Alcohols, Phenols and Ethers

Alcohols and Phenols are among the most widely used organic compounds in industry as well as in day to day life. The sugar we eat, the fabric we use, paper, books, photographs, etc., most of the things around us are made of compounds containing OH group, the functional group present in alcohols and phenols. Alcohols and phenols are formed when a hydrogen atom is replaced by OH group. An alcohol contains one or more OH groups attached to aliphatic C-chain, while a phenol contains OH group attached to C of an aromatic system.

Classification of Alcohols or Phenols

(i) On the basis of number of OH groups present

(ii) On the basis of the nature of C-atom to which OH group is attached

(iii) Vinylic alcohols: In vinylic alcohols OH group is bonded to an vinylic carbon or to an aryl carbon.

Nomenclature
For naming alcohols C of alkane (corresponding to the number of C-atoms present in alcohol) is replaced by suffix ol. The longest continuous C-chain containing OH group is taken as parent chain. Examples:

Cyclic compounds are named using the prefix cyclo before the name of parent alkane.

For polyhydric alcohols e of alkane is retained and the ending ol is added.

Phenols

Dihydroxy derivatives are written as derivatives of benzene.

Ethers In IUPAC system these are named as Alkoxyalkane in which alkane is the bigger alkyl group of the ether and alkoxy the other alkyl group.

Structures of Functional Group Alcohol

The order of bond angles is as follows It is due to repulsion between the unshared pair of electrons of oxygen.

The angle is slightly bigger due to the bulkier benzene ring. CO bond length in phenol is shorter due to conjugation of electron pair at O with benzene ring. Also in phenol, C is while in alcohol it is Bond angle is slightly bigger than tetrahedral geometry due to the repulsions between bulky alkyl group CO bond length is almost same as in CO bond length in alcohols.

Preparation of Alcohols and Phenols

A. Preparation of alcohols I. From Alkenes (i) By acid catalysed hydration

Addition takes place according to Markovnikovs rule

Mechanism: Step 1. Protonation

Step 2. Nucleophilic attack

Step 3. Deprotonation

(ii) By Hydroboration-Oxidation

The addition takes place according to antimarkonikovs rule. II From Carbonyl Compounds

III From Grignard Reagent: 1, 2 and 3 all three types of alcohols can be produced by this method.

For 1 alcohol

For 2 alcohol

For 3 alcohol

B. Preparation of Phenols I. From Haloarenes

II. From Benzene Sulphonic acid

III. From Diazonium Salts

IV. From Cumene

Physical Properties of Alcohols and Phenols

Alcohols and phenols have higher boiling point than hydrocarbons, ethers, haloalkanes and haloarenes of comparable molecular mass. This is because alcohols and phenols have intermolecular H-bonding.

The boiling points of alcohols and phenols increase with increase in B.P. with increasing number of carbon atoms as with increase in C-atoms van der Waal's force increases. In isomeric alcohols B.P. decreases with increasing branching (as van der Waal's forces get weaker with decrease in surface area).

Solubility
Alcohols and phenols are soluble in water as they can form H-bonds with water molecules. The solubility decreases with increase in number of C-atoms in alkyl/aryl groups.

Chemical Reactions of Alcohols and Phenols

Alcohols behave as both electrophiles and nucleophiles. Alchols as necleophile

Alcohols as electrophile Protonated alcohol acts as electophile.

I. Acidity of Alcohols and Phenols Acidity of Alcohols The acidic character of alcohols is due to polarity of OH bond. Bigger is the Rgroup higher is +I effect which decreases polarity of OH bond and thus acidic strength of alcohols decrease. Alcohols are weaker acids than water due to presence of Rgroup which has +I effect

Acidity of Phenols Phenols are acidic due to polarity of OH bond. OH bond in phenols is more polar than in alcohol. In phenols electron pair at O moves towards the conjugated benzene ring and shows resonance. Due to resonance. O at OH gets the change making OH bond more polar.

The acidic character of alcohols and phenols is justified by their reaction with metal (Na, K) and then hydroxides.

Comparison of Acidic Character of Alcohols and Phenols The ionisation of an alcohol and a phenol takes place as follows:

The electron density on O is less in phenol due to increases the polarity of OH bond in phenol making the release of

hybridised C than

hybridised C in alcohol. This

In phenols after release of ion phenoxide ion is formed which is resonance stabilised while in alcohol alkoxide ion formed is not resonance stabilised.

