Ice. dry

Solid carbon dioxide (Dry Ice, Drikold) is employed when very low temperatures are required. If it is suspended in solvents, such as alcohol or a mixture of equal volumes of chloroform and carbon tetrachloride, temperatures down to — 50° can be easily attained. Lower temperatures still are reached if intimate mixtures of solid carbon dioxide and organic solvents are employed with ethyl alcohol, — 72° with... 

For some purposes in the Grignard reaction) solid carbon dioxide, narketed as Dry Ice or Drikold, may be employed. 

A set-up for distillation under reduced pressure is shown in Fig. 11,60,3 it is generally more convenient to use a Kon receiver or a Perkin triangle (Fig. 11, 56, 31). The vessel at the side, connected to the assembly by rubber pressure tubing, may be immersed in a Dry Ice-acetone bath and serves as a trap for volatile materials. 

The gas is dried by passage through wash bottles containing concentrated sulphuric acid. Alternatively and more simply, the technique (described below for n.valeric acid) utilising solid carbon dioxide (Dry Ice or Drikold) may be employed. 

Dry Ice should be handled with gloves or with a dry towel if Dry Ice is held for a long time in the hand, it may cause frost bite. 

Alternatively, the solution of the Grignard reagent may be poured on to solid carbon dioxide (Dry Ice)—for experimental details, see under n-Valeric Acid, Section 111,84. 

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 . 

Pentyn-l-ol. Prepare a solution of sodamide in liquid ammonia as detailed for n-Butylacetylene. Use a 3-htre three-necked flask, equipped with a Dewar type of reflux condenser (Fig. II, 1, 4, h) cooled with Dry Ice... 

C bol the solution of re-butyl-hthium to — 35° in a Dry Ice - acetone bath and add, whilst stirring vigorously, a solution of 48 g. of ni-chlorobromo-benzene (Section IV,62) in 75 ml. of anhydrous ether. Stir for 8-10 minutes and pour the mixture with stirring on to a large excess of sohd carbon dioxide in the form of a Dry Ice - ether slush contained in a -htre beaker. Isolate the acid as detailed above for p-Toluic acid and recrystal-lise it from hot water. The yield of ni-chlorobenzoic acid, m.p. 150-151°, is 27 g. 

Cholestenone. Place a mixture of 1 0 g. of purified cholesterol and 0-2 g. of cupric oxide in a test-tube clamped securely at the top, add a fragment of Dry Ice in order to displace the air by carbon dioxide, and insert a plug of cotton wool in the mouth of the tube. Heat in a metal bath at 300-315° for 15 minutes and allow to cool rotate the test-tube occasionally in order to spread the melt on the sides. Warm with a few ml. of benzene and pour the black suspension directly into the top of a previously prepared chromatographic column (1) rinse the test-tube with a little more benzene and pour the rinsings into the column. With the aid of shght suction (> 3-4 cm. of mercury), draw the solution into the alumina column stir the top 0 -5 cm. or so with a stout copper wire to... 

To a solution of ethylnagnesium bromide in 350 ml of THF, prepared from 0.5 mol of ethyl bromide (see Chapter 11, Exp. 6) was added in 10 min at 10°C 0.47 mol of 1-hexyne (Exp. 62) and at 0°C 0.47 mol of trimethylsilylacetylene (Exp. 31) or a solution of 0.60 mol of propyne in 70 ml of THF (cooled below -20°C). With trimethyl si lylacetylene an exothermic reaction started almost immediately, so that efficient cooling in a bath of dry-ice and acetone was necessary in order to keep the temperature between 10 and 15°C. When the exothermic reaction had subsided, the mixture was warmed to 20°C and was kept at that temperature for 1 h. With 1-hexyne the cooling bath was removed directly after the addition and the temperature was allowed to rise to 40-45°C and was maintained at that level for 1 h. 

After the addition of the propyne the thermometer-gas outlet combination was replaced with a "cold finger" filled with dry-ice and acetone. The top of this reflux condenser was connected via a plastic tube with a cold trap (-75°C) containing 50 ml of dry THF. The cooling bath was removed and the conversion of propyne started... 

A suspension of 2.3 mol of sodamide in about 1.5 1 of liquid amnonia was prepared as described in Chapter II, Exp. 11. To this suspension was added 1 g of triphenylmethane. Acetylene (4-5 1/min) was introduced until the red colour of the triphenylmethane anion had disappeared. The flask was then placed in a cooling bath with dry-ice and acetone (-50°C) and the introduction of acetylene (1-1/min) was continued for an additional 10 min. Dry DMSO (200 ml) was then poured into... 

Apparatus 3-1 round-bottomed, three-necked flask, provided with a dropping funnel, a mechanical stirrer and a reflux condenser, cooled with dry-ice and acetone (cold finger). The upper end of this condenser was connected with a drying tube filled with anhydrous calcium chloride. 

Note 3. Liquid nitrogen may be used for cooling.. In the case of dry-ice-acetone the addition to the dibromo compound will take more than 15 min. 

To a mixture of 250 ml of ether and 3 moles of freshly distilled acrolein ivere added about 3 moles of bromine at a rate such that the temperature could easily be maintained between -30 and -90°C (bath of dry-ice-acetone or liquid Nj). After persisting of the browncolour, the temperature was allowed to rise to 0°C. Freshly distilled ethyl orthoformate (3.25 moles) and 96% ethanol (30 ml) were added. 

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