Temperature bath

If Lh c con Stan t Ictn pcratti re a Igori Lli rn is used in a trajectory analysis, then the initial conditions arc constantly being modified according to the sirn ulation of th c con stan t tern perattirc bath an d th e relaxation of th e m olecu lar system to that bath temperature, fhe effect of such a bath on a trajectory analysis is less studied than for th c sirn 11 lation of cqu i libriii m behavior. 

Make a thin paste of 21 5 g. of finely-powdered o-tolidine (a commercial product) with 300 ml. of water in a 1-litre beaker, add 25 g. (21 ml.) of concentrated hydrochloric acid, and warm until dissolved. Cool the solution to 10° with ice, stir mechanically, and add a further 25 g. (21 ml.) of concentrated hydrochloric acid (1) partial separation of o tolidine dihydrochloride will occur. Add a solution of 15 g, of sodium nitrite in 30 ml. of water as rapidly as possible, but keep the temperature below 15° a slight excess of nitrous acid is not harmful in this preparation. Add the clear, orange tetrazonium solution to 175 ml. of 30 per cent, hypophosphorous acid (2), and allow the mixture to stand, loosely stoppered, at room temperature for 16-18 hours. Transfer to a separatory funnel, and remove the upper red oily layer. Extract the aqueous layer with 50 ml, of benzene. Dry the combined upper layer and benzene extract with anhydrous magnesium sulphate, and remove the benzene by distillation (compare Fig. II, 13, 4) from a Widmer or similar flask (Figs. II, 24, 3-5) heat in an oil bath to 150° to ensure the removal of the last traces of benzene. Distil the residue at ca. 3 mm. pressure and a temperature of 155°. Collect the 3 3 -dimethyldiphenyl as a pale yellow liquid at 114-115°/3 mm. raise the bath temperature to about 170° when the temperature of the thermometer in the flask commences to fall. The yield is 14 g. 

In a 250 ml. conical flask, fitted with an air condenser of wide bore, place 50 g. (51 -5 ml.) of acetonylacetone (see Section V,9, Note 2) and 100 g. of ammonium carbonate (lump form). Heat the mixture in an oil bath at 100° until effervescence stops (60-90 minutes) some ammonium carbonate (or carbamate) sublimes into the condenser and this must be pushed back into the reaction mixture by means of a stout glass rod. Replace the air condenser by a Liebig s condenser with wide bore inner tube and reflux the mixture gently (bath temperature, 115°) for a further 30 minutes dissolve the solid which has sublimed into the condenser in about 5 ml. of hot water and return the solution to the reaction mixture. 

Sodamide. Assemble the apparatus shown in Fig. VI, 16, 1, a. Fill the bath to a point about half-way up the side of the flask with methyl alcohol (or methylated spirit) and add solid carbon dioxide (Dry Ice or Drikold) in lump form until a white frost commences to form on the outside of the bath (2) the bath temperature should be about — 35 . 

Sodium acetyllde. Replace the ammonia - addition tube by a wide tube reaching almost to the bottom of the flask (or use the device depicted in Fig. II, 7, 12, b) and pass acetylene (Fig. VI, 16, 1, c) into the suspension of sodamide in liquid ammonia maintain the bath temperature at about — 35° so that little ammonia is lost. Continue the passage of acetylene until a uniformly black liquid is formed (usually 4r-5 hours) (7). Carefully watch the wide gas entry tube if much solid collects inside this tube, remove it before the tube is completely blocked. Add liquid ammonia, if necessary, to restore the original volume (ca. 3 5 litres). 

The aqueous layer was extracted with diethyl ether. The combined ethereal solutions were dried over potassium carbonate, after which the greater part of the diethyl ether was distilled off at normal pressure through a 40-cm Vigreux column (bath temperature < 90°C). Careful distillation of the remaining liquid afforded the bis-ether, b.p. 47-49°C/18 mmHg, Op 1.4469, in 78% yield. 

Note 3. During the distillation of the sulfide with R = CH3 the bath temperature should be kept below 70°C. Too strong heating may result in explosive decomposition of the residue. 

Note 1. A considerable part of the diamine can be recovered by distilling it off from the reaction mixture, using a bath temperature not exceeding 5Q°C. 

In a similar way H2C=C=CH-SC2H5, b.p. 30 c/12 nmHg, n 1.5210, was prepared in 864 yield from CH3C=C-SC2H5. After the greater part of the solvent had been distilled off at normal pressure (bath temperature below 70°C), the remaining liquid was distilled at water-pump pressure and collected in a single receiver... 

The extracts were kept below 0°C (note 5). The combined extracts were washed with 5i acetic acid and subsequently dried over magnesium sulfate (note 6). The extract was concentrated in a water-pump vacuum to about 60 ml by means of the rotary evaporator, care being taken that the bath temperature remained below 25°C. The remaining pale yellow solution was warmed to about 35°C (internal temperature). The temperature rose gradually but was kept at about 45°C by occasional cooling. When after about 45 min the exothermic reaction had subsided, the flask was placed in a water-bath at 55°C. After 30 min the remaining pentane was removed in a water--pump vacuum. The orange residue, n 1.5878, yield aa. 92% was almost pure allenic dithioester. 

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