Catalytic Hydrogenation Apparatusfrom Organic Syntheses, CV 1, 61
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(A) Apparatus. A Prest-o-lite tank A from which the filling has been removed (Note 1), or any other similar tank of about 8- to 10-l. capacity, may be conveniently used as a container for hydrogen. The top of the tank contains two openings B and C. In B is welded a tube holding a gauge and valve, and through this tube the hydrogen from a large cylinder D is introduced into the tank. In C is welded another tube controlled by a needle valve. E is used for the vacuum, a manometer G being introduced into this system, and F for a tube leading to the reaction bottle H. These outlets are so arranged that it is possible to shut off the tank from either outlet and also to make a direct connection between the vacuum and the bottle H, leaving tank A out of the circuit. The connection between the tank A and the bottle H is a heavy taped rubber tube (Note 2) which is in turn connected to a glass tube inserted through the stopper of the bottle. The rubber tube and stopper should be of high grade and must be carefully boiled with alkali before being used (Note 3). The arrangement for shaking the bottle is shown in the diagram (Note 4). The driving pulley is connected to the reaction bottle by a wooden or preferably a metal rod. The rod in turn is attached by a yoke to a metal ring which circles the bottom of the bottle. The ring opens on the back side of the bottle and is held together by a wing-nut and bolt. In order to hold the stopper in the bottle when the latter is filled with hydrogen under pressure, a metal strip I is clamped tightly over the stopper. This strip is screwed to the long wooden bottle holder which extends between the bearings, and a short wooden piece which fits around the neck of the bottle is attached to the longer one by means of screws held by wingnuts. This arrangement permits removal of the bottle from the apparatus without detaching the metal strip.
The chief precautions in setting up this reduction outfit are, first, to have every piece free from catalytic poisons, and second, to be certain that there are no leaks (Note 5). The latter are sometimes an annoying factor, and the complete apparatus should be carefully tested before attempting any reductions for standardizing the hydrogen tank. The apparatus is put together in final form with the empty reduction bottle attached to the hydrogen tank exactly as it is arranged in a reduction. The tank is then filled with hydrogen until the gauge reads 2.5–3 atm. (40–45 lb.) and the temperature of the tank recorded. The reading of the gauge is observed as soon as equilibrium is reached and the bottle is then shaken for six to eight hours. Observations are made of the drop in pressure, taking into account any change of temperature which may occur during this time. In general if the drop in pressure is less than 0.03 atm. (0.5 lb.) in the time indicated the apparatus may be considered sufficiently free from leaks for ordinary work.
For some reactions it is advantageous to heat the mixture, and the following arrangement is very satisfactory for this purpose. The bottle H is wrapped with moistened asbestos paper to a thickness of about 3 mm. and the paper is then allowed to dry. When the asbestos is thoroughly dry the bottle is wound with a coil of No. 24 Nichrome wire, beginning the coil at the bottom of the bottle and making the turns about 9 mm. apart. The wire is then covered with a 3-mm. layer of asbestos, which is moistened and allowed to dry, after which the wire is wound around the bottle in another coil from top to bottom. The second coil is covered with asbestos as before, and the ends of the wire are connected to the terminal wires from a source of current. These wires are led along the bottle to the neck and held by means of tape in order to avoid excessive shaking. A variable resistance in the circuit is used to regulate the temperature.
(B) Use of Apparatus. The tank A is filled with hydrogen to a pressure of 3–3.5 atm. from the cylinder D (Note 6). The solution in a suitable solvent, of the substance to be reduced is poured into the bottle H and the platinum oxide (p. 463) is added (Note 7) and (Note 8). The bottle is attached to the apparatus and evacuated by opening valves E and F and closing C. In the case of low-boiling solvents, the evacuation is continued only until the solvent begins to boil; in other cases it is continued until the pressure as recorded by the manometer remains fairly constant. The valve E is then closed and hydrogen is admitted to the bottle H from the tank A by opening valve C (Note 9) and (Note 10). When the pressure in the bottle has become adjusted the pressure of the hydrogen and the temperature of the tank A are recorded. Shaking is started. Within a few minutes the brown platinum oxide turns black (see Note 6 on p. 467), and the absorption of hydrogen begins. The shaking is continued until the theoretical amount of hydrogen has been absorbed.
The hydrogen remaining in the bottle is removed, air is admitted and the mixture allowed to stand or, if necessary, shaken for a few minutes in order to aid the settling of the catalyst. In certain cases where the catalyst settles spontaneously at the end of the reduction it is not necessary to shake the mixture with air. The solution may be decanted from the main portion of the catalyst and a second reduction carried out. In cases where the catalyst cannot be used directly for another reduction (see Note 9 on p. 468) the solution is filtered, preferably through an asbestos filter (Note 11), and fresh solvent is used for washing. The reduction product is isolated from the filtrate, usually by distilling off the solvent. The reduction of ethyl p-nitrobenzoate to ethyl p-aminobenzoate and benzalacetophenone to benzylacetophenone (p. 101) is described in detail.
(C) Standardization of Apparatus. After making certain that there are no leaks in the apparatus (Note 5) the hydrogen tank may be standardized by reducing 11.6 g. (0.1 mole) of pure maleic acid (Note 12) dissolved in 150 cc. of 95 percent alcohol using 0.1 g. of catalyst (p. 463). The reduction is carried out according to the procedure described in part (B). Shaking of the mixture is continued until no more hydrogen is absorbed; the theoretical amount is absorbed by 0.1 mole of maleic acid within twenty or thirty minutes. The temperature of the tank is recorded. The decrease in pressure corresponds to 0.1 mole of hydrogen at the observed temperature. If the succinic acid is desired it may be recovered merely by filtering the platinum, evaporating the alcohol and crystallizing from about 10–15 cc. of boiling water. The yield of product is 10–11.5 g. (84–98 per cent of the theoretical amount) depending on the care used in crystallization.