Chlorides acids

The acid chloride is available commercially, but it is more economical to prepare it from the acid as and when required. Furthermore, 3 5-dini-trobenzoyl chloride tends to undergo hydrolysis if kept for long periods, particularly if the stock bottle is frequently opened. The substance may, however, be stored under light petroleum. 

Acid chlorides (but not acid anhydrides) precipitate silver chloride on treatment with aqueous AgNOg acidified with HNO3- 

Acid chlorides, and some anhydrides, condense with aniline to give anilides. 

Acid chlorides and anhydrides give hydroxamic acids with 

A) ACID CHLORIDES. Acetyl chloride benzoyl chloride (and substituted benzoyl chlorides). 

Amides. TVeat the acid chloride cautiously with about 20 parts of concentrated ammonia solution (sp. gr. 0 - 88) and warm for a few moments. If no solid separates on cooling, evaporate to dryness on a water bath. Recrystallise the crude amide from water or dilute alcohol. 

Alternatively, dissolve or suspend the acid chloride in 5-10 ml. of dry ether or dry benzene, and pass in dry ammonia gas. If no solid separates, evaporate the solvent. Recrystallise the amide from water or dilute alcohol. 

Amides, anilides and p toluidides. The dry acid is first converted by excess of thionyl chloride into the acid chloride  

It will also reduce acid chlorides, acid anhydrides and aldehydes to primary alcohols, ketones to secondary alcohols, and amides to the corresponding amines R-CONHi -> R CHiNH. Nitro-hydrocarbons if aromatic are 

Method (1) is most frequently used for aliphatic acid amides, while Methods (2a), (2b) and (zc) are used most frequently for aromatic acid amides. Of the last three methods, the Acid Chloride Method (zb) is the most rapid and certain. The Ester Method (za) is practicable only when the amide is insoluble in water, and even then is often very slow unless the ester itself is appreciabb soluble in the aqueous ammonia solution. 

The chemical reactions of the acid chlorides and anhydrides are so closely parallel that they are considered together. 

A similar coloration is given by acid chlorides, acid anhydrides. ind many amides, but these classes of substances are readily detected by other means and cannot be confused with esters. 

Corrosive liquids and solids (acids, acid chlorides, etc.) are easily manipulated, and no impurities are introduced into the product from the apparatus. 

It should be emphasised that whereas the interaction of a sodium salt and an acid chloride is a convenient general laboratory method for preparing all classes of anhydrides, acetic anhydride is prepared on a large scale by other and cheaper methods. Industrial processes are based on reactions indicated by the equations  

One disadvantage of this method is that it is sometimes difficult to separate the acid chloride sharply from the phosphorus oxychloride by fractional dis tillation, and unless the boiling oints of these two substances are fairly wide apart, traces of the oxychloride will occasionally pass over in the vapour of the acid chloride. If, however, thionyl chloride is used instead of phosphorus 

One of the general methods for the preparation of acid chlorides is the action of phosphorus pentachloride on the corresponding carboxylic acid  

The preparation of acetophenone (p. 255) is a modification of this method, the alkyl halide being replaced by an acid chloride, with the consequent formation of a ketone. 

Esters can also be prepared by the action of alcohols on acid chlorides and anhydrides. 

The Schotten-Baumann reaction may also be carried out, using, for example, benzene sulphonyl chloride, CeH,SO,Cl (. e., the acid chloride of benzene sulphonic acid, C H5SOjOH) in place of benzoyl chloride, and similar deri a-tives are obtained. Thus when phenol is dissolved in an excess of 10% sodium hydroxide solution, and then shaken with a small excess of benzene sulphonyl 

Reacts slowly on heating without evolution of gas. Esters some acid chlorides and anhydrides benzaldehyde (undergoes Cannizzaro s reaction, p. 342). 

Stopper the side arm of a 25 or 50 ml. distilling flask and fit a vertical water condenser into the neck. Place 0-5-1 -0 g. of the dry acid (finely powdered if it is a solid) into the flask, add 2-5-5 0 ml. of redistilled thionyl chloride and reflux gently for 30 minutes it is advisable to place a plug of cotton wool in the top of the condenser to exclude moisture. Rearrange the condenser and distil off the excess of thionyl chloride t (b.p. 78°). The residue in the flask consists of the acid chloride and can be converted into any of the derivatives given below. 

The by-products are both gaseous and the excess of thiouyl chloride (b.p. 78°) may be readily removed by distillation. Interaction of the acid chloride with ammonia solution, aniline or p-toluidiiie yields the amide, anilide or p-toluidide respectively  

Hydroxamic acid formation resembles amide formation (pp. 117-119) and therefore certain other classes of substances will respond to the test, e.g., acid chlorides and acid anhydrides, but these substances are readily distinguished by other reactions. 

Sulphur oxide dichloride is used as a chlorinating agent in organic chemistry, for example in the preparation of acid chlorides  

L. Treat with hydroxylamine and ferric chloride (pp. 334, 353). Violet or red colorations given particularly by esters. Deep colorations also given by acid chlorides, acid anhydrides and by some acid amides (usually aliphatic) and by a few of the simpler anilides. 

The choice of type of derivative should be based on whether the chloride or anhydride is aliphatic or aromatic, because this factoi largely determines the reactivity. Aliphatic acid chlorides are best converted into their anilides, as in 4 above aromatic acid chloride may be similarly converted into their anilides, or they may be converted into their amides by shaking with an excess of ammonia (p, 120). (M.ps., pp. 544-545.) Aliphatic acid anhydrides should be converted into their crystalline anilides, but aromatic acid anhydrides arc best hydrolysed to the acid, which can then be converted into one of the standard derivatives (p. 349). 

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