Out of phenoxide ion and phenol, phenoxide ion is more resonance stabilised. This is because there is charge separation in phenol while in phenoxide ion it is charge dispersal.
In phenols, presence of electron donating group decreases the acidic strength because this increases ve charge density in the phenoxide ion, thereby destabilising it.

In phenols, presence of electron withdrawing group increases the acidic strength because this decreases ve charge density in the phenoxide ion, thereby stabilising it. The effect of substituents is more pronounced at ortho and para position.

II. Esterification Alcohols and Phenols react with carboxylic acids and acid anhydrides in presence of produce esters. Reaction is reversible so water formed is removed to get better yield. to

Alcohols and phenols form ester with acid chloride also but in the presence of a base pyridine so as to neutralise HCl formed during reaction. This shifts the equilibrium to the right.

III. Reactions involving cleavage of CO bond This type of reactions are given by alcohols only phenols do not give this type of reactions as CO bond in phenols has partial double bond character due to resonance. So is difficult to break. Phenol shows this type of reaction only with Zn.

(i) Alcohols with HX

The three classes of alcohols can be differentiated by using Lucas reagent as follows:

(iii) Dehydration: The order of dehydration of alcohols follows the following order. This is because 3 carbocations are more stable than 2 and 1 thus 3 alcohols are easiest to dehydrate.

Mechanism:

Oxidation

Strong oxidising agents like

(acidified) is used for getting carboxylic acid.

with PCC (Pyridinium chlorochromate)

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Tertiary alcohols do not undergo oxidation. Under drastic conditions various CC bonds break and mixture of carboxylic acids are formed. When vapours of 1 or 2 alcohols are passed over heated Cu at 573 K dehydrogenation takes place.

3 alcohols undergo dehydration.

V. Some Important Reactions of Phenols: Electrophilic substitution reaction takes place in benzene ring in phenols. The OH group is electron donating and due to resonance activates the benzene ring, it directs the incoming electrophile to ortho and para positions in the benzene ring.

Halogenation:

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Kolbes Reaction

Phenol is converted to phenoxide ion because phenoxide ion is more reactive than phenol. Riemer Tiemann reaction

Some Commercial Alcohols

I. Methanol
Also known as wood spirit Obtained by destructive distillation of wood. Can be obtained by catalytic hydrogenation of carbon monoxide.

It is colourless liquid that boils at 337 K. It is poisonous and can cause blindness or even death also. It is used as a solvent in paints, varnishes and to prepare formaldehyde.

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II. Ethanol Commercially prepared by fermentation of sugar

Fermentation takes place in anaerobic conditions. It is a colourless liquid and boils at 351 K. It is used as a solvent in paints and to prepare a number of organic compounds. Commercial alcohol is made unfit for drinking by mixing some smell). It is known as denaturation. (for colour) and some Pyridine (for foul

7. Preparation and Properties of Ethers (I) Preparation of Ethers (i) By Dehydration of Alcohols

It is a nucleophilic bimolecular reaction

Mechanism is as follows:

This method is suitable for the preparation of ethers having primary alkyl groups only. (ii) Williamsons synthesis: It is a good laboratory method for the preparation of all types of ethers symmetrical and unsymmetrical

For ethers containing a sec- or tert- alkyl group, better results are obtained if the alkyl halide is primary.

Aromatic ethers can also be prepared by this method. Phenol is first converted to sodium phenoxide, and then to aromatic ether.

(II) Physical Properties

Ethers are polar and have a net dipole moment.

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Symmetrical ethers are also polar. Ethers have higher boiling points than the alkanes of comparable masses but are lower than the boiling points of corresponding alcohols. Ehters are miscible with water as O of ethers can form H-bonding with water molecule.

(III) Chemical Properties Ethers are the least reactive functional groups:

(ii) Alkyl aryl ethers are cleaved at the alkyl-oxygen bond as aryl-oxygen bond is stronger due to partial double character (due to resonance).

The order of reactivity of HX is In the cleavage of mixed ethers with two different alkyl groups, alcohol and alkyl halide are formed. When different alkyl groups are present it is the lower alkyl group that forms alkyl-iodide When one of the alkyl groups is tertiary the halide formed is a tertiary-halide.

In case of aryl alkyl ethers phenol and alkyl halide are formed.

(iii) Electrophilic substitution: OR group is ortho-para directing and activates the benzene ring.

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(iv) Nitration:

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