.

An advantage of the described alkylation process is that by the selected reaction conditions alkylation can lead to high selectivity in the preparation of the desired dibutyltin dichloride and tributyltin chloride, and it is not preferred to conduct the alkylation up to 100% tin conversion to increase selectivity. The unreacted tin introduced into the reaction is active and can be used after addition of fresh tin for further alkylations.

The subject matter of the invention is described in the examples.

He did

92.6 g (1 mol) of dry distilled butyl chloride, 18.5 g (0.1 mol) of tributylamine, 8.2 g (0.05 mol) of 2-ethoxyethylmercaptoacetate were weighed into a stainless steel autoclave with a propeller stirrer and an electric heater with a regulator. , 3.7 g (0.02 mol) butyl iodide and 40 g (0.33 gram) tin powder.

The tin powder was purified twice by shaking with a 10% NaOH solution, washed with water, twice by shaking with methanol and drying with hot air. The reaction mixture is stirred at a rotational speed of 1000 - 50 minutes ^- ^ maintained at 160 ° C for 6 hours, the autoclave pressure reached about 1 MPa. The reaction mixture in the autoclave was dielíacom funnel and diluted with 30 ^cc of concentrated hydrochloric acid / 37% / in 200 cc of water and after shaking three times extra3 _f.

After drying with a drying agent such as CaCl2, Na2SO4, the ether was distilled off. The distillation residue was weighed and subjected to chromatographic analysis on a gas chromatograph [Conditions 10% 0V-17 on Chromaton N.AW-DMSC (0.1-0.125 mm), column length 600 mm, diameter 4/6, dosing temperature 250 ° C , column temperature 0 to 150 ° C with a gradient of 10 ° C / min., carrier gas nitrogen 30 cm @ -1 min.

Individual products were obtained by vacuum distillation, the physical constants of butyltin chloride are shown in Table 1.

Table 1

Substance molecular weight go to ta at / ° C / mp / ° c / boiling point at 1.3 kPa / ° C / 0.1 kPa butyltin trichloride 282, 17 ,, 70 ²⁰ -63 95 225 dibutyltin dichloride 303.83 1,36 ⁵⁰ 40 to 42 140 280 tributyltin chloride 325,50 1,21 ²⁰ -15 155 300 tetrabutylc ί n 347, 1 6 1,05 ²⁰ -13 145 285

From the obtained 105 g of a mixture containing 3.0% by weight of butyltin trichloride, 23.3% by weight of dibutyltin dichloride and 16.8% by weight of tributyltin chloride, 3.0 g of butyltin trichloride, 23 g of butyltin trichloride, 15.0 g of tributyltin chloride were obtained by vacuum distillation. distillation residue. The tin conversion was 100%. The yield of dibutyltin dichloride and tributyltin chloride calculated on tin was 36.2%.

Example 2

92.6 g (1 mol) of butyl chloride, 9.3 g (0.05 mol) of tributylamine, 8.2 g (0.05 mol) of 2-ethoxymercaptoacetate, 3.7 g (0) were weighed into the apparatus of Example 1. , 02 mol / butyl iodide and 40 g (0.33 gram) tin, the reaction temperature was 160 ° C and the reaction time was 6 hours. The procedure was as in Example 1 and 104 g of a mixture containing 19.71% by weight of dibutyltin dichloride and 15.53% by weight of tert-butylamine were obtained. The tin conversion was 100% and the selectivity of the preparation of dibutyltin dichloride and tributyltin chloride was 0.34.

Example 3

The procedure was as in Example 1, with the weightings as in Example 2 except that the amount of tributylamine was replaced with 7.9 g (0.05 mol) of benzyldimethylamine. The reaction temperature was 160 ° C and the reaction time was 6 hours. In a similar manner to Example 1, 62 g of a product mixture containing 39.6% by weight, dibutyl chloride and 10.74% by weight of tributyltin chloride were obtained. The tin conversion was 100% and the selectivity of the preparation of the two derivatives was 0.30.

Example4

The procedure was as in Example 1 except that a reaction mixture of 92.6 g (1 mol) butyl chloride, 8.2 g (0.05 mol) 2-ethoxyethyl mercaptoacetate, 10.5 g (0.05 mol) was used. LiCl, 3.7 g (0.02 mol) butyl iodide and 40 g (0.33 gram) tin. The reaction temperature was 160 ° C and the reaction time was 6 hours, as in Example 1, 84 g of a product mixture containing 2.6% by weight of butyl chloride, 31.62% by weight of dibutyltin dichloride and 11.62% by weight were obtained. From tributyltin chloride. The tin conversion was 100Z and the selectivity was direct. The di-butylindride and tributyltin chloride was 0.35.

Example5

The procedure was as in the example. The reaction temperature was 180 ° C, the reaction time was 4 hours and at the end of the alkylation the pressure was 1.8 MPa. In an analogous manner to Example 1, 100 g of a product mixture containing 26.8% by weight of dibutyltin dichloride and 16.6% by weight of tributyltin chloride were obtained. The tin conversion was 100Z and the selectivity of the preparation of said derivatives was 0.43.

