Alcohols and phenols are formed when a hydrogen atom in a hydrocarbon, aliphatic and aromatic respectively, is replaced by –OH group. From the ordinary spirit used for polishing wooden furniture, a compound containing hydroxyl group, ethanol to the sugar we eat, the cotton used for fabrics, the paper we use for writing, are all made up of compounds containing hydroxyl groups.

An alcohol contains one or more hydroxyl (-OH) group(s) directly attached to carbon atom(s), of an aliphatic system (R-OH) while a phenol contains –OH group(s) directly attached to carbon atom(s) of an aromatic system (Ph-OH or Ar-OH).

Classification

Number of Hydroxyl Groups

Alcohols and phenols may be classified as mono–, di–, tri- or poly-hydric compounds depending on whether they contain one, two, three or many hydroxyl (-OH) groups respectively in their structures as given below:alcoclas1

Monohydric alcohols may be further classified according to the hybridisation of the carbon atom to which the hydroxyl group is attached.

Compounds containing C (sp3-hybridized) -OH bond

Primary, secondary and tertiary alcohols: In these three types of alcohols, the –OH group is attached to primary, secondary and tertiary carbon atom, respectively as depicted below:alcoclas2

Allylic alcohols: In these alcohols, the —OH group is attached to a sp3-hybridised carbon next to the carbon-carbon double bond, i.e. to an allylic carbon.

alcoclas3.png

Benzylic alcohols: In these alcohols, the —OH group is attached to a sp3-hybridised C-atom next to an aromatic ring.

alcoclas4.png

Compounds containing C (sp2-hybridized) -OH bond

These alcohols contain —OH group bonded to a carbon-carbon double bond i.e., to a vinylic carbon or to an aryl carbon. These alcohols are also known as vinylic alcohols.

alcoclas5.png

Methods of Preparation of Alcohol

From Alkenes (Acidic Hydration)

Alkenes react with water in the presence of acid as catalyst to form alcohols. In case of unsymmetrical alkenes, the addition reaction takes place in accordance with Markovnikov’s rule.alcomop1.png

Mechanism:

alcomop2.png

Hydroboration–Oxidation Reaction

Diborane (BH3)2 reacts with alkenes to give trialkyl boranes as addition product. This is oxidised to alcohol by hydrogen peroxide in the presence of aqueous sodium hydroxide. The addition of borane to the double bond takes place in such a manner that the boron atom gets attached to the sp2 carbon carrying greater number of hydrogen atoms. The alcohol so formed looks as if it has been formed by the addition of water to the alkene in a way opposite to the Markovnikov’s rule. In this reaction, alcohol is obtained in excellent yield.
alcomop3.png

From carbonyl compounds

We follow the AAA rule in which Alcohol oxidises to Aldehyde oxides to Acid and the other way round, Acid reduces to Aldehyde reduces to Alcohol.

Aldehydes and ketones are reduced to the corresponding alcohols by addition of hydrogen in the presence of catalysts (catalytic hydrogenation). The usual catalyst is a finely divided metal such as platinum, palladium or nickel. It is also prepared by treating aldehydes and ketones with sodium borohydride (NaBH4) or lithium aluminium hydride (LiAlH4). Aldehydes yield primary alcohols whereas ketones give secondary alcohols.

Carboxylic acids are reduced to primary alcohols in excellent yields by lithium aluminium hydride, a strong reducing agent. However, LiAlH4 is an expensive reagent, and therefore, used for preparing special chemicals only. Commercially, acids are reduced to alcohols by converting them to the esters, followed by their reduction using hydrogen in the presence of catalyst (catalytic hydrogenation).

alcomop4.png

From Grignard reagents (R-Mg-X)

Alcohols are produced by the reaction of Grignard reagents with aldehydes and ketones. The first step of the reaction is the nucleophilic addition of Grignard reagent to the carbonyl group to form an adduct. Hydrolysis of the adduct yields an alcohol.

alcomop5.png

Methods of Preparation of Phenols

From Haloarenes

Chlorobenzene is fused with NaOH at 623K and 320 atmospheric pressure. Phenol is obtained by acidification of sodium phenoxide so produced. This is also known as Dow’s Process.

