CS199800B1 - Method of producing sodium tetraamido gallitate - Google Patents

Description

The invention relates to a process for the production of sodium tetraamidogallite from sodium, gallium and ammonia.

Sodium tetraamidogallite was prepared in small amounts in liquid ammonia from sodium, gallium and ammonia. The reaction was carried out in sealed T-shaped glass tubes and the reaction time was several days (Quarino R., Rouxel J.: CRAcad.Sci. Ser.C 264 (17) 1488 (1967) ·, Molinie P. et al.: Acta Crystallogr., Sect.B 2g (5) 925 (1973)). The low reaction rate and the method of carrying out the reaction do not allow the preparation of sodium tetraamidogallite on a larger scale.

The above disadvantages are overcome by the invention for the production of sodium tetraamidogallite from sodium, gallium in excess and liquid ammonia according to which the minimum amount of ammonia per present sodium is 10: 1 molar and the reaction is carried out in the presence of a transition metal ion, for example iron.

An advantage of the process according to the invention is that the reaction time of the preparation of sodium tetraamidogallite is shortened to several hours. The reaction temperature is maintained between 50 and 60 ° C. The amount of transition metal ion ee ranges from 0.01 to 0.6 g per 1 mol of sodium tetraamidogallite. Most preferably, the transition metal ion is added in the form of a halide or ester.

The sodium tetraamidogallite thus obtained can be used as a raw material for the preparation of compounds for electronic purposes.

199 800

Ιββ * 80

Several examples of embodiments of the method according to the invention are described below.

Example 1

2.3 g of Na (0.1 mol), 10.5 g of gallium (0.15 mol) and 0.06 g of cesium chloride were charged to a 200 µL shaking autoclave containing 3 steel stirrers of 1.2 µm diameter. After closing, the autoclave was capillary-coupled to a pressure ampoule and weighed with an amount of anhydrous ammonia (45 g, i.e. 2.6 nol), which was forced through the differential pressure to the reaction mixture. The reaction temperature was maintained at 50-60%. The pressure in the autoclave was read at 20 minute intervals, and the reaction was terminated after obtaining three identical pressure values at a constant temperature. The final pressure in the autoclave after 9 hours reached 7.1 MPa. Upon completion of the reaction, the liberated hydrogen was evacuated with ammonia, and after all ammonia had evaporated, the autoclave was opened and the solidified reaction mixture was crushed and poured into a glass extractor. Extraction with ammonia gave 14.1 g of a white crystalline solid with an analysis of 15.11% Na, 44.10% Ga and 34.83% N; ratio Na: Ga t N * 1.04: 1 »3.93. The yield of the reaction to the present sodium was 92.6%.

Example 2

2.3 g Na (0.1 mol), 10.5 g gallium (0.15 mol) and 0.06 g titanium (IV) propoxyxide were charged to a 200 µL shaking autoclave containing 3 1.2 cm diameter steel mixing balls. After sealing, the autoclave was connected by capillary to a pressure ampoule and weighed with an amount of anhydrous ammonia (49 g, 2.9 mol), which was overpressed by differential pressure to the reaction emission. The temperature of the reaction mixture was maintained at 55-60 ° C. The reaction was complete after obtaining three equal pressure values at a constant temperature. The pressure in the autoclave was read at 20 minute intervals and reached 8.3 MPa after 8.3 hours. Upon completion of the reaction, the liberated hydrogen together with ammonia was discharged and after all ammonia had evaporated, the autoclave was opened and the solidified reaction mixture was crushed and poured into a glass extractor. Extraction with ammonia gave 13 * 9 g of a white crystalline solid with an analysis of 15 * 20% Na, 44 * 22% Ga and 35 * 11% N; ratio Na: Ga: N »1 * 04 t 1: 3 * 95. The yield of the reaction to the present bard was

91.8%.

Example 3

To a 200 ml shake autoclave containing 3 steel stirrers of 1 * 2 µm diameter was charged 2.3 g of Na (0 * 1 mol) * 10.5 g of gallium (0.15 molX and 0.06 g of vanadium chloride). After closing, the capillary was connected to a pressure ampoule and weighed with an amount of anhydrous ammonia (42 g, i.e. 2.5 mol), which was pressurized to a reaction mixture by pressure difference. The reaction temperature was maintained between 55 and 60. The final pressure after 10 hours reached 6.9 MPa After completion of the reaction, the evolved hydrogen was released together with ammonia, and after all the ammonia had evaporated, the autoclave was opened and the solidified reaction ammonium was crushed and poured into a glass extractor. 13.5 g of a white crystalline solid was obtained with an analysis of 15.41% Na, 44.17% Ga and 35.46 g Nj of a Na: Ga: N ratio of 1.06: 1: 3.99. Eny aodík was 90.4% ·

Claims (1)

When B D MAKE THE INVENTION A process for the production of sodium tetra-tallowallite from sodium, gallium in excess and liquid ammonia, characterized in that the minimum amount of ammonia per present hydrogen is 10: 1 molar and the reaction is carried out in the presence of a transition metal ion, for example iron chloride.