Acid chloride, alcohols from reaction with water

Most aromatic acid chlorides impart a strongly acid reaction when shaken with water (compare Section 111,88). All are completely hydrolysed by boiling with solutions of caustic alkalis and yield no product volatile from the alkaline solution (compare Eaters, Sections 111,106 and IV, 183). They may be distinguished from acids by their facile reactions with alcohols (compare Section 111,27), phenols (compare Section IV,114), and amines (compare Sections 111,123 and IV.lOO). 

CHLOROTRIAZINE (108-77-0) Reacts with moist air, forming fumes of hydrogen chloride fumes. Violent exothermic reaction with water above 86°F/30°C or steam, forming hydrogen chloride and cyanic acid. Violent reaction with ethanol, dimethylformamide, dimethylsulfoxide, methanol. Isolate from alcohols and caustic materials. 

Propargyl alcohol (11.2 g, 0.20 mol) was added with stirring to a mixture of copper(I) chloride (25 g, 0.13 mol), ammonium chloride (40 g, 0.75 mol), concentrated ammonium hydroxide (12.5 mL, 0.18 mol NH3), and water (200 mL). The mixture was stirred under a slight (30 Torr) positive pressure of oxygen for 20 h. The blue-green reaction mixture was acidified with dilute hydrochloric acid, diluted to 750 mL with water and extracted with ether in a continuous extractor for 24 h. Evaporation of ether from the extract left a solid which, when recrystallized from hot water, gave 9.1 g (83%) of the title compound, mp 111.5-112 °C. 

Dissolve 0 01 g. equivalent of the amino acid in 0 03 g. equivalent of N sodium hydroxide solution and cool to 5° in a bath of ice. Add, with rapid stirring, 0 -01 g. equivalent of 2 4-dichlorophenoxyacetyl chloride dissolved in 5 ml. of dry benzene at such a rate (5-10 minutes) that the temperature of the mixture does not rise above 15° if the reaction mixture gels after the addition of the acid chloride, add water to thin it. Remove the ice bath and stir for 2-3 hours. Extract the resulting mixture with ether, and acidify the aqueous solution to Congo red with dilute hydrochloric acid. Collect the precipitate by filtration and recrystallise it from dilute alcohol. 

The apparatus required is similar to that described for Diphenylmelhane (Section IV,4). Place a mixture of 200 g. (230 ml.) of dry benzene and 40 g. (26 ml.) of dry chloroform (1) in the flask, and add 35 g. of anhydrous aluminium chloride in portions of about 6 g. at intervals of 5 minutes with constant shaking. The reaction sets in upon the addition of the aluminium chloride and the liquid boils with the evolution of hydrogen chloride. Complete the reaction by refluxing for 30 minutes on a water bath. When cold, pour the contents of the flask very cautiously on to 250 g. of crushed ice and 10 ml. of concentrated hydrochloric acid. Separate the upper benzene layer, dry it with anhydrous calcium chloride or magnesium sulphate, and remove the benzene in a 100 ml. Claisen flask (see Fig. II, 13, 4) at atmospheric pressure. Distil the remaining oil under reduced pressure use the apparatus shown in Fig. 11,19, 1, and collect the fraction b.p. 190-215°/10 mm. separately. This is crude triphenylmethane and solidifies on cooling. Recrystallise it from about four times its weight of ethyl alcohol (2) the triphenylmethane separates in needles and melts at 92°. The yield is 30 g. 

Reflux 1 g. of the sulphonamide with 2-5 ml. of acetyl chloride for 30 minutes if solution is not complete within 5 minutes, add up to 2-5 ml. of glacial acetic acid. Remove the excess of acetyl chloride by distillation on a water bath, and pour the cold reaction mixture into water. Collect the product, wash with water and dissolve it in warm sodium bicarbonate solution. Acidify the Altered solution with glacial acetic acid Alter oflF the precipitated sulphonacetamide and recrystaUise it from aqueous alcohol. 

Method 2. Place a 3 0 g. sample of the mixture of amines in a flask, add 6g. (4-5 ml.) of benzenesulphonyl chloride (or 6 g. of p-toluenesulphonyl chloride) and 100 ml. of a 5 per cent, solution of sodium hydroxide. Stopper the flask and shake vigorously until the odour of the acid chloride has disappeared open the flask occasionally to release the pressure developed by the heat of the reaction. AUow the mixture to cool, and dissolve any insoluble material in 60-75 ml. of ether. If a solid insoluble in both the aqueous and ether layer appears at this point (it is probably the sparingly soluble salt of a primary amine, e.g., a long chain compound of the type CjH5(CH2) NHj), add 25 ml. of water and shake if it does not dissolve, filter it off. Separate the ether and aqueous layers. The ether layer will contain the unchanged tertiary amine and the sulphonamide of the secondary amine. Acidify the alkaline aqueous layer with dilute hydrochloric acid, filter off the sulphonamide of the primary amine, and recrystaUise it from dilute alcohol. Extract the ether layer with sufficient 5 per cent, hydrochloric acid to remove all the tertiary amine present. Evaporate the ether to obtain the sulphonamide of the secondary amine recrystaUise it from alcohol or dilute alcohol. FinaUy, render the hydrochloric acid extract alkaline by the addition of dilute sodium hydroxide solution, and isolate the tertiary amine. 

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