Example 6

The procedure was as in Example 1, using a reaction mixture of 46.3 g (0.5 mol) isobutyl chloride, 4.65 g (0.025 mol) tributyl amine, 4.3 g 0.025 mol / 2- butoxyethyl mercaptoacetate, 1.85 g (0.01 mol) butyl iodide and 20 g (0.165 gram) tin. The reaction temperature was 160 ° C and the reaction time was 6 hours. As in Example 1, 22.3 g of a product mixture containing 41.3% by weight of dibutyltin dichloride and 30.2% by weight of tributyltin chloride were obtained. The unreacted tin was 8.0 g, representing a 60Z conversion of tin. The selectivity of the preparation of dibutyltin dichloride and tributyltin chloride is 0.85.

Example7.

The procedure was as in Example 1 using a reaction mixture of 46.3 g (0.5 mol) butyl chloride, 4.65 g (0.025 mol) tributylamine, 4.1 g (0.025 mol) 2-ethoxymercaptoacetate, 1.85 g (0.01 mol) butyl iodide and 20 g (0.165 gram) of tin, the reaction temperature was 170 ° C and reaction time 3 hours. In a similar manner to Example 1, 23.0 g of a mixture of products containing 36.45% by weight were obtained. From dibutyltin dichloride and 21.0% by weight of tributyltin chloride. 8.8 g of tin did not react, representing 56fc conversion of tin, the selectivity of dibutyltin dichloride and tributyltin chloride was 0.79.

To 8.8 g of unreacted tin washed with butyl chloride was added after drying 11.2 g of fresh tin (together with 0.165 grams). The other reactants were added as in Experiment 6 and the reaction mixture was worked up as in Example 1. As in Example 1, 30.3 g of a product mixture containing 34.2% by weight of dibutyltin dichloride and 19.3% by weight of tributyltin chloride were obtained. The unreacted tin was 6.6 g, which represents a 67% conversion of tin. The selectivity of dibutyltin dichloride and tributyltin chloride was 0.68.

As before, 6.6 g of unreacted tin was supplemented with fresh tin and all other substances in the same weights as in Example 6, and the reaction mixture was worked up under the same conditions. As in Example 1, 33.5 g of a product mixture containing 33.3% by weight of dibutyltin dichloride and 15.8% by weight of tributyltin chloride were obtained. 6.6 g of tin did not react, representing a selectivity at 0.65 at a 70Z tin conversion for dibutyltin dichloride and tributyltin chloride.

Example 8

The procedure was as in Example 1, using a reaction mixture of 74.4 g (0.5 mol) octyl chloride, 4.65 g (0.025 mol) tributylamine, 8.9 g (0.05 mol) 2- ethoxyethyl-3-mercaptopropionate, 1.85 g (0.01 mol) butyl iodide, 5.25 g (0.025 mol) lithium chloride and 20 g (0.156 gram) tin. The reaction temperature was 180 ° C and the reaction time was 6 hours. In an analogous manner to that of Example 1, 54.8 g of a mixture of products containing 6.6% by weight of octyltin trichloride, 25.8% by weight of tyridine trichloride and 19.7 wt. From trioctyltin chloride. The unreacted tin was 0.8 g, which represents a 96 Z conversion of tin. The selectivity of the preparation of dioctyltin dichloride and trioctyltin chloride is 0.35.

10368

The process according to the invention can be used in the preparation of organotin compounds belonging to important polyvinyl chloride spabilizers.

Claims (1)

OBJECT OF THE INVENTION A process for the preparation of alkyl tin chlorides of the general formula R 1 Sn-Cl 2 wherein R is alkyl of 3 to 8 carbon atoms m = 1 to 3an = 1 to 3 + n = 4, tin alkylalkyl and alkyl chloride in the presence of a catalyst. and an activator, characterized in that 1 to 2 moles of n- or even 3 to 8 carbon atoms of chlorine chloride is treated with 1 tin gram in the presence of 0.1 to 0.3 moles of a catalyst consisting of 2- alkoxyethyl mercaptoacetone and 1 or 2-alkoxyethyl -3-mercapto-propionate in each case having 1 to 4 carbon atoms in the alkoxy group, based on 1 gram tin, or in the presence of 0.1 to 0.3 mol of a catalyst composed of 1 part 2-alkoxyethyl mercaptoacetate or 2- alkoxyethyl-3-mercaptopropionate having from 1 to 4 carbon atoms in the alkoxy group and from 1 part of a tertiary amine of 2 to 6 carbon atoms in the alkyl, 6 carbon atoms in the aryl and 6 to 8 carbon atoms in the cycloalkyl of the tertiary amine; 0.05 to 0.1 mol of a 3 to 8 carbon alkyl iodide activator per molecule based on 1 gram of tin, or 0.05 to 0.3 mol of a lithium halide activator wherein the halogen the ene is chlorine, bromine, iodine based on 1 gram gram of tin in an enclosure equipped with an agitator at a speed of 800 to 1000 min -1 at temperatures of 130 to 1.80 ° C for 2 to 8 hours.