Alcohols, Phenols and Ethers Flashcards
how are Alcohols and phenols formed
Alcohols and phenols are formed
when a hydrogen atom in a hydrocarbon, aliphatic and aromatic respectively, is replaced by –OH group.
what are ethers
The substitution of a hydrogen atom in a
hydrocarbon by an alkoxy or aryloxy group
(R–O/Ar–O) yields another class of compounds known
as ‘ethers
how are ethers formed
ethers as compounds formed by substituting the hydrogen atom of hydroxyl group of an alcohol or phenol by an alkyl or aryl group.
classification of Compounds containing C sp3 -OH bond
alkyl group
Allylic alcohols
Benzylic alcohols
what is alkyl group alcohol
the –OH group is attached to an sp-3 hybridized carbon atom of an
alkyl group… three types of
alcohols, the –OH group is attached to primary, secondary and
tertiary carbon atom
what is allylic alcohols
the —OH group is attached to
a sp-3 hybridized carbon adjacent to the carbon-carbon double
bond, that is to an allylic carbon
what is benzylic alcohols
, the —OH group is attached
to a sp3—hybridized carbon atom next to an aromatic ring
classification of Compounds containing C sp2 -OH bond
Vinylic alcohol
what is Vinylic alcohol
These alcohols contain —OH group bonded to a carbon-carbon double bond, i.e., to a
vinylic carbon or to an aryl carbon
what is phenol
The simplest hydroxy derivative of benzene is phenol.
Structures of Functional Groups in alcohol
the oxygen of the –OH group is attached to carbon by a sigma bond formed by the overlap of a sp3 hybridized orbital of carbon with a sp3 hybridized orbital of oxygen
what is the bond angle in alcohol
The bond angle in alcohols is slightly less than the tetrahedral angle (109°-28°).It is due to the repulsion between the unshared
electron pairs of oxygen
The carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol. why?
This is due to (i) partial double bond character on account of the conjugation
of unshared electron pair of oxygen with the aromatic ring
(ii) sp2 hybridized state of carbon to which oxygen is attached.
Structures of Functional Groups in ethers
the two bond pairs and two lone pairs of electrons on oxygen are arranged approximately in a tetrahedral arrangement
…The bond angle is slightly greater than the
tetrahedral angle due to the repulsive interaction between the two bulky (–R) groups….The C–O bond length (141 pm) is almost the same as in alcohols
Preparation of Alcohols list types
From alkenes
(i) By acid catalyzed hydration
(ii) By hydroboration–oxidation:
From carbonyl compounds
(i) By reduction of aldehydes and ketones
(ii) By reduction of carboxylic acids and esters
From Grignard reagents
Preparation of Alcohols From alkenes By acid catalyzed hydration
Alkenes react with water in the presence of acid as catalyst to form alcohols
Mechanism;- Step 1: Protonation of alkene to form carbocation by electrophilic
attack of H3O
Step 2: Nucleophilic attack of water on carbocation.
Step 3: Deprotonation to form an alcohol.
Preparation of Alcohols From alkenes By hydroboration–oxidation
Diborane (BH3)2 reacts with alkenes
to give trialkyl boranes as addition product. This is oxidized to alcohol by hydrogen peroxide in the presence of aqueous sodium hydroxide
Preparation of Alcohols From carbonyl compounds By reduction of aldehydes and ketones:
Aldehydes and ketones are reduced to the corresponding alcohols by addition of hydrogen in the presence of catalysts 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 aluminum hydride (LiAlH4)
Aldehydes yield ________alcohols
whereas ketones give ______ alcohols
primary and secondary
Preparation of Alcohols From carbonyl compounds By reduction of carboxylic acids and esters
Carboxylic acids are reduced to primary alcohols in excellent yields by lithium
aluminum hydride, a strong reducing agent LiAlH4 is an expensive reagent, and therefore Commercially, acids are reduced to alcohols by converting them to the esters followed by their reduction using hydrogen in the presence of catalyst
Preparation of Alcohols From carbonyl compounds From Grignard reagents
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
Phenol, also known as
carbolic acid
Preparation of Phenols
From haloarenes
From benzene sulphonic acid
From diazonium salts
From cumene
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
Preparation of Phenols From benzene sulphonic 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.
Preparation of Phenols From cumene
Phenol is manufactured from the hydrocarbon, cumene. Cumene
(isopropyl benzene) is oxidized in the presence of air to cumene hydroperoxide. It is converted to phenol and acetone by treating it with dilute acid
Preparation of Phenols From diazonium salts
A diazonium salt is formed by treating an aromatic primary amine with nitrous acid (NaNO2 + HCl) at 273-278K. Diazonium salts are hydrolyzed to phenols by warming with water or by treating with dilute acids
The properties of alcohols and phenols are chiefly due to the _______ group
hydroxyl
The high boiling points of alcohols are mainly due to the presence of?
The high boiling points of alcohols are mainly due to the presence of intermolecular hydrogen bonding in them which is lacking in ethers and hydrocarbons.
Boiling Points in alcohols and phenols
The boiling points of alcohols and phenols increase with increase in the number of carbon atoms (increase in van der Waals forces)
In alcohols, the boiling points decrease with increase of branching in carbon chain
(because of decrease in van der Waals forces with decrease in surface
area)
explain Solubility of alcohols and phenols in water?
Solubility of alcohols and phenols in
water is due to their ability to form
hydrogen bonds with water molecules The solubility decreases with increase in size of alkyl/aryl
in alcohols The bond between O–H is broken when alcohols react with
nucleophiles
in alcohol The bond between C–O is broken when they react as
electrophiles
alcohol and phenol Reaction with metals
Alcohols and phenols react with active
metals such as sodium, potassium and aluminum to yield corresponding alkoxides/phenoxides and hydrogen
what is Brönsted acids
compounds can donate a proton to a stronger base