From Benzenesulphonic Acid

Benzene is sulphonated with oleum and benzene sulphonic acid so formed is converted to sodium phenoxide on heating with molten sodium hydroxide. Acidification of the sodium salt gives phenol.

From Diazonium Salts

A diazonium salt is formed by treating an aromatic primary amine with nitrous acid (NaNO2 + HCl) at 273-278 K. Diazonium salts are hydrolysed to phenols by warming with water or by treating with dilute acids.

From Cumene

Phenol is manufactured from the hydrocarbon, cumene. Cumene (isopropylbenzene) is oxidised in the presence of air to cumene hydroperoxide. It is converted to phenol and acetone by treating it with dilute acid. Acetone, a by-product of this reaction, is also obtained in large quantities by this method.alcomop6.png

Important Compounds

Methanol

Methanol, CH3OH, also known as ‘wood spirit’, was produced by destructive distillation of wood. Today, most of the methanol is produced by catalytic hydrogenation of carbon monoxide at high pressure and temperature and in the presence of ZnO – Cr2O3 catalyst. Methanol is a colourless liquid and boils at 337 K. It is highly poisonous in nature. Ingestion of even small quantities of methanol can cause blindness and large quantities causes even death. Methanol is used as a solvent in paints, varnishes and chiefly for making formaldehyde.

alcoimpo1.png

Biological oxidation of methanol and ethanol in the body produces the corresponding aldehyde followed by the acid. At times the alcoholics, by mistake, drink ethanol, mixed with methanol also called denatured alcohol. In the body, methanol is oxidised first to methanal and then to methanoic acid, which may cause blindness and death. A methanol poisoned patient is treated by giving intravenous infusions of diluted ethanol. The enzyme responsible for oxidation of aldehyde (HCHO) to acid is swamped allowing time for kidneys to excrete methanol

Ethanol

Ethanol, C2H5OH, is obtained commercially by fermentation, the oldest method is from sugars. The sugar in molasses, sugarcane or fruits such as grapes is converted to glucose and fructose, (both of which have the formula C6H12O6), in the presence of an enzyme, invertase.

Glucose and fructose undergo fermentation in the presence of another enzyme, zymase, which is found in yeast. In wine making, grapes are the source of sugars and yeast. As grapes ripen, the quantity of sugar increases and yeast grows on the outer skin. When grapes are crushed, sugar and the enzyme come in contact and fermentation starts.

alcoimpo2.png

Fermentation takes place in anaerobic conditions i.e. in absence of air. Carbon dioxide is released during fermentation. The action of zymase is inhibited once the percentage of alcohol formed exceeds 14 percent. If air gets into fermentation mixture, the oxygen of air oxidises ethanol to ethanoic acid which in turn destroys the taste of alcoholic drinks.

Ethanol is a colourless liquid with boiling point 351 K. It is used as a solvent in paint industry and in the preparation of a number of carbon compounds. The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to give it a colour) and pyridine (a foul smelling liquid). It is known as denaturation of alcohol. Nowadays, large quantities of ethanol are obtained by hydration of ethene.

Ingestion of ethanol acts on the central nervous system. In moderate amounts, it affects judgment and lowers inhibitions. Higher concentrations cause nausea and loss of consciousness. Even at higher concentrations, it interferes with spontaneous respiration and can be fatal.

One thought on “Alcohols and Phenols

Leave a Reply

Fill in your details below or click an icon to log in:

WordPress.com Logo

You are commenting using your WordPress.com account. Log Out / Change )

Twitter picture

You are commenting using your Twitter account. Log Out / Change )

Facebook photo

You are commenting using your Facebook account. Log Out / Change )

Google+ photo

You are commenting using your Google+ account. Log Out / Change )

Connecting to %s