Diethylene glycol

CH3.O-CH2.CH2-O.CH2-CHj-O.CH3. Dimethyl ether of diethylene glycol. A colour-less liquid b.p. 160 C. Typical ether, useful as a high-temperature solvent. 

The diethyl ether of diethylene glycol (diethyl carbitol), b.p. 186°/ 760 mm., is completely miscible with water. The above three ethers may be purified by distillation from sodium. 

Place 36 -0 g. of redistilled acetophenone, b.p. 201° (Section IV,136), 300 ml. of diethylene glycol, 30 ml. of 90 per cent, hydrazine hydrate and 40 g. of potassium hydroxide pellets in a 500 ml. Claisen flask provided with a reflux condenser and a thermometer dipping into the liquid (compare Fig. Ill, 31, 1). Warm the mixture on a boiling water bath until most of the potassium hydroxide has dissolved and then reflux (free flame) for one hour. Arrange the apparatus for distillation and distil until the temperature in the liquid rises to 175° (1) keep the distillate (ca. 50 ml.). Replace the reflux condenser in the flask and continue the refluxing for 3 hours. 

The reaction represented is that with hydrazine solution, produced from hydrazine sulphate and sodium acetate in the presence of aqueous alcohol. Excellent results are also obtained by interaction of the commercially available 60-64 per cent, hydrazine solution with a solution of 2 4 dinitrochloro-benzene in triethylene glycol or in diethylene glycol at about 20°. 

The following alternative method of preparation is recommended. Dissolve 50 g. of purified 2 4-dinitrochlorobenzene (1) in 100 ml. of triethylene glycol (gentle warming nia be necessary alternatively, 125 ml. of warm diethylene glycol may be used) in a 600 ml. beaker and cool, with mechanical stirring, in an ice bath to 15-18°. Place 15 ml. of commercial 60-65 per cent, hydrazine solution in a small separatory funnel supported over the beaker. Add the hydrazine solution to the stirred solution in the beaker at such a rate that the temperature is maintained between 15° and 20° (20-30 minutes). When... 

Diethylene glycol method. Place 0-5 g. of potassium hydroxide pellets, 3 ml. of diethylene glycol and 0 5 ml. of water in a 10 or 25 ml. distilling flask heat the mixture gently until the alkali has dissolved and cool. Add 1-2 g. of the ester and mix well. Fit the flask with a thermometer and a small water-cooled condenser in the usual way. Heat the flask over a small flame whilst shaking gently to mix the contents. When only one liquid phase, or one hquid phase and one solid phase, remains in the flask, heat the mixture more strongly so that the alcohol distils. Identify the alcohol in the distillate by the preparation of the 3 5 dinitrobenzoate (Section 111,27,2). 

The residue in the flask is either a solution or a suspension of the potassium salt of the acid derived from the ester in diethylene glycol. Add 10 ml. of water and 10 ml. of ethyl alcohol to the residue and shake until thoroughly mixed. Then add a drop or two of phenolphthalein and dilute sulphuric acid, dropwise, until just acid. Allow the mixture to stand for about 5 minutes and then Alter the potassium sulphate. Use the clear filtrate for the preparation of a sohd derivative or two of the acid (see Section 111,85,4). 

The determination of the saponification equivalent of an ester by the alcohohc potassium hydroxide method is described in Section 111,106 an alternative procedure using diethylene glycol is given below. This constant should be determined if possible in the prehminary examination, since a knowledge of its value together with the boihng point provides a basis for a fairly good approximation of the size of the ester molecule. 

Determination of the Saponification Equivalent of an Ester BY THE Diethylene Glycol Method... 

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