0.8 Organic reactions

Organic reactions

Objectives

• Synthesis of some important esters.
• Oxidation of a primary alcohol first to an aldehyde and then a carboxylic acid.
• To saponify a typical vegetable oil.

  Grading

You will be assessed on

• detailed answers required in the lab report.
• the correctness and thoroughness of your observations.

Introduction

Esters are an important class of organic compounds commonly prepared from the esterification reaction of an organic acid with an alcohol in the presence of a strong mineral acid (usually $H_2{\text{SO}}_4$ ). They are chiefly responsible for the pleasant aromas associated with various fruits, and as such are used in perfumes and flavorings. Some esters also have useful physiological effects. The best known example is the analgesic ("pain killing") and anti-pyretic ("fever reducing") drug acetylsalicylic acid, otherwise known by its trade name aspirin.

Liniments used for topical relief of sore muscles contain the ester methyl salicylate ("oil of wintergreen"), which is prepared from the reaction of methyl alcohol with the acid group of salicylic acid. Methyl salicylate acts as an analgesic and is absorbed through the skin; however, methyl salicylate is also a skin irritant (like many organic substances), which in this instance provides the beneficial side effect of the sensation of warming in the area of the skin where the liniment is applied.

Oxidation of a primary alcohol may yield either an aldehyde or a carboxylic acid, depending on the reaction conditions. For example, mild oxidation of ethanol produces acetaldehyde, which under more vigorous conditions may be further oxidised to acetic acid. The oxidation of ethanol to acetic acid is responsible for causing wine to turn sour, producing vinegar.

A number of oxidising agents may be used. Acidified sodium dichromate (VI) solution at room temperature will oxidise primary alcohols to aldehydes and secondary alcohols to ketones. At higher temperatures primary alcohols are oxides further to acids.

The dichromate solution turns from the orange color of the ${\text{Cr}}_2{O}_7^{2-}$ (aq) to the blue color of the ${\text{Cr}}^{3+}$ (aq). This color change is the basis for the "breathalyser test". The police can ask a motorist to exhale through a tube containing some orange crystals. If the crystals turn blue, it shows that the breath contains a considerable amount of ethanol vapor.

Soaps are produced by the reaction of metallic hydroxides with animal fats and vegetable oils. The major components of these fats and oils are triglycerides. Triglycerides are esters of the trihydroxy alcohol called glycerol and various long-chain fatty acids. Tristearin is a typical triglyceride. Upon reaction with sodium hydroxide, the ester bonds of tristearin are broken. The products of the reaction are the soap, sodium stearate, and glycerol. This type of reaction is called saponification (Greek: sapon, soap) and it is depicted below.

Soap is made commercially by heating beef tallow in large kettles with an excess of sodium hydroxide. When sodium chloride is added to this mixture (called the "saponified" mixture), the sodium salts of the fatty acids separate as a thick curd of crude soap. Glycerol is an important by-product of the reaction. It is recovered by evaporating the water layer. The crude soap is purified, and coloring agents and perfumes are added to meet market demands.