Scribd
Upload
25 views13 pages

Alcohol Phenol Ether Part I

The document discusses the properties and preparation methods of alcohols, phenols, and ethers. It describes how alcohols and phenols are formed by replacing a hydrogen atom with a hydroxyl group in hydrocarbons. It also discusses the classification and preparation of primary, secondary, and tertiary alcohols using Grignard reagents, reduction of carbonyl compounds, and oxidation reactions.

Uploaded by

Ayush Kr. Dubey
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
25 views13 pages

Alcohol Phenol Ether Part I

The document discusses the properties and preparation methods of alcohols, phenols, and ethers. It describes how alcohols and phenols are formed by replacing a hydrogen atom with a hydroxyl group in hydrocarbons. It also discusses the classification and preparation of primary, secondary, and tertiary alcohols using Grignard reagents, reduction of carbonyl compounds, and oxidation reactions.

Uploaded by

Ayush Kr. Dubey
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 13

Alcohols, Phenols

& Ethers

Dr. Piya Seth, Assistant Professor, SNGGDCG


•Alcohols and Phenols are formed when hydrogen atom in aliphatic or
aromatic hydrocarbon is replaced by hydroxyl group (-OH).
R H R OH
H OH

• An alcohol contains one or more hydroxyl group (s) (-OH) directly


attached to carbon atoms (s) of an aliphatic system (e.g. CH3OH).

• Phenol contains hydroxyl group (s) (-OH) directly attached to carbon


atom (s) of an aromatic system (e.g. C6H5OH).

• 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’ (e.g.CH3OCH3).
R H R OR'
H OR' OAr'
,
Dr. Piya Seth, Assistant Professor, SNGGDCG
• Alcohols may be classified as mono-, di-, tri-, or polyhydric compounds
depending on whether they contain one or two or three or many hydroxyl
group respectively
• The monohydric alcohols form a homologous series with the general
formula CnH2n+2O, but their functional group is the hydroxy group, their
general formula is more aptly written as CnH2n+1OH or ROH.
e.g. when n=1, CH3OH; n=2, CH3CH2OH,
n=3, CH3CH2CH2OH, n=4, CH3CH2CH2CH2OH.
• Monohydric alcohols are subdivided into primary, secondary and tertiary
alcohols according as the alkyl group attached to the hydroxyl group is a
primary (1o), secondary (2o) or tertiary (3o) group respectively.
Primary alcohol (1o): Ethanol (CH3CH2OH)
Secondary alcohol (2o): Isopropanol (CH3)2CHOH
Tertiary alcohol (3o): t-butanol (CH3)3COH

Dr. Piya Seth, Assistant Professor, SNGGDCG


Preparation of alcohols using Grignard Reagent

What is Grignard Reagent: The alkyl magnesium halides, R-Mg-X, or


Grignard reagents are extremely valuable in organic synthesis. (X= halides)

Preparation of Grignard Reagent: A Grignard reagent is generally


prepared by reaction between magnesium (1 atom) and alkyl halide
(1 molecule) in dry, alcohol-free ether.
Example: CH3MgBr, C2H5MgCl etc
•For the given same alkyl group the ease of formation of Grignard reagent is
alkyl iodied > alkyl bromide > alkyl chloride.

•Addition of the R group of RMgX takes place to a compound containing multiple


bond group like carbonyl (C=O) or nitrile (C≡N) at the less electronegative (i.e.C
centre) and that of the MgX Group at the more electronegative atom (i.e. O or N
centre). This is evident on the basis that R and MgX are respectively the negative
and positive ends of the dipole in RMgX

Dr. Piya Seth, Assistant Professor, SNGGDCG


Synthesis of Primary alcohol (1o) by Grignard reagnet
•Etheral solution of Grignard reagent is treated with formaldehyde (obtained by heating
the polymer Formalin), followed by decomposing the magnesium complex with dilute
acid to get primary alcohol containing one carbon atom morethan the Grignard alkyl
group.
•Magnesium can coordinate to the carbonyl’s oxygen atom giving the carbonyl group
positive charge and therefore making it more electrophilic. The negatice dipolar end i.e.
alkyl (R) groupof Grignard reagent eventually attached to the carbonyl carbon resulting
in the -O-Mg complex.

