CARBOXYLIC ACID

Carboxylic Acid

Carboxylic acids are organic acids characterized by the presence of at least one carboxyl group. The general formula of a carboxylic acid is R-COOH, where R is some monovalent functional group. Carboxylic acids are Brnsted-Lowry acids because they are proton donors. They are the most common type of organic acid. Among the simplest examples are formic acid H-COOH, that occurs in ants, and acetic acid CH3-COOH, that gives vinegar its sour taste. Acids with two or more carboxyl groups are called dicarboxylic,tricarboxylic, etc.

Preparation Properties

Uses

compounds which contain a -COOH group that is attached either to a hydrogen atom or to an alkyl group.

Oxidation of alkenes

The oxidation of primary alcohols and aldehydes

Preparation

The oxidation of alkyl benzenes

Hydrolysis of nitriles

Carboxylic acid

The carbonation of Grignard reagents

Solubility in Water

Boiling point

Properties

Melting point

Uses

Acidity

Odour

Preparation of Carboxylic acid

Oxidation of alkenes Alkenes are oxidized to acids by heating them with solutions of potassium permanganate (KMnO4) or potassium dichromate (K2Cr2O7).

Oxidation of alkenes The ozonolysis of alkenes produces aldehydes that can easily be further oxidized to acids.

The oxidation of primary alcohols and aldehydes The oxidation of primary alcohols leads to the formation of alde-hydes that undergo further oxidation to yield acids. All strong oxidizing agents (potassium permanganate, potassium dichromate, and chromium trioxide) can easily oxidize the aldehydes that are formed

The oxidation of alkyl benzenes Alkyl groups that contain benzylic hydrogenshydrogen(s) on a carbon to a benzene ringundergo oxidation to acids with strong oxidizing agents.

In the above example, t-butylbenzene does not contain a benzylic hydrogen and therefore doesn't undergo oxidation

The carbonation of Grignard reagents Grignard reagents react with carbon dioxide to yield acid salts, which, upon acidification, produce carboxylic acids.

Hydrolysis of nitriles

The hydrolysis of nitriles containing a cyano group, leads to carboxylic acid formation. It can take place in either acidic or basic solutions.

The mechanism follows these steps:

The nitrogen atom of the nitrile group is protonated.

The carbocation generated in Step 1 attracts a water molecule.

The oxonium ion loses a proton to the nitrogen atom, forming an enol.

The enol tautomerizes to the more stable keto form.

The amide is protonated by the acid, forming a carbocation.

A water molecule is attracted to the carbocation.

The oxonium ion loses a proton.

The amine group is protonated.

An electron pair on one of the oxygens displaces the ammonium group from the molecule.

Higher fatty acids

manufacture of soaps. Soaps are sodium potassium salts of higher fatty acids such as stearic acid.

used in foods, cold drinks

Organic acids Uses Organic acids

used as preservatives.

used for the preparation of many drugs such as aspirin, phenacetin etc.

coagulant in the manufacture of rubber.

Acetic acid
manufacture of various dye stuffs, perfumes and rayon.

Ester

Esters are chemical

compounds derived

by

reacting

an oxoacid with

a hydroxyl compound such as an alcohol or phenol. Esters are usually derived from an inorganic acid or organic acid in which at least one -OH (hydroxyl) group is replaced by an -O- alkyl (alkoxy) group, and most commonly from carboxylic acids and alcohols. That is, esters are formed by condensing an acid with an alcohol.

Preparation

Uses

Properties

Carboxylic acids + alcohols

Heat

ester + water
Catalyst (concentrated H2SO4)

Preparation
The equation for the reaction between an acid RCOOH and an alcohol R'OH (where R and R' can be the same or different) is:

Example: ethanoic acid + ethanol

ethyl ethanoate + water

Step in producing ester

Reflux

Separation

Purification

The reaction mixture consisting of the alkanol, the alkanoic acid and a small amount of concentrated sulfuric acid is heated in a vessel with a watercooled condenser (Liebig condenser) to prevent loss of volatile material.

After heating, the reaction mixture is then poured into a separating funnel. Calcium carbonate (CaCO3), or a similar neutralizing agent, is added to the mixture to react with any unreacted acid present in the mixture.

The organic layer separated in the separating funnel above contains the ester. This organic layer is distilled to obtain the pure ester. A sharp boiling point is an indication of the purity of the ester.

Properties

more volatile than carboxylic acids

colourless and exist in liquid state at room temperature.

polar due to the presence of carbonyl (=C=O)group and act as hydrogen bond acceptors not as donors.

Properties
have low boiling and melting points

highly soluble in organic solvents and partly soluble in water.

sweet odour

Uses

Use of ester

To make a substance less water soluble meaning the carboxylic acid is more soluble then its ester.

To combine two substances together Eg. Procaine with Penicillin so 1 drug 2 effects

To create surfactants Eg. Soap

used in flavouring and perfumes

Amides

Amides are derived from carboxylic acids. A carboxylic acid contain the COOH group and in an amide the OH part of that group is replaced by an NH2 group. Soamides contain the CONH2 group.

Three simplest amides are: HCONH2 CH3CONH2 CH3CH2CONH2 methanamide ethanamide propanamide

Notice that, the name derived from the acid by replacing the oic acid ending by amide

Preparation Properties

Uses

Preparation

The ammonium salt is formed by adding solid ammonium carbonate to an excess of the acid.

When the reaction is complete, the mixture is heated and the ammonium salt dehydrates producing ethanamide.

The carboxylic acid is first converted into an ammonium salt which then produces an amide on heating.

The excess of ethanoic acid is there to prevent dissociation of the ammonium salt before it dehydrates. The dissociation is reversible: The presence of the excess ethanoic acid helps to prevent this from happening by moving the position of equilibrium to the left.

Ammonium salts tend to split into ammonia and the parent acid on heating, recombining on cooling.

The melting points of the amides are high

much stronger bases than carboxy lic acids, esters, aldehydes, and ketones

Properties of Amides

The small amides are soluble in water because they have the ability to hydrogen bond with the water molecules.

weak bases

Uses of Amides color, in crayons, pencils and inks, paper industry , plastic and rubber industry, and water and sewage treatment.

Amides use as

used in the treatment of drinking water and sewage. In paper industry polyacrylamide is used as a binder and for retention for fibres. It is also used to retain the color pigments on the paper. Polyacryla as a coating on many household appliances and car parts with thermosetting mide acrylics. used to make tyre cords (the inner structure of a vehicle tyre which is underneath the rubber) Nylons are to make ropes and nylon can be cast easily into solid shapes and used for cogs polyamides and bearings in machines.

used in the cosmetic industry to prepare hair products, soaps, and pre-shave lotions. Acrylamide printing inks, explosives, latex thickeners, adhesives and emulsion stabilizers. s

Kevlar

a form of polyamide. Is a very strong material which is about five times as strong as steel, weight for weight. It is used in composites for boat construction, in manufacture of bulletproof vests, and in lightweight mountaineering ropes and skis and racquets.

used as asanalgesic (pain-killer) used as active ingredient in products such as Amadil, Datril, Cetadol, Naprinol, Acetamino Tylenol, and Panadol. Another amide analgesic is phenacetin, used in products phen an such as Empirin and APC (aspirin, phenacetin, and caffeine) tablets. amide N,N-dimethyl-m-toluamide, used as insect repellant) lidocaine (Xylocaine) and dibucaine (Nupercaine), used as the local anesthetics Other the tranquilizer meprobromate (Equaine, Miltown), and Sevin and Mipcin used commercial as insecticides. ly used