A primary alcohol from fromaldehyde:

Dr. Piya Seth, Assistant Professor, SNGGDCG


•A primary alcohol containing two carbon atom more than the Grignard alkyl group can
be prepared by reacting ethelyne oxide with Grignard reagent

Ethylene oxide

•Similarly primary alcohol containing three carbon atom more than the Grignard alkyl
group can be prepared from the Grignard reagent by using trimethylene oxide.

Dr. Piya Seth, Assistant Professor, SNGGDCG


Synthesis of Secondary alcohol (2o) by Grignard reagnet
•When a Grignard reagent is treated with any aldehyde other than formaldehyde, a
secondary alcohol is formed

•Secondary alcohols may also be prepared by interaction of 2 molecules of Grignard


reagents with 1 molecule of ethyl formate.

Dr. Piya Seth, Assistant Professor, SNGGDCG


Synthesis of Tertiary alcohol (3o) by Grignard reagnet
A tertiary alcohol may be prepared by the action of Grignard reagent on a ketone

•As t-alcohols are readily dehydrated to alkenes by acids, the complex is often broken up
with aqueous ammonium chloride or buffered acid solution.
•Tertiary alcohols containing at least two identical alkyl groups may be prepared by the
reaction between a Grignard reagent (2 molecules) and any ester other than formic ester.

•Tertiary alcohols containing three identical alkyl groups may be prepared by the reaction
between 3 molecules of Grignard reagent and 1 molecule of ethyl carbonate.

Dr. Piya Seth, Assistant Professor, SNGGDCG


Preparation of alcohols by reduction of carbonyl compounds
(i) By reduction of aldehyde and ketone:
•Aldehydes and ketones are reduced to corresponding alcohol by addition of hydrogen
in presence of catalyst (catalytic hydrogenation). The usual catalysts are Platinum,
Palladium or Nickel.

•Lithium aluminium hydride (LiAlH4) and Sodium borohydride (NaBH4) are also used
to reduce aldehydes and ketones .

•Aldehydes give primary alcohols


• Ketones give secondary alcohols

•LiAlH4 is most versatile reducing agent which


reduces most functional groups but does not
normally reduce the olefinic bond. However
NaBH4 is comparatively selective and easy to
handle

Dr. Piya Seth, Assistant Professor, SNGGDCG


(ii) By reduction of carboxylic acid and ester:

•Carboxylic acids are reduced to primary alcohols in excellent yield by LiAlH4

•However LiAlH4 is expensive not difficult to handle

• Commercially carboxylic acids are reduced to alcohols by converting acids to


corresponding esters followed by reduction using hydrogen in presence of metal
catalyst

Dr. Piya Seth, Assistant Professor, SNGGDCG


Reaction of alcohols with sodium metal:
The acidity of alcohols is shown by their reaction with sodium in which sodium
alkoxide is formed and hydrogen gas liberates
R-O-H + Na → R-O-Na + ½ H2
When water is added to an alkoxide, sodium hydroxide forms with the parent alcohol.
The weaker acid R-OH, is displaced from its salt by the stronger acod, H-O-H.

•Relative acidities: H2O > ROH > NH3 > RH •Relative basicities: R- > NH2- > OR- > OH-
•Grignard reagent quench hydrogen from alcohol to give alkane following the acidic
property.

Dr. Piya Seth, Assistant Professor, SNGGDCG


Oxidation of alcohols :
The oxidation of an alcohol involves the loss of one or more α-hydrogens from the carbon
bearing –OH group. The kind of product that is formed depends upon whether the alcohol
is primary, secondary or tertiary.
• A primary alcohol contains two α- Hs and can either lose one of them to form an
aldehyde or both of them to form a carboxylic acid.
• A secondary alcohol can lose its only α- Hs to form ketone
• A tertiary alcohol contains no α- Hs and is not oxidized

Dr. Piya Seth, Assistant Professor, SNGGDCG


Diols: Pinacol-pinacolone rearrangement
• t- butyl methyl ketone i.e. pinacolone can be prepared by distilling pinacol
with sulphuric acid

•The conversion of pinacol into pinacolone is an example of the 1,2-shift and is known
as pinacol-pinacolone rearrangement. Mechanistically, the first step is the addition of
proton to one of the hydroxyl group of pinacol, followed by loss of water.
The resulting carbotaion follows 1,2 shift of methyl ghoup which leads to the product
pinacolone. The second reversible step is the rate determining one.

Dr. Piya Seth, Assistant Professor, SNGGDCG

You might also like